CA1096078A - Sag resistant compositions - Google Patents
Sag resistant compositionsInfo
- Publication number
- CA1096078A CA1096078A CA293,325A CA293325A CA1096078A CA 1096078 A CA1096078 A CA 1096078A CA 293325 A CA293325 A CA 293325A CA 1096078 A CA1096078 A CA 1096078A
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- Prior art keywords
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- compositions
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- composition
- hydraulic
- Prior art date
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Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Paints Or Removers (AREA)
Abstract
COMPOSITE
OF: Jeffrey R. Ellis and Herman B. Wagner FOR: SAG RESISTANT COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
There is provided a new sag resistance imparting agent selected from among gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the agent being useful for providing sag resistance in adhesive compositions including: (i) dry-set cementitious mortar compositions com-prising an hydraulic cement, at least one water soluble high molecular weight polymer, and optionally, at least one sub-stantially water insoluble polymer; (ii) hydraulic non-dry-set compositions comprising an hydraulic cement or plaster of paris, and (iii) non-hydraulic compositions comprising a room tem-perature hardening polymer in the form of a resinous liquid or an emulsion, suspension, dispersion, partial solution or total solution. Methods of imparting sag resistance to adhesive compositions such as the aforementioned and methods of use for sag resistant compositions in the installation of wall and floor covering surfaces are also provided.
OF: Jeffrey R. Ellis and Herman B. Wagner FOR: SAG RESISTANT COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
There is provided a new sag resistance imparting agent selected from among gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the agent being useful for providing sag resistance in adhesive compositions including: (i) dry-set cementitious mortar compositions com-prising an hydraulic cement, at least one water soluble high molecular weight polymer, and optionally, at least one sub-stantially water insoluble polymer; (ii) hydraulic non-dry-set compositions comprising an hydraulic cement or plaster of paris, and (iii) non-hydraulic compositions comprising a room tem-perature hardening polymer in the form of a resinous liquid or an emulsion, suspension, dispersion, partial solution or total solution. Methods of imparting sag resistance to adhesive compositions such as the aforementioned and methods of use for sag resistant compositions in the installation of wall and floor covering surfaces are also provided.
Description
26 .
27 B~CKGROU~D `OF ~TH$ ~NVE~T.~ON
29 In the installation of wall and floor covering surfaces .
such as ceramic tile, slate, marble and the like, numerous com-~ k ';
. . ... . ~
- :
,, -"' . " ~' ,', " ' " ' ~
: ` ' : . .
~
~l ~ ~ ~ 6~ 7~3 l ~ositions have been developed which utilize a hydraulic cement
27 B~CKGROU~D `OF ~TH$ ~NVE~T.~ON
29 In the installation of wall and floor covering surfaces .
such as ceramic tile, slate, marble and the like, numerous com-~ k ';
. . ... . ~
- :
,, -"' . " ~' ,', " ' " ' ~
: ` ' : . .
~
~l ~ ~ ~ 6~ 7~3 l ~ositions have been developed which utilize a hydraulic cement
2 such as Portland cement as the principal factor in the bonding
3 adhesives. Ordinary Portland cement per se, or together with
4 sand or limestone fillers, is generally ineffective for this purpose since it does not have the ability to retain the wa~er 6 used in mixing it for sufficient time to enable an adequate bond-7 ing cure to occur. In order to overcome this disadvantage, there 8 was developed a type of adhesive now known in the art as dry-set Portland cement mortar. These mortars possess certain advan~ag- , eous properties: they may be exposed to air after mixing with ll water for a period of time; they may be applied to the substratesl 12 without undue hurry; they remain plastic for a sufficient period `1 13 of time to permit small movements to be made in tbe tile ins~alla-14 tion ater the initial substrate to surface contact; they develop ~trong bonding between the tile or similar surfacing and the sub-l I
16 strate surface to which lt is bonded; and they possess a reason-17 ably predictable initial set time, minimum drying shrinkage, and 18 some sag resistance. A number of such dry-set co~positions have 19 been developed starting with the init~al composi~ion of one of the co-inventors herein as disclosed ln U.S. Pa~ent No. 2,820,713.
22 One of the many properties required by mortar for 23 se~tting tile is that it be sag resistant. Sag resistance is a 24 term used in the trade and de~ined by a test method that is part of the American ~ational Standard Specificati~n fQr Dry-set 26 Portland Mortar Cement - ~ 118.1. Sag resistance is a property 27 or charac~eristic relating to ~he a~ility of the ~ortar to resist 28 movement under load until a certain load level is reached. This 2~ property or characteristic is vitally important in dr~-set mortars and also to a latex Por~land cement moxtar since a mor~arl _~
.
. : :
~ 7~
1~ ~ o be practica11y functlonal must be in a s1urry ~r paRte form 2 on the one hand, but also must be capable of supporting the load 3 imposPd on it by the tiles being set. It is vital that the morta~
4 support the tile withou~ any appreciable sinking of the tile into~
the mortar during the period in which the mortar sets. In wall 6 applications sag resistance is even more critical because ~he mortar must hold the tile in position on the wall during the 8 period in which the mortar is setting.
In the course of development of dry-set mortars, it ' ll was found that the sag resistance, that is to say, the resistance 12 to downward movement of an initially set tile during the curing 13 process, could be substantially minimized by the addition to the 14 composition of asbestos fibers. Since ~he time of this initial discovery, it has been found that asbestos possesses a long-term 16 but hidden carcinogenic effect ancl therefore the use of asbestos, 17 particularly in fiber form, has been s~rictly controlled if not 18 prohibited under certain circumstances, I-t has therefore become ¦
l9 most important in this particular art to find substitutes for asbestos fiber to provide the desired sag resistance. This 21 problem has been solved in the presen~ invention by the use of 22 certain salts which under appropriate conditions form gelatinous 23 or hydrated hydroxides, as well as gelatinous me~al hydroxides ~4 per se.
26 D~SCRIPTION ~F mE PRIOR ART
28 The use of certain metal sal~s, in particular, aluminum¦
29 salts in mortar compositions generally, ls, in cer~ain circum-stances, known. The use of such sal~s however in composi~ions !
........
.:
~ ;
~ ~ 9 ~ 7 8 1 of the type set forth in the present invention is not known, and 2 the use`of such metal salts as well as the metal hydroxides 3 herein described for the purpose of increasing sag resistance 4 in dry-set mortars as well as other adhesive compositions is ¦
16 strate surface to which lt is bonded; and they possess a reason-17 ably predictable initial set time, minimum drying shrinkage, and 18 some sag resistance. A number of such dry-set co~positions have 19 been developed starting with the init~al composi~ion of one of the co-inventors herein as disclosed ln U.S. Pa~ent No. 2,820,713.
22 One of the many properties required by mortar for 23 se~tting tile is that it be sag resistant. Sag resistance is a 24 term used in the trade and de~ined by a test method that is part of the American ~ational Standard Specificati~n fQr Dry-set 26 Portland Mortar Cement - ~ 118.1. Sag resistance is a property 27 or charac~eristic relating to ~he a~ility of the ~ortar to resist 28 movement under load until a certain load level is reached. This 2~ property or characteristic is vitally important in dr~-set mortars and also to a latex Por~land cement moxtar since a mor~arl _~
.
. : :
~ 7~
1~ ~ o be practica11y functlonal must be in a s1urry ~r paRte form 2 on the one hand, but also must be capable of supporting the load 3 imposPd on it by the tiles being set. It is vital that the morta~
4 support the tile withou~ any appreciable sinking of the tile into~
the mortar during the period in which the mortar sets. In wall 6 applications sag resistance is even more critical because ~he mortar must hold the tile in position on the wall during the 8 period in which the mortar is setting.
In the course of development of dry-set mortars, it ' ll was found that the sag resistance, that is to say, the resistance 12 to downward movement of an initially set tile during the curing 13 process, could be substantially minimized by the addition to the 14 composition of asbestos fibers. Since ~he time of this initial discovery, it has been found that asbestos possesses a long-term 16 but hidden carcinogenic effect ancl therefore the use of asbestos, 17 particularly in fiber form, has been s~rictly controlled if not 18 prohibited under certain circumstances, I-t has therefore become ¦
l9 most important in this particular art to find substitutes for asbestos fiber to provide the desired sag resistance. This 21 problem has been solved in the presen~ invention by the use of 22 certain salts which under appropriate conditions form gelatinous 23 or hydrated hydroxides, as well as gelatinous me~al hydroxides ~4 per se.
26 D~SCRIPTION ~F mE PRIOR ART
28 The use of certain metal sal~s, in particular, aluminum¦
29 salts in mortar compositions generally, ls, in cer~ain circum-stances, known. The use of such sal~s however in composi~ions !
........
.:
~ ;
~ ~ 9 ~ 7 8 1 of the type set forth in the present invention is not known, and 2 the use`of such metal salts as well as the metal hydroxides 3 herein described for the purpose of increasing sag resistance 4 in dry-set mortars as well as other adhesive compositions is ¦
5 nowhere taught in the art. ¦
7 In U.S. Patent No. 1,901,890 to Barnhart, a mixture ¦
8 of certain sulphates, for example, sulphates of an alkali metal, ¦
9 aluminum and magnesium are taught for the purpose of creating a glaze forming and water-proofing composition for cementitious 11 material. In U.S. Patent No. 2,890,965, to Underdown, certaln 12 salts, inter alia, aluminum sulphate, are utilized to improve 13 the plasticity and flowability of certain cementitious materials.
14 The use of certain aluminum, iron, and chromium salts is dis- ¦
15 closed in U.S. Patent No. 2,390,138 to Vallandigham Eor the l ¦
.16 purpose of acceleratlng the setting of certain algenate salts 17 used in the manu~acture of dental casts.
19 U.S, Paten~ No, 3,114,647 to Mecham discloses the use of certain double metal salts, that is to say, salts of 21 ammonium and certain trivalent metals such as al~minum, iron, 22 manganese and chromium, as well as aluminum sulphate per se 23 for increasing the hardness of materials made from Portland 24 cement, The Mecham composition specifies the use of sulfuric acid as well as certain specified quantities of calcium chloride 26 in order to achieve the desired effect, 27 .
28 U.S. Patent No, 3,313,638 to Konrad discloses the 29 use of ext~emely low amounts of aluminum chloride in novel com-positions for castable refractory material with reduced physical .
~,4, , . . I I
., .
~ ' ~ 3~7 1 separation of cement from calcined kaolin clays.
2 . .
3 U.S. Patent No. 3,782,991 to Burge discloses the 4 specific use of anhydrous aluminum sulphate as an accelerator for low te~perature concreting.
7 In U.S. Patent No. 1,901,890 to Barnhart, a mixture ¦
8 of certain sulphates, for example, sulphates of an alkali metal, ¦
9 aluminum and magnesium are taught for the purpose of creating a glaze forming and water-proofing composition for cementitious 11 material. In U.S. Patent No. 2,890,965, to Underdown, certaln 12 salts, inter alia, aluminum sulphate, are utilized to improve 13 the plasticity and flowability of certain cementitious materials.
14 The use of certain aluminum, iron, and chromium salts is dis- ¦
15 closed in U.S. Patent No. 2,390,138 to Vallandigham Eor the l ¦
.16 purpose of acceleratlng the setting of certain algenate salts 17 used in the manu~acture of dental casts.
19 U.S, Paten~ No, 3,114,647 to Mecham discloses the use of certain double metal salts, that is to say, salts of 21 ammonium and certain trivalent metals such as al~minum, iron, 22 manganese and chromium, as well as aluminum sulphate per se 23 for increasing the hardness of materials made from Portland 24 cement, The Mecham composition specifies the use of sulfuric acid as well as certain specified quantities of calcium chloride 26 in order to achieve the desired effect, 27 .
28 U.S. Patent No, 3,313,638 to Konrad discloses the 29 use of ext~emely low amounts of aluminum chloride in novel com-positions for castable refractory material with reduced physical .
~,4, , . . I I
., .
~ ' ~ 3~7 1 separation of cement from calcined kaolin clays.
2 . .
3 U.S. Patent No. 3,782,991 to Burge discloses the 4 specific use of anhydrous aluminum sulphate as an accelerator for low te~perature concreting.
6 .
B S~MARY OF THE INVENTION ¦ .
9 There is provided a class of additives for room tem-perature hardening compositlons which replaces the undesirable 11 asbestos fibers as sag resistance impacting agents. These 12 additive materials maintain the desired èag resistant proper~ies 13 heretofore provided by the asbes~os fibers without exposing 14 the persons handling said materia'Ls ~o long term carcinogenic effects.
16 .
17 The novel additives of ~he p~e~ent invention are 18 gelatlnous metal l~ydroxides and metal salts which are capable ¦
19 of fo~ming a gelat~nous or hydr~ted hydr~ide in ~he presence o aqueous base. Said salts may be water soluble, they may be I
21 hydrated, or they may be anhydrous~ The cations of the gelatinou ~ .
22 metal hydxoxides and metal salts of the present invention are 23 selected from the groups consistlng of aluminum cations, cations 24 of the transition e~e~en~s of period 4 other ~han copper, ~he cations ~f cerium or antimony? and mi~d cations of the classi~
26 fication MI MIII, where MI ls an alkali metal or ammonium cation 27 and MIII is a ~rivalent me~allic ca~ion of periods 3 or 4. .
29 In the case of the me~al salts, the anions are selected 30 rom ~he anions of strong m~neral acids, and carboxylic, pre-~ ~5. ~' . .
IIY ' ' . l ~ V~7~
1 ferably alkanoic acids having up to 20 carbon atoms in the chain.
2 . . `
3 In their broadest aspects, the compositions of the 4 present invention comprise, in admixture:
(A~ an adhesive composition selected
B S~MARY OF THE INVENTION ¦ .
9 There is provided a class of additives for room tem-perature hardening compositlons which replaces the undesirable 11 asbestos fibers as sag resistance impacting agents. These 12 additive materials maintain the desired èag resistant proper~ies 13 heretofore provided by the asbes~os fibers without exposing 14 the persons handling said materia'Ls ~o long term carcinogenic effects.
16 .
17 The novel additives of ~he p~e~ent invention are 18 gelatlnous metal l~ydroxides and metal salts which are capable ¦
19 of fo~ming a gelat~nous or hydr~ted hydr~ide in ~he presence o aqueous base. Said salts may be water soluble, they may be I
21 hydrated, or they may be anhydrous~ The cations of the gelatinou ~ .
22 metal hydxoxides and metal salts of the present invention are 23 selected from the groups consistlng of aluminum cations, cations 24 of the transition e~e~en~s of period 4 other ~han copper, ~he cations ~f cerium or antimony? and mi~d cations of the classi~
26 fication MI MIII, where MI ls an alkali metal or ammonium cation 27 and MIII is a ~rivalent me~allic ca~ion of periods 3 or 4. .
29 In the case of the me~al salts, the anions are selected 30 rom ~he anions of strong m~neral acids, and carboxylic, pre-~ ~5. ~' . .
IIY ' ' . l ~ V~7~
1 ferably alkanoic acids having up to 20 carbon atoms in the chain.
2 . . `
3 In their broadest aspects, the compositions of the 4 present invention comprise, in admixture:
(A~ an adhesive composition selected
7 from among
8 !
9 (i) dry-set cementitious mortar compositions comprising an hydraulic 11 cement and at least one water soluble 12 high molecular weight polymer;
13 (ii) hydraulic non-dry-set compo-14 sitions comprising an hydraulic cement .
or plaster of paris; and 16 (iii) non hydraulic non~dry~set 17 compos.~,o~s c~p~is~ng a, ~oom ~e,~mpera~ure 18 . . ha~dening polym~ nd ¦
' (B~ at least one non-fibrous compound selected 21 from the group consisting of gelatinous metal hydroxides 22 and me~al salts capable of forming a gelatinous or 23 hydrated hydroxide in the presence of a water soluble 24 alkaline material, the compound or compounds being present in an amount at least sufficient to pro~ide 26 the desired sag resistance, 28 The term "hydraulic" is used herein in its conventional 29 sense to refer to compositions or ~aterials which cure or harden in the presence of and upon interaction with added water, I
~6~
1 The roo~ tempe~u~e h~rden~n~ R~ly~e~ ~ the n~on~
2 hydraulic composition of (iii) can be in the form o a resinous 3 liquid or an emulsion, suspension, dlspersion, partial solution 4 or total solution~
6 In still other embodiments, sag resistan~ compositions 7 (i) o this invention comprise, in addition to the described 8 sag resistance imparting additives, an hydraulic cement~ e~g., 9 Portland cement, at least one water soluble high molecular weight polymer, and at least one substantially water insoluble polymer, 11 the latter preferably in the form of a "latex", i~e., a dis-12 persion of the polymer in water.
14 It i8 also contemplated that the dry compositions of ¦
the present invention further comF)rise inert fillers.
.1~ . .
17 The present invention ~s further viewed as extending 18 to said dry compositions when mixed with water, to methods of 19 utilizing said water mixed composit~ons, and the assemblies or the like, resulting from the in~erposltion of said wet cementit-21 ious compositions between a covering surfacing such as a tile 22 or the like and a covered substrate such as a wall or the like.
24 DESCRIPTION OF THE PREFERRED EM~ODIME~TS
. I
26 In general, amounts of component ~ of at least about ¦
27 0,2, and pre~erably from about 0,2 to about 5.0% by weight of 28 the composition, are employed to provide the desired values of 29 sag resistance.
~ 9 ~O~i~3 1 The metal salts of component (B) can be water soluble, 2 hydrated or anhydrous. The cations of the salts of this inventior 3 are selected from the groups consisting of aluminum cations, 4 cations o the transition elements other than copper of Period 4 I, of the Periodic Table o the Elements: scandium, titanium, 6 vanadium, chromium, manganese, iron, cobalt, nickel and zinc, and 7 preferably, chromium, man~anese, iron, nickel and zinc; the 8 cations of cerium and antimony; and the mixed cations of mono and trivalent metals, designated herein as MIMIII mixed salts, where
13 (ii) hydraulic non-dry-set compo-14 sitions comprising an hydraulic cement .
or plaster of paris; and 16 (iii) non hydraulic non~dry~set 17 compos.~,o~s c~p~is~ng a, ~oom ~e,~mpera~ure 18 . . ha~dening polym~ nd ¦
' (B~ at least one non-fibrous compound selected 21 from the group consisting of gelatinous metal hydroxides 22 and me~al salts capable of forming a gelatinous or 23 hydrated hydroxide in the presence of a water soluble 24 alkaline material, the compound or compounds being present in an amount at least sufficient to pro~ide 26 the desired sag resistance, 28 The term "hydraulic" is used herein in its conventional 29 sense to refer to compositions or ~aterials which cure or harden in the presence of and upon interaction with added water, I
~6~
1 The roo~ tempe~u~e h~rden~n~ R~ly~e~ ~ the n~on~
2 hydraulic composition of (iii) can be in the form o a resinous 3 liquid or an emulsion, suspension, dlspersion, partial solution 4 or total solution~
6 In still other embodiments, sag resistan~ compositions 7 (i) o this invention comprise, in addition to the described 8 sag resistance imparting additives, an hydraulic cement~ e~g., 9 Portland cement, at least one water soluble high molecular weight polymer, and at least one substantially water insoluble polymer, 11 the latter preferably in the form of a "latex", i~e., a dis-12 persion of the polymer in water.
14 It i8 also contemplated that the dry compositions of ¦
the present invention further comF)rise inert fillers.
.1~ . .
17 The present invention ~s further viewed as extending 18 to said dry compositions when mixed with water, to methods of 19 utilizing said water mixed composit~ons, and the assemblies or the like, resulting from the in~erposltion of said wet cementit-21 ious compositions between a covering surfacing such as a tile 22 or the like and a covered substrate such as a wall or the like.
24 DESCRIPTION OF THE PREFERRED EM~ODIME~TS
. I
26 In general, amounts of component ~ of at least about ¦
27 0,2, and pre~erably from about 0,2 to about 5.0% by weight of 28 the composition, are employed to provide the desired values of 29 sag resistance.
~ 9 ~O~i~3 1 The metal salts of component (B) can be water soluble, 2 hydrated or anhydrous. The cations of the salts of this inventior 3 are selected from the groups consisting of aluminum cations, 4 cations o the transition elements other than copper of Period 4 I, of the Periodic Table o the Elements: scandium, titanium, 6 vanadium, chromium, manganese, iron, cobalt, nickel and zinc, and 7 preferably, chromium, man~anese, iron, nickel and zinc; the 8 cations of cerium and antimony; and the mixed cations of mono and trivalent metals, designated herein as MIMIII mixed salts, where
10 Ml is an alkali metal, e.g., sodium, potassium or ammonium, and ,
11 the like, and where MIII is a trivalent metallic cation of
12 Periods 3 or 4 of the Periodic Table of the Elemen~s, preferably
13 aluminum, chromium or iron.
14 The anions which are used in these salts are preferably 16 ~elected from among the anions of strong mineral acids, e.g., 17 sulphate, chloride and nitrate, a~; well as carboxylic acids, 18 preferably alkanoic acids having up to 20 carbon atoms in the 19 chain, including formates and oxalate~, Especially preferred among the organic anions are oxalate and stearate.
~1 , ., 22 Special me~tion is made of aluminum hydroxide and 23 aluminum sulfate, especially powdered aluminum sulfate, as 24 highly preferred compounds for use as the sag resistance impar~ing agent.
27 As mentioned above, the addi~ive salts of this in-28 vention possess a common chemical characteristic in that all 29 of these salts are capable of forming a gelatinous or hydrated hydroxide in the presence of an alkaline material, and more 6~78 ~, 1 specifically, an aqueous solution of a base. The watex soluble 2 alkaIine materials with which the metal salts are capable of 3 co-reacting to form gelatinous or hydrated hydroxides can be 4 organic or inorganic. Examples of inorganic compounds include I ;
but are not limi~ed to lime, i.e., calcium oxide, as well as 6 both monobasic wa~er soluble compounds such as ammonium hydroxide 7 and alkali metal and alkaline earth metal hydroxides or salts, 8 e.g., sodium hydroxide, potassium hydroxide, soda ash and the 9 like. Among these, lime is preferred.
10 . ll 11 Examples of organic alkaline materials include but are ¦
12 not limited to aliphatic and cycloaliphatic primary and secondary 13 amine~ such as diethylene triamine, morpholine, diethanol amine, 14 monoethanol amine, 2-methyl-2-amino propanol, and the like.
16 In general, enough of the alkaline material should be ¦
17 present in the aqueous composition, i,e., after water has been 18 added to the dry mix, to provide a pH of at least about 7.1, 19 preferably from about 8 to about 13.
'~0 21 In the case of sag resistant compositions according to , ;
22 this invention based on the use of (A)(i), sucl compositions pre-~
23 ferably comprise at least 20%, and more preferably, between abou~
24 20 and about 99% by weight of Portland cement. The compositions !
further comprise at least 0.2% by weight of at least one water 26 soluble high molecular weight polymer. The molecular weigh~ of thl 27 polymer is not critical, however i~ is desirable ~hat the viscositly 28 range of a 2% by weight aqueous solution of said polymers has 29 a viscosity of between 80 and 30,000 centipoises. Among the water soluble cellulose ethe~s which are particularly preEerred, .
)961i~8 1 may be mentioned the methyl ether of cellulose, hydroxypropyl-2 methyl cellulose, hydroxypropyl cellulosQ, and hydroxyethyl ' 3 cellulose. Other polymers which can be used are polyvinyl 4 alcohol and polyacrylamide. It has been found that the fore- ~ I
5 going polymers may be used not only singly but also in com- , I
6 bination of one or more of said polymers within the composition 7 as a whole. It should be stressed that the recitation of the 8 foregoing preferred polymers is in no way intended to limit the 9 scope of the present invention.
i, 1 11 The~e are u~ed, ~n ~h~ pr~e~ed e~Qd~ t~ of the 12 l~ention, at leas~ 0~2%, ~u~bly ~etween abou~ 0,2 and 6%
13 by weight of said polymer or polymers of (A)(i) relative to 14 the dry weight of the composition as a whole. In one particularly preferred embodiment of the invention there is u~ilized the ,l 16 methyl ether of cellulose, and in yet another embodiment poly- j 17 acrylamide. It has al~o been found particularly valuable to 18 utilize a combination of one of the aforesaid cellulose ethers 19 with polyvinyl alcohol, suitably substantially hydrolyzed I i 20 polyvinyl alcohol, most suitably 70 to 90% hydrolyzed grade ' ¦
21 polyvinyl alcohol. 1 ¦
23 In still other preferred embodiments, there are used, 24 in admixture, based on the total weight of dry solids, from about 20 to about 99% by weight of Portland cement, from about 0.2 to 26 about 6% by weight of a high molecular weight water soluble 27 polymer and from about 0.5 to about 50% by weight of a substant-28 ially water insoluble polymer, preferably in the form of a latex.
29 By way of illustration, t~e water insoluble polymer is selected from among polymeric materials including copolymers of s~yrene : .
. i ,., . :
~ 7;15 1 and butadiene, epoxy resins, polyvinyl chlorides, polyvinylidene 2 chlorides, neoprene elastomers and polyvinyl acetate.
4 In the case of compositions according to the invention based on the use of (A) (ii), these include Portland cement-6 based patching plasters and stucco compositions, as well as 7 plaster of paris-based patching and spackling formulations.
9 In the case of compositions according to the invention based on the use of (A) (iii), such non-hydraulic compositions 11 include any polymer-based adhesive composition capable of hard-12 ening at room temperature to form a connecting medium between 13 surfaces and in which sag resistance is desired. Such polymers 14 include, for example:
16 urea-formaldehyde resins 17 melamine-formaldehyde resins 18 polysiloxanes 19 phenolic resins ~-polyamides 21 polyesters 22 polyurethanes 23 polyacrylates 24 epoxy resins polyacetals 26 polyacrylonitrile 27 polyalkyl methacrylates 28 polyalkyl acrylates 29 polyvinyl alcohol esters polyvinyl chloride ~J961~78 1 polyolefins 2 styrene-butadiene copolymers 3 neoprene elastomers (preferably in latex form) 4 polyvinyl acetate, and combinations of any of the foregoing 6 l li 7 The molecular weight range of the polymers used in 8 this invention can vary from 500 to one million, depending on 9 the particular polymer. For the purposes of tllis invention, the preferred polymers are those which are either commercially 11 available or readily prepared using known techniques. The 12 molecular weight is not critical, but rather it is the a~ility 13 of the polymer to coalesce or harden at temperatures in the 14 range of from about 30F. to about 140F.
16 The polymer can be in the form of a resinous liquid ~ ~
17 or in the form of an emulsion, suspension; dispersion, partial I ¦
18 solution or total solution.
20 Water is a preferred liquid medium for use in non I
21 hydraulic polymeric compositions. However, organic solvents, ¦
22 and especially polar solvents, e.g., alcohols, ketones, esters, 23 liquid amides, and the like, can also be used. Regardless of 24 which materials are used as the primary liquid constituent, the non-hydraulic polymeric composition should contain water 26 or a polar solvent in an amount at least sufficient to support 27 gel formation in the presence o the sag resistance imparting 28 agent.
Preferred embodiments of such compositions will com-:~096(~
1 prise from about 20 to about 100% by weight of an hydraulic 2 cement or plaster of paris, (A)(ii), or from about 5 to about 100 3 by weight, preferably frQm about 5 to about 80% by weight of a 4 room temperature hardening polymer, (A)(iii), in combination with from about 0.2 to about 5.0% by weight of the sag resistance 6 imparting agent on a dry solids basis.
8 The compositions of this invention can also fur~her 9 include other ingredients for their conventionally employed purposes, such as inert fillers, coloring agents, stabilizers, 11 foam breakers, dispersants, wetting agents, emulsifiers, fungi- I
12 cides, and the like. The filler, by way of illustration, can l I
13 be selected from among sand, perlite, vermiculite, glass beads, 14 powdered walnut shells, limestone, powdered inert me~als, pig-ments such as titanium dioxide, and the like. In those compo- l 'I
16 sitions where an hydraulic cement is employed, a weight ratio of 17 cement to inert filler in the range of from about 0.15:1 to about 18 4:1 is preferred.
In the case of the hydraulic non-dry-set compositions, 21 the amount of water to be admixed with the dry blend prior to use 22 will vary in accordance with the particular compositions. In 23 general, the amount o water is influenced by the amount of inert 24 filler present. Thus, where no filler or only minor amounts of filler are used, the proportion of water added to the dry blend 2~ ranges from about 20 to about 60% by weight, based on the weight ¦
27 of the dry blend, On the other hand, where large amounts of 28 filler are used, the amount of water normally ranges from about 29 10 to about 40% by weight of the dry blend, .. . . .
,, ~,; . . : :
.~
61~78 1 The amount of water utilized with the compositions ¦
2 defined hereinabove in order to achieve the working composition 3 will vary somewhat depending upon the constitution of the dry 4 composition. The amount of water utilized to give an adhesive of the desired properties is however principally influenced by 6 the amount of inert filler employed. Thus, where there is l~
7 employed no filler or substantially no filler, the proportion ~ ¦
8 of water added to the dry mix will suitably be from about 30% ¦
9 to about 50% of the initial weight of the dry mix, on the other hand, where substantial amounts of coarse filler are employed, 11 the amount of water utilized may be reduced to the order of from 1 ¦
12 about 15 to about 40% by weight of the dry composition. ¦ !
14 The compositions of the present invention are converted into the adhesive composition by addlng the aforementioned 16 amounts of water thereto in the mcmner generally accepted by 17 those skilled in the art. The adhesive thus formed may be 18 applied to any suitable covering s,urfacing which it is desired 19 to affix to a second substrate surface. Since ~he general pur-pose of the present invention is to provide an adhesive compo-21 sition with good sag resistance, it is generally presumed that 22 such adhesive compositions will be employed where it is desirable 23 to affix ~he first surfacing ~o a second surface from which it 24 is likely to slide or settle were it not for the sag resistance properties. Again, while it is the general prac~ice in the 26 art to apply the adhesive to the second substrate which will be 27 covered by the first surface, again the invention is not limited 28 thereto and procedures whe~eby the adhe~ive is initial~y placed 29 upon said f~rst surfaçe are to be con~id~red to be within the 30 scope of the present invention. I
~L09~078 1 It is generally co~templ~d ~h~t th~ f~s~ s~r~
2 ¦ that is-to say, the surface to be applied to the substrate will 3 ¦ be the rearward surface of a surfacing unit such as ceramic tile, 4 slate, marble, and the like. It is further contemplated that the most general use will be with ceramic tile, specifically ceramic 6 tile having at least one unglazed surface upon which the adhesive 7 will be applied, it is further contemplated that said unglazed I ¦
8 surface may have a substantially irregular surface to permit 9 better adhesion of the adhesive thereto. Notwithstanding said irregularity, the surface of said irregular unit will be either 11 substantially flat, or, when it is intended to be applied to a 12 second substrate having a curved surface, said first surface will 13 have a degree of curvature substantially conforming to the 14 degree of curvature of the substrate upon which it is to be placed.
17 It is further contemplated that the amount of adhesive 18 to be placed upon said surace shall generally be less than 3/8 19 of an inch in thickness when applied in an even layer but generally not be less than 1/32 of an inch in ~hickness. It is 21 contemplated that the adhesive be applied to the substrate with 22 a trowel, suitably a notched trowel, whereby th~ adhesive is 23 formed into ribbons of adhesive deposited by said trowel upon 24 said substrate, Said controlled irregularity of thickness is known tQ improve the adhesion of the surfacing unit to the sub-26 strate to which it is ~o be attached.
28 This invention also provides a method of imparting sag I
29 resi~tance to adhesive compositions not contalning a wa-ter re- I
tentive agent, the method comprising addi.ng a sag resistance im-~ ~ 15 ~
. j: . .
1 parting agent as described to one or more of ~A)~ii) or 3 (A)(iiiS.
4 In still another aspect of this invention, there is provided an improvement in th method of installing wall and floor 6 covering surfaces, such as ceramic tiles and the like, slate, I
7 marble, etc., using the sag resistant compositions as described.
9 FORMULATION OF DRY SET MOP~TAR MIY~ES
10 . il 1.
The dry set Portland cement mortar dry mix designated 14 herein below as DSM I has the fol'Lowing formulation:
16 ~ 1,00 rams Type I Portland ~ement 17 1,000 grams Graded Silica sand ~grade 30 mesh) 18 6 grams Methocel ~ (65 :HG, 4,000 cps).
The dry set Portland cemen~ mortar dry mix designated 21 herein below as DSM II has the following formulation:
23 2,000 grams Type I Portland cement 24 20 ~rams Methocel ~ (65 HG) ~ I
. I `
27 ll 28 The Portland cement mortar dry mix designated MDMI, 29 for use between two water impervious surfaces, has the following formulation:
ll .,......... I , .,, . , . .,. , ~ . I
l~ l ~ l l ~6~7~
1 1,000 grams Type I Portland cement 2 1 000 grams Graded silica sand (grade 30 mesh) 6 Test procedure for sag resistance on vertical surfaces l I
7 for dry set Portland cement mortar (A118.1-1967). l i 9 "Sag on Ver~ical Surfaces. Prepare mortar as in 5-1.2 and trowel onto the vertical 11 surface of a dry cinder block between guide I I
12 strips 1/4 inch thick. Lightly tap a tile I j 13 (Type B) onto the mortar, surface immediate'Ly ¦ ¦
14 after applying mor~ar, with any back rlbs on tile vertical. Accurately mark the to 16 edge of the tlle and reeord any downward ¦
17 displacement of the til~i m~asured 2 hours 18 after placement as the Sag."
19 l l 21 TEST PROCEDU~E II
23 This test procedure is identical to test procedure I
24 except that a metal or glàss plate or a vitreous tile are sub-2S stituted for a dry cinder block and an unglazed ceramic tile, 2S respectively.
.
~09~iO7 1 , ~, I
3 .
4 DSM I and II were compounded with and without asbestos S fiber, mixed with water and tested for sag resistance in accord-6 ance with the foregoing test procedure in proportions set forth 7 below to give sag results noted in the final column.
8 . '.
AMOUNT AMOUNT AMOUNT AMOUNT
10400 ~m~, 100 gms. -- -- F/O
11400 gms. 100 gms. asbestos 2 g N/S
13 400 gms.140 gms. -- __ F/O
400 gms.140 gms. asbes~os 4 g N/S
14 fiber lS
F/O ~ fell off .16 .
17 N/S - no sag 18 .
MDM I waQ tested as above.
~9 AMOUNT
AMOUNT MDM I AMOUNT WATERADDITIVE ADDITIVE SAG
21 ~
400 ~, 100 -- -- F/O
400 100Aluminum 23 Sulfate 500 g N/S
27 DSM I & II - Aluminum Salts.
.......
DSM I & II were compounded with hydrated and anhydrous .. I
. . ..
IL~396078 1¦ aluminum salts, mixed with w:lter and tested for sag resistance 2 in accordance with Test Procedure I in the proportions set forth 3 below to give the sag results reported in the final column.
AMOUNT ADDITIVE SAG
61 DSM I (gm) WATER (gm) ADDITIUE (gm) (inches~
7~ 99.75 25 l~(SO4)3- 0.25 5/16 8 99 50 25 . oAl~(oO4)3 1/8 99.25 25 o~(S4)3 0.75 0 11 98.0 25 Al~(SO4)3' 2.0 0 13 . 98.0 25 12(S04)3 2.0 0 ~5 99.5 25 Al~(SO4)3- 0-5 F/0 .16 99.0 25 18 H2O 1.0 3/16 18 98.5 25 18 H20 1.5 1/32 19 98.0 25 A12(S04)3 2.0 0 21 99.2 25 41~oC2H32)4 0.8 1/16 98.5 25 Al stearate 1.5 1/32 22 (high gel) 23 ! 98.5 25 Al stearate 1.5 1/16 24 (lo~ gel~
99.5 25 AlC13 6H2 0.5 F/0 26 99.0 25 AlC13-6H2O 1.0 7/16 27 1 98.5 25 AlC13-6H2O 1.5 1/32 28 I 98.0 2S AlCl 6H2O 2.0 1 98.5 37 1l82Hso4)3 5/16 30~1 ~ I, 9 ~7 ~
AMOUNT ADDITIVE SAG
2 DSM II ~m3 WATER (gm) ADDITIVE(gm) (inches) 3 182H204 31.0 1/~
5~ 98.5 37 182( 04)3 1.5 1/16 6 98.0 37 2 2.0 0 11 DSM I & II - Aluminum Salt Solution.
12 . .
13 DSM 1 & II was compounded with a 25% (w/w) aqueous 14 aluminum salt 801ution, mixed ~ith water and tested for sag resistance in accordance wi~h Test Procedure I in ~he proportions 16 set forth below to gi~e the sag results reported in the ~inal 17 column.
AMOUNT ADDITIVE SAG
19 DSM I (gm~ W TER (gm) ADDITI~E (gm) _ (inches) 99.5 25 AlCl 0.5 F/0 22 99,0 25 A1~13 1.0 7/16 241 98.5 25 AlCl~ 1.5 0 25 1 98.0 25 ~lC13- 2.0 0 26 ~ 6 H20 27 ¦DSM II
28¦~ 99 5 37 6 H30 1/8 29 1¦ 99 o 37 61C123O 1.0 3/32 Il - 20 -..
. ' 6~7~
~ EXAMPLE 4 23~ DSM I & II - Transiti~n Metal Salts.
4 ~ DSM I & II were compounded with hydra~ed transition 5 imetal salt~, mi~ed with water and tested for sag resistance in 6 laccordance with Test Procedure I in the proportions set forth 7 below to give the sag results reported in the final column.
8 .
9 AMOUNT AiDDITIVE SA&
10 DSM~ WATER (gm) ADDITIVE (gm) ~inches) 11 98 25 MnS4'~2 2.0 5/16 12 98 25 18 H2O 2.0 1/16 13 98 25 Co SO4 2.0 1/32 98 25 6iSO42~ 2,0 5/8 16 98 25 znso4~ 2~0 1/16 17¦ 7 H2O
181 98.0 25 Sb2(S04~3'2.0 l/32 l9 99,5 25 9 H204 3 F/O
21 99'0 25 Fe2(SO4)3 1.0 1 1/8 22 98~5 25 Fe2~(SO4)3~ 1.5 3/16 IIDSM II
25j 26l 99 5 37 ge2(So4)3 7/32 28l 9 H2 l.O 1/8 29~ 98,5 37 9 H2 1.5 1/8 98,0 37 Fe2(SO4)3~2.0 1/16 ~ 36~7~
I III
DSM I - M M Salts 6 DSM I was compounded with hydrated mixed salts of the 7 M M type, mixed with water and t~sted for sag resistance in 8 accordance with Test Procedure I in the proportions set forth 9 below to give the sag results reported in the final column.
AMO~NT ADDITIVE SAG
DSM I (gm) WATER (gm) ADDITIVE (gm) (inches) 11 99.5 25K~S04. ) 0-5 F/0 12 AI2(S04)3 ) 13 9900 25K~S(4o ) ) 1.0 15/16 98.5 25K S0 0 ) 105 3/16 16 A~ (S0 ) ) 18 98,0 25 K2S0~ } 2.0 1/32 19 99.5 25 Na2(S04) ) 0-5 F/0 24 H20 ) 21 99.0 25 Na2(S04) ) 1.0 1/8 22 24 H20 ) 23 98,5 25 Na2(S04) ) 1.5 1/32 24 A12(S04)3 ) 98.0 25 i Na2(S04) ) 2.0 0 26 A12(s04)3 ) 28 99.5 25 A12(S04)3. ) F/0 320 99 0 25 (NH~)2(S4} 1.0 11/16 lU960~8 1¦ E2AMPLE 5 (cont'd.) 3¦1 bSM I ~ ? WATER (gm) ADDITIVE(~m) ~ ) 4~l 98.5 25 A12(S04)3-4) 1.5 1/8 6 1 98.0 25 (NH )2(S04~ 2.0 1/16 7 A12(~04)3 8~ 98.5 25 124He(so4)2 1.5 7/8 ll 98 5 25 K~SO4cr2(s04)3 1.5 3/16 12 ¦ In accordance with the above procedure, bu~ using DSM I~
13 in place of DSM I, the following results are obtained.
~1 , ., 22 Special me~tion is made of aluminum hydroxide and 23 aluminum sulfate, especially powdered aluminum sulfate, as 24 highly preferred compounds for use as the sag resistance impar~ing agent.
27 As mentioned above, the addi~ive salts of this in-28 vention possess a common chemical characteristic in that all 29 of these salts are capable of forming a gelatinous or hydrated hydroxide in the presence of an alkaline material, and more 6~78 ~, 1 specifically, an aqueous solution of a base. The watex soluble 2 alkaIine materials with which the metal salts are capable of 3 co-reacting to form gelatinous or hydrated hydroxides can be 4 organic or inorganic. Examples of inorganic compounds include I ;
but are not limi~ed to lime, i.e., calcium oxide, as well as 6 both monobasic wa~er soluble compounds such as ammonium hydroxide 7 and alkali metal and alkaline earth metal hydroxides or salts, 8 e.g., sodium hydroxide, potassium hydroxide, soda ash and the 9 like. Among these, lime is preferred.
10 . ll 11 Examples of organic alkaline materials include but are ¦
12 not limited to aliphatic and cycloaliphatic primary and secondary 13 amine~ such as diethylene triamine, morpholine, diethanol amine, 14 monoethanol amine, 2-methyl-2-amino propanol, and the like.
16 In general, enough of the alkaline material should be ¦
17 present in the aqueous composition, i,e., after water has been 18 added to the dry mix, to provide a pH of at least about 7.1, 19 preferably from about 8 to about 13.
'~0 21 In the case of sag resistant compositions according to , ;
22 this invention based on the use of (A)(i), sucl compositions pre-~
23 ferably comprise at least 20%, and more preferably, between abou~
24 20 and about 99% by weight of Portland cement. The compositions !
further comprise at least 0.2% by weight of at least one water 26 soluble high molecular weight polymer. The molecular weigh~ of thl 27 polymer is not critical, however i~ is desirable ~hat the viscositly 28 range of a 2% by weight aqueous solution of said polymers has 29 a viscosity of between 80 and 30,000 centipoises. Among the water soluble cellulose ethe~s which are particularly preEerred, .
)961i~8 1 may be mentioned the methyl ether of cellulose, hydroxypropyl-2 methyl cellulose, hydroxypropyl cellulosQ, and hydroxyethyl ' 3 cellulose. Other polymers which can be used are polyvinyl 4 alcohol and polyacrylamide. It has been found that the fore- ~ I
5 going polymers may be used not only singly but also in com- , I
6 bination of one or more of said polymers within the composition 7 as a whole. It should be stressed that the recitation of the 8 foregoing preferred polymers is in no way intended to limit the 9 scope of the present invention.
i, 1 11 The~e are u~ed, ~n ~h~ pr~e~ed e~Qd~ t~ of the 12 l~ention, at leas~ 0~2%, ~u~bly ~etween abou~ 0,2 and 6%
13 by weight of said polymer or polymers of (A)(i) relative to 14 the dry weight of the composition as a whole. In one particularly preferred embodiment of the invention there is u~ilized the ,l 16 methyl ether of cellulose, and in yet another embodiment poly- j 17 acrylamide. It has al~o been found particularly valuable to 18 utilize a combination of one of the aforesaid cellulose ethers 19 with polyvinyl alcohol, suitably substantially hydrolyzed I i 20 polyvinyl alcohol, most suitably 70 to 90% hydrolyzed grade ' ¦
21 polyvinyl alcohol. 1 ¦
23 In still other preferred embodiments, there are used, 24 in admixture, based on the total weight of dry solids, from about 20 to about 99% by weight of Portland cement, from about 0.2 to 26 about 6% by weight of a high molecular weight water soluble 27 polymer and from about 0.5 to about 50% by weight of a substant-28 ially water insoluble polymer, preferably in the form of a latex.
29 By way of illustration, t~e water insoluble polymer is selected from among polymeric materials including copolymers of s~yrene : .
. i ,., . :
~ 7;15 1 and butadiene, epoxy resins, polyvinyl chlorides, polyvinylidene 2 chlorides, neoprene elastomers and polyvinyl acetate.
4 In the case of compositions according to the invention based on the use of (A) (ii), these include Portland cement-6 based patching plasters and stucco compositions, as well as 7 plaster of paris-based patching and spackling formulations.
9 In the case of compositions according to the invention based on the use of (A) (iii), such non-hydraulic compositions 11 include any polymer-based adhesive composition capable of hard-12 ening at room temperature to form a connecting medium between 13 surfaces and in which sag resistance is desired. Such polymers 14 include, for example:
16 urea-formaldehyde resins 17 melamine-formaldehyde resins 18 polysiloxanes 19 phenolic resins ~-polyamides 21 polyesters 22 polyurethanes 23 polyacrylates 24 epoxy resins polyacetals 26 polyacrylonitrile 27 polyalkyl methacrylates 28 polyalkyl acrylates 29 polyvinyl alcohol esters polyvinyl chloride ~J961~78 1 polyolefins 2 styrene-butadiene copolymers 3 neoprene elastomers (preferably in latex form) 4 polyvinyl acetate, and combinations of any of the foregoing 6 l li 7 The molecular weight range of the polymers used in 8 this invention can vary from 500 to one million, depending on 9 the particular polymer. For the purposes of tllis invention, the preferred polymers are those which are either commercially 11 available or readily prepared using known techniques. The 12 molecular weight is not critical, but rather it is the a~ility 13 of the polymer to coalesce or harden at temperatures in the 14 range of from about 30F. to about 140F.
16 The polymer can be in the form of a resinous liquid ~ ~
17 or in the form of an emulsion, suspension; dispersion, partial I ¦
18 solution or total solution.
20 Water is a preferred liquid medium for use in non I
21 hydraulic polymeric compositions. However, organic solvents, ¦
22 and especially polar solvents, e.g., alcohols, ketones, esters, 23 liquid amides, and the like, can also be used. Regardless of 24 which materials are used as the primary liquid constituent, the non-hydraulic polymeric composition should contain water 26 or a polar solvent in an amount at least sufficient to support 27 gel formation in the presence o the sag resistance imparting 28 agent.
Preferred embodiments of such compositions will com-:~096(~
1 prise from about 20 to about 100% by weight of an hydraulic 2 cement or plaster of paris, (A)(ii), or from about 5 to about 100 3 by weight, preferably frQm about 5 to about 80% by weight of a 4 room temperature hardening polymer, (A)(iii), in combination with from about 0.2 to about 5.0% by weight of the sag resistance 6 imparting agent on a dry solids basis.
8 The compositions of this invention can also fur~her 9 include other ingredients for their conventionally employed purposes, such as inert fillers, coloring agents, stabilizers, 11 foam breakers, dispersants, wetting agents, emulsifiers, fungi- I
12 cides, and the like. The filler, by way of illustration, can l I
13 be selected from among sand, perlite, vermiculite, glass beads, 14 powdered walnut shells, limestone, powdered inert me~als, pig-ments such as titanium dioxide, and the like. In those compo- l 'I
16 sitions where an hydraulic cement is employed, a weight ratio of 17 cement to inert filler in the range of from about 0.15:1 to about 18 4:1 is preferred.
In the case of the hydraulic non-dry-set compositions, 21 the amount of water to be admixed with the dry blend prior to use 22 will vary in accordance with the particular compositions. In 23 general, the amount o water is influenced by the amount of inert 24 filler present. Thus, where no filler or only minor amounts of filler are used, the proportion of water added to the dry blend 2~ ranges from about 20 to about 60% by weight, based on the weight ¦
27 of the dry blend, On the other hand, where large amounts of 28 filler are used, the amount of water normally ranges from about 29 10 to about 40% by weight of the dry blend, .. . . .
,, ~,; . . : :
.~
61~78 1 The amount of water utilized with the compositions ¦
2 defined hereinabove in order to achieve the working composition 3 will vary somewhat depending upon the constitution of the dry 4 composition. The amount of water utilized to give an adhesive of the desired properties is however principally influenced by 6 the amount of inert filler employed. Thus, where there is l~
7 employed no filler or substantially no filler, the proportion ~ ¦
8 of water added to the dry mix will suitably be from about 30% ¦
9 to about 50% of the initial weight of the dry mix, on the other hand, where substantial amounts of coarse filler are employed, 11 the amount of water utilized may be reduced to the order of from 1 ¦
12 about 15 to about 40% by weight of the dry composition. ¦ !
14 The compositions of the present invention are converted into the adhesive composition by addlng the aforementioned 16 amounts of water thereto in the mcmner generally accepted by 17 those skilled in the art. The adhesive thus formed may be 18 applied to any suitable covering s,urfacing which it is desired 19 to affix to a second substrate surface. Since ~he general pur-pose of the present invention is to provide an adhesive compo-21 sition with good sag resistance, it is generally presumed that 22 such adhesive compositions will be employed where it is desirable 23 to affix ~he first surfacing ~o a second surface from which it 24 is likely to slide or settle were it not for the sag resistance properties. Again, while it is the general prac~ice in the 26 art to apply the adhesive to the second substrate which will be 27 covered by the first surface, again the invention is not limited 28 thereto and procedures whe~eby the adhe~ive is initial~y placed 29 upon said f~rst surfaçe are to be con~id~red to be within the 30 scope of the present invention. I
~L09~078 1 It is generally co~templ~d ~h~t th~ f~s~ s~r~
2 ¦ that is-to say, the surface to be applied to the substrate will 3 ¦ be the rearward surface of a surfacing unit such as ceramic tile, 4 slate, marble, and the like. It is further contemplated that the most general use will be with ceramic tile, specifically ceramic 6 tile having at least one unglazed surface upon which the adhesive 7 will be applied, it is further contemplated that said unglazed I ¦
8 surface may have a substantially irregular surface to permit 9 better adhesion of the adhesive thereto. Notwithstanding said irregularity, the surface of said irregular unit will be either 11 substantially flat, or, when it is intended to be applied to a 12 second substrate having a curved surface, said first surface will 13 have a degree of curvature substantially conforming to the 14 degree of curvature of the substrate upon which it is to be placed.
17 It is further contemplated that the amount of adhesive 18 to be placed upon said surace shall generally be less than 3/8 19 of an inch in thickness when applied in an even layer but generally not be less than 1/32 of an inch in ~hickness. It is 21 contemplated that the adhesive be applied to the substrate with 22 a trowel, suitably a notched trowel, whereby th~ adhesive is 23 formed into ribbons of adhesive deposited by said trowel upon 24 said substrate, Said controlled irregularity of thickness is known tQ improve the adhesion of the surfacing unit to the sub-26 strate to which it is ~o be attached.
28 This invention also provides a method of imparting sag I
29 resi~tance to adhesive compositions not contalning a wa-ter re- I
tentive agent, the method comprising addi.ng a sag resistance im-~ ~ 15 ~
. j: . .
1 parting agent as described to one or more of ~A)~ii) or 3 (A)(iiiS.
4 In still another aspect of this invention, there is provided an improvement in th method of installing wall and floor 6 covering surfaces, such as ceramic tiles and the like, slate, I
7 marble, etc., using the sag resistant compositions as described.
9 FORMULATION OF DRY SET MOP~TAR MIY~ES
10 . il 1.
The dry set Portland cement mortar dry mix designated 14 herein below as DSM I has the fol'Lowing formulation:
16 ~ 1,00 rams Type I Portland ~ement 17 1,000 grams Graded Silica sand ~grade 30 mesh) 18 6 grams Methocel ~ (65 :HG, 4,000 cps).
The dry set Portland cemen~ mortar dry mix designated 21 herein below as DSM II has the following formulation:
23 2,000 grams Type I Portland cement 24 20 ~rams Methocel ~ (65 HG) ~ I
. I `
27 ll 28 The Portland cement mortar dry mix designated MDMI, 29 for use between two water impervious surfaces, has the following formulation:
ll .,......... I , .,, . , . .,. , ~ . I
l~ l ~ l l ~6~7~
1 1,000 grams Type I Portland cement 2 1 000 grams Graded silica sand (grade 30 mesh) 6 Test procedure for sag resistance on vertical surfaces l I
7 for dry set Portland cement mortar (A118.1-1967). l i 9 "Sag on Ver~ical Surfaces. Prepare mortar as in 5-1.2 and trowel onto the vertical 11 surface of a dry cinder block between guide I I
12 strips 1/4 inch thick. Lightly tap a tile I j 13 (Type B) onto the mortar, surface immediate'Ly ¦ ¦
14 after applying mor~ar, with any back rlbs on tile vertical. Accurately mark the to 16 edge of the tlle and reeord any downward ¦
17 displacement of the til~i m~asured 2 hours 18 after placement as the Sag."
19 l l 21 TEST PROCEDU~E II
23 This test procedure is identical to test procedure I
24 except that a metal or glàss plate or a vitreous tile are sub-2S stituted for a dry cinder block and an unglazed ceramic tile, 2S respectively.
.
~09~iO7 1 , ~, I
3 .
4 DSM I and II were compounded with and without asbestos S fiber, mixed with water and tested for sag resistance in accord-6 ance with the foregoing test procedure in proportions set forth 7 below to give sag results noted in the final column.
8 . '.
AMOUNT AMOUNT AMOUNT AMOUNT
10400 ~m~, 100 gms. -- -- F/O
11400 gms. 100 gms. asbestos 2 g N/S
13 400 gms.140 gms. -- __ F/O
400 gms.140 gms. asbes~os 4 g N/S
14 fiber lS
F/O ~ fell off .16 .
17 N/S - no sag 18 .
MDM I waQ tested as above.
~9 AMOUNT
AMOUNT MDM I AMOUNT WATERADDITIVE ADDITIVE SAG
21 ~
400 ~, 100 -- -- F/O
400 100Aluminum 23 Sulfate 500 g N/S
27 DSM I & II - Aluminum Salts.
.......
DSM I & II were compounded with hydrated and anhydrous .. I
. . ..
IL~396078 1¦ aluminum salts, mixed with w:lter and tested for sag resistance 2 in accordance with Test Procedure I in the proportions set forth 3 below to give the sag results reported in the final column.
AMOUNT ADDITIVE SAG
61 DSM I (gm) WATER (gm) ADDITIUE (gm) (inches~
7~ 99.75 25 l~(SO4)3- 0.25 5/16 8 99 50 25 . oAl~(oO4)3 1/8 99.25 25 o~(S4)3 0.75 0 11 98.0 25 Al~(SO4)3' 2.0 0 13 . 98.0 25 12(S04)3 2.0 0 ~5 99.5 25 Al~(SO4)3- 0-5 F/0 .16 99.0 25 18 H2O 1.0 3/16 18 98.5 25 18 H20 1.5 1/32 19 98.0 25 A12(S04)3 2.0 0 21 99.2 25 41~oC2H32)4 0.8 1/16 98.5 25 Al stearate 1.5 1/32 22 (high gel) 23 ! 98.5 25 Al stearate 1.5 1/16 24 (lo~ gel~
99.5 25 AlC13 6H2 0.5 F/0 26 99.0 25 AlC13-6H2O 1.0 7/16 27 1 98.5 25 AlC13-6H2O 1.5 1/32 28 I 98.0 2S AlCl 6H2O 2.0 1 98.5 37 1l82Hso4)3 5/16 30~1 ~ I, 9 ~7 ~
AMOUNT ADDITIVE SAG
2 DSM II ~m3 WATER (gm) ADDITIVE(gm) (inches) 3 182H204 31.0 1/~
5~ 98.5 37 182( 04)3 1.5 1/16 6 98.0 37 2 2.0 0 11 DSM I & II - Aluminum Salt Solution.
12 . .
13 DSM 1 & II was compounded with a 25% (w/w) aqueous 14 aluminum salt 801ution, mixed ~ith water and tested for sag resistance in accordance wi~h Test Procedure I in ~he proportions 16 set forth below to gi~e the sag results reported in the ~inal 17 column.
AMOUNT ADDITIVE SAG
19 DSM I (gm~ W TER (gm) ADDITI~E (gm) _ (inches) 99.5 25 AlCl 0.5 F/0 22 99,0 25 A1~13 1.0 7/16 241 98.5 25 AlCl~ 1.5 0 25 1 98.0 25 ~lC13- 2.0 0 26 ~ 6 H20 27 ¦DSM II
28¦~ 99 5 37 6 H30 1/8 29 1¦ 99 o 37 61C123O 1.0 3/32 Il - 20 -..
. ' 6~7~
~ EXAMPLE 4 23~ DSM I & II - Transiti~n Metal Salts.
4 ~ DSM I & II were compounded with hydra~ed transition 5 imetal salt~, mi~ed with water and tested for sag resistance in 6 laccordance with Test Procedure I in the proportions set forth 7 below to give the sag results reported in the final column.
8 .
9 AMOUNT AiDDITIVE SA&
10 DSM~ WATER (gm) ADDITIVE (gm) ~inches) 11 98 25 MnS4'~2 2.0 5/16 12 98 25 18 H2O 2.0 1/16 13 98 25 Co SO4 2.0 1/32 98 25 6iSO42~ 2,0 5/8 16 98 25 znso4~ 2~0 1/16 17¦ 7 H2O
181 98.0 25 Sb2(S04~3'2.0 l/32 l9 99,5 25 9 H204 3 F/O
21 99'0 25 Fe2(SO4)3 1.0 1 1/8 22 98~5 25 Fe2~(SO4)3~ 1.5 3/16 IIDSM II
25j 26l 99 5 37 ge2(So4)3 7/32 28l 9 H2 l.O 1/8 29~ 98,5 37 9 H2 1.5 1/8 98,0 37 Fe2(SO4)3~2.0 1/16 ~ 36~7~
I III
DSM I - M M Salts 6 DSM I was compounded with hydrated mixed salts of the 7 M M type, mixed with water and t~sted for sag resistance in 8 accordance with Test Procedure I in the proportions set forth 9 below to give the sag results reported in the final column.
AMO~NT ADDITIVE SAG
DSM I (gm) WATER (gm) ADDITIVE (gm) (inches) 11 99.5 25K~S04. ) 0-5 F/0 12 AI2(S04)3 ) 13 9900 25K~S(4o ) ) 1.0 15/16 98.5 25K S0 0 ) 105 3/16 16 A~ (S0 ) ) 18 98,0 25 K2S0~ } 2.0 1/32 19 99.5 25 Na2(S04) ) 0-5 F/0 24 H20 ) 21 99.0 25 Na2(S04) ) 1.0 1/8 22 24 H20 ) 23 98,5 25 Na2(S04) ) 1.5 1/32 24 A12(S04)3 ) 98.0 25 i Na2(S04) ) 2.0 0 26 A12(s04)3 ) 28 99.5 25 A12(S04)3. ) F/0 320 99 0 25 (NH~)2(S4} 1.0 11/16 lU960~8 1¦ E2AMPLE 5 (cont'd.) 3¦1 bSM I ~ ? WATER (gm) ADDITIVE(~m) ~ ) 4~l 98.5 25 A12(S04)3-4) 1.5 1/8 6 1 98.0 25 (NH )2(S04~ 2.0 1/16 7 A12(~04)3 8~ 98.5 25 124He(so4)2 1.5 7/8 ll 98 5 25 K~SO4cr2(s04)3 1.5 3/16 12 ¦ In accordance with the above procedure, bu~ using DSM I~
13 in place of DSM I, the following results are obtained.
15 DSM II ~gm) WATER (~m) ADDI~'IVE (gm) (inches)l
16 1 99.5 37 K~SO~ ) 0.5 5/16
17 24 H20
18 99.0 37 K~SO~ ) 1.0 3/16
19 ' 24 H20
20 ¦ ~9~.5 37 K SO ) 1.5 1/16
21 I A~ (SO ) 23 1 98.0 37 24 H20 3 2.0 1/32 24 ~ 99.5 37 Na2 54 ) 0 5 3/8
22~5i 242(So4)3 27 ~l 99'0 37 Na2 S04 ) 1.0 1/B
28 Ij A12(S04)3 1 Na2 S4 ) 1.5 1~32 30 'I A12(S04)3
28 Ij A12(S04)3 1 Na2 S4 ) 1.5 1~32 30 'I A12(S04)3
- 23 ll l . . .
:l~g6~8 1 EXAMPLE 5 ~cont'd.) , AMOUNT ADDITIVE SAG
3 DS~ m~ WATER (gm) ADDITIVE (f~m) (inches~
4 98.0 37 Na2 S04 ) 2.0 0 ~ .
A12(S~4)3 ) 99.0 37 (NH4),fSO~ 1.0 3/16 9 . 242H(~4~3 98.5 37 (NH4) S04 1.5 3/32 121 A42~S~
13 98.0 37 A12 (~04$3 2.0 1/16 ¦
14~ 8.5 37 124~e(so4)2 1.5 7/8 19 Experiments were carried out using DSM Ia, a dry set mortar mix of the compo~ition of Formulation I wherein the 21 Methocel ~ is replaced with another polymer and the added salt 22 was A12($04)3 14 H20. The results using Test Procedure I are 23 as follows:
:l~g6~8 1 EXAMPLE 5 ~cont'd.) , AMOUNT ADDITIVE SAG
3 DS~ m~ WATER (gm) ADDITIVE (f~m) (inches~
4 98.0 37 Na2 S04 ) 2.0 0 ~ .
A12(S~4)3 ) 99.0 37 (NH4),fSO~ 1.0 3/16 9 . 242H(~4~3 98.5 37 (NH4) S04 1.5 3/32 121 A42~S~
13 98.0 37 A12 (~04$3 2.0 1/16 ¦
14~ 8.5 37 124~e(so4)2 1.5 7/8 19 Experiments were carried out using DSM Ia, a dry set mortar mix of the compo~ition of Formulation I wherein the 21 Methocel ~ is replaced with another polymer and the added salt 22 was A12($04)3 14 H20. The results using Test Procedure I are 23 as follows:
24 : f
25 DSM I a WATE~ AMOUNT SALT POLYMER SAG
26 98.5 25 1.5 Natrosol O
27 98,5 25 1,5 Klucel O
28 l98.5 25 1 Reten O
29,1
30 I(~atrosol ~ is a hydroxye~hyl n.ethyl cellulose and K1UCP1~iS ::
~1 1 , :: . . . . . , .. . .; . :.
I 1, lC~60~
l a hydro~ypropyl methyl cellulose, both manufactured by Hercules, 2 Inc. Reten ~ i~ a polyacrylamide also manufactured by Hercules, 3 Inc.
7 The following dry-set mortar mix was prepared and 8 tested for necessary properties including sag resistance in 9 accordance ~ith Test Procedure I.
. . Ii 11 381 gm~. of Portland cement 12 5 gms. of methyl hydroxypropyl cellulose*
13 2 gms. of polyvinyl alcohol, 87% hydro~yzed 14 12 gms. of powde~d ~ u~ sul~te ~h ~ waters o 15 ~ 600 8ms of -30 mesh sand hydrati~n 17 To the 1000 gms of mix was added 250 gms of water. The mortar 18 ~howed good bond to ab~orptive and`non-absorptive tile, adequate 19 open time and adjustability, good initial set time and excellent ~ag resis~ance.
22 * ~o~ Chem. Co,, Me~hocel ~ 4000 cps, 90 HG grade.
24 EXAMP~E 8 26 Po~land Cement, Sand together with Clay and Alum 2B A ~ry set mortar mix co~si~ting o equ~l parts o 29 I Por~la~d ce~ent and fi~e sand as well as ~ethocel ~ (4000 cps 30 ¦I go HG, 0,~%) was preparedt Hyd~ted ~lu~inu~ sulfate and finely 25 ~
~. , .
.: , : ~ ' ~ - :' , ~ 960~8 1 divided clay (attapulgite or kaolin) were added and the resultant 2 dry mixture combined with water. The resultan~ mortar was sub- ~
3 mitted to Test Procedure I with the following results: j AMOUNT
5 CEMENT/SAND CLAY AMOUNTAMOUNT OF SA~
AMT. ~ms. METHOCEL ADDITIVE CLAY SALT (gms.) (inche 6 98~8 0.6 Attagel 150 0.6 0.0 F/O
8 98.5 0.6 Attagel 150 0.6 0.3 1/8 98.3 0.6 Attagel lS0 l.l 0.0 l/4 9 98.4 0.6 Georgia 1.0 0.0 5/16 ¦
Kaolin ll 98.1 0.6 Georgia 1.0 0.3 3/32 12 ~ ~aolin 14 EXAMPL~
16 MDM I - Aluminum Salt~
18 MDM I wa~ compounded wilth hydrated aluminum salts and 19 gelatinou~ aluminum hydroxide (prepared in situ) mixed with 20 water and tested for sag resistance in accordance with Tes~ I
21 Procedure II in the proportions set forth below to give the sag re~ults reported in ~he final column.
23 AMOUNT ~DDITIVE S~G
24 ~D~ I (g~ WATER (gm) ADD~TIVE ~gm) (inches 25 98.6 25 A12(SO4)3 1.2 No sag 26 98.28 25 A12(SO4)31.25 No sag 27 Ca (~H2) 0.47 29 In aceordance with the above procedure but where, in place of 301,A12(S04)3 14 H20, there is utilized MnS04H20, Cr2(S04)3, .
l l l l l ~ 26- ! I
`, ...... , ., .. ..... . .. ~, . ..... ..... . .
... . . ... ,.. ;.` .~. . . . ..
2 18 H20, CuS04 5H20, NlS04 6H20, ZnS04 7H~0 Sb2 (S04)3, 3 Fe2(S04~3 9H20. K2S4 A12(S04)3 24H20, Na2~S04)A12 (S04)3 -4 24H20- (NH4)2 S04 A12 (S04) 24H20, NH2Fe (S04)2 12H~O and K2S04Cr2(S04)3 24H20, there are obtain~d similar results.
6 ~ , 9 DSM I - Gelatinous Aluminum Hydroxide.
10 . , I .
11 DSM I was comp~unded with gelatinous aluminum hydroxide,¦
12 mixed with water and te~ted for ~ag resistance in acrordance with 13 Te8~ Procedure I in the proportions set forth below to give the 14 sag resultq reported in the inal column.
.16 DSM I ~gm) WATER (gm~ ADDITIVE AMOUNT ADDITIYE (Inches) 98.2 25 Gelatinous 1.2 0 17 ~l(OH),3 18 .
19 In accordance with the above procedure, bu~ where in place of 20 gel~tinous aluminum hydroxide there is employed a gela~inous l l 21 hydroxide of iron, cobalt~nickel or chromium, similar results are 1, ¦
22 obtai~ed, 23 .
24 E~IPL~
25 .
26 Experimen~s were carxied out using DSM Ib~ a dry set ~or~r m~x of the compo~itlon of Formula~ion I wherein half ~he 29 ~mount o Me~hocel ~ is u~ed and is supplemented with a hydroxy-! alky~ ~ellulose polyme~ and the added sal~ was Al~(S04)3 14H~O.
l ll Ij ~ 27 ~ , .
- ~ . :,, IL09~713 1 DSM I b WATER AMOUNT SALT POLYMER SAG
2 9~.8 - 25 l.Z hydroxy 0 3 propyl cellulose 98.8 25 1.2hydroxy ethyl 4 cellulose 0 8 Latex-containing sag resistant cementi~ious composi-9 tions are obtained using DSM I. Where the latex is a styrene-butadiens latex either a salt or a gelatinous hydroxide is 11 added. With vinyl chloride~based latexes gelatinous hydroxide 12 i~ substantially preferred.
14 A) Styrene-butadiene copolymer latex (aqueous dispersion) 16 DSM I WATER LATEX A12(SO4) ALUM. HYDROXIDE
_ 3 17 100 25 ~- -- F/~
18 98.8 28 1`.2 -- 0 19 ~8.8 27 -- 1.2 0 21 B) Polyvinyl chloride latex ~aqueous dispersion) 22 I .
23 DSM I ATER LATEX ALUM. HYDROXIDE SAG
100 25 26 1.2 0 26 .
2~
29j! Sag resistance is imparted to non-cementitious adhesives 30 ¦i by the addition of ~ gel~tinous met~ hydroxide or lime ~nd a sal~
l l l - 2~ - l l l . . - . . ..
~ ~ 6o~7~3 1 eonvertlble to a ge~atinous or metal hydroxide.
3 Polyvinyl acetate resin based adhesive 4 1.
51 ; A12(S04) GELATINOUS SAG
61 ADHESIVE 14 H20 3 Al(OH)3 (Inches~
7 100 ~ F/O
8 98.75 1.25 -- 1/16 9 98.28 1.25 0.47 1/16 11 EXAMPL~ 14 12 . I j 13A Portland cement-based patching plaster according to 14 thi~ invention i8 prepared using the following ingredients in dry 15 admixture:
.16 .
17 In~xedients Amoun~, % By Weight . I
18 white Portland cement 23.2 19 slaked lime 5.8 20 sanda 69,8 21 aluminum -~u~fate 1.2 22 1.
23a comprising about 95% ~y weight o~ particles havin~ .
a partlcle size of 140 mesh or less, U.S. Standard 24~ieve, and about 5% by weight of particles having 25- a mash ~ize of greater ~han 140 mesh. I
27 ¦Water in the amount of 21,9% by weight, based on the 28 ¦weight of the dry blend, is added to obtain a workable viscosity, 29 ,and the ~esulting aqueou~ compo~itio~ is t~owelled onto a 30~l~ertlcally di~possd glaR~ pla~e be~ween guide strips 1/4 inch I _ ~9 las~7~
1 thick, A Type B t~le, in accorda~ce with American National 2 St~ndart Speclfication A 118.1 (1967), iQ tapped llghtly onto 3 the ~urfa~ o~ the t~o~elled patching plaster immediately after 4 application, The top edge of the tile is accurately marked, and 5 any downwa~d displacement-of the tile two hours after placement 6 ls me~u~d as the sag. No sag i~ ob~erved afte~ ~wo hours.
8 ~y way of comp~ison, fl cont~ol form~lation con~aining 9 ~he same ing~edients in the sa~e ~mounts, but without aluminum sul~ate, 13 te~ed and the tile is obse~ed to sag and fall off 11 the gla~s p:Late within two hours. ,`
14 , ' A plaster of paris-based patching and spackling com-.16 position in accordance with this invention is prepared using the 17 following ingredients in dry admixture:
19 Ingredients Amount, % By Weight 20 plaster of paris 79.0 21 casein glue~ 9.9 22 limestoneb 9 9 23 aluminum sulate 1.2 ~41 Il . . . .
2s,¦ b compr~sing approximately 95% by weight o calcium I carbonate and about 5% by weight of magnesium car- I
26 I bonate, partlcle slze 200 mesh, U.S. Standard Sieve.
28 I Water in the amount of 34.0% by weight, based on the 29 dry blend, ~B added to obtain a workable ViSc09ity and the 30 l reBulting aqueous composition is e~aluated for sag resistance 1~
j - 30 -I
l l . .. . ~ , , , ~ ~ 9 6~7 8 2 uslng the te~t procedure de~cribed ln Example 14. After two 3 hourfl, a ~g of 3/8 inch i~ observed, By way of comparison, a control formulation is pre- l I
S pared u~i~g the same ing~edients and the same amounts, but wi~h- I I
6 out ~luminum sulfate added. The aqueous c~mposition is trowelled:
8 o~o ~ g~a~ plate wlth~ut a lo~d being imposed upon it, i.e., n~ tlle ~8 applied. The control ~ompo~i~ion is observed to sag 9 4 inche~ w~hi~ a period of ~wo hours even withou~ an imposed lo~d, 11 l i 12 . EXAMP~E 16 1 ¦
13 .
14 A Portland cement~based stucco composi~ion according to this invention is prepared uslng the f~llowing ingredients .16 in dry admixSure: ¦
18 Xn~redien~s Amount, % By Weight l9 Portlan~ cement 23.5 1 ' 20 ~nda 70.5 1 11 21 limeston~b ~ 4.8 22 al~minum ~ulfa~e 1.2 ¦
23 ~
24 a `as in ~xample 1 b ~3 in Example 2 27 I Water in ~he amoun~ o~ 20,Qb by ~eig~, based on the 28 ¦dry blend, ls added to obtain a workable ~iscosity, and the 29 laqueou3 composition 1~ evalua~ed for 3~g resistance using the proc~dur~ de~crib~d in ExAmple 14. No s~g i~ observed.
~ - 31 -I , , ~, ,. , ., I
~ 9 6 ~ 3 1 By way of comparison, a control formulation without ¦ ' 2 aluminu~ sulfate is observed to sag and fall off the plate with- I i 3 in two hours even though no load is imposed.
E ~ ~LE 17 7 An organic polymer-based adhesive composition accord-8 ing to this invention is prepared using the following ingredients:
IO Ingredients Amount, % By Weight 11 Vinyl acetate resin 65.38 12 Water 32.93 1 1 13 Aluminum sulfate 1.23 1 ¦-14 Calcium hydroxide 0.46 16 Using the procedure described in Example 14, the compo-17 sition i9 evaluated for sag resistance, and a sag of 1/4 inch 18 within a 2-hour period is observed.
For purposes of comparison, a control composition con- I
21 taining the same ingredients in the same amounts is prepared, ~ I
22 except that aluminum sulfate and calcium hydroxide are not I ¦
23 included. The control composition is evaluated for sag resist-24 ance using the same test procedure, with the result that the 25 tile falls off within 2 hours, indicating complete failure. I
26 I ;`
27 Other modifications and variations of this invention 28 will suggest themselves to those of ordinary skill in the art 29 in the light of the above disclosure. It is to `be understood, therefore, that changes may be made in the particular embodiments - 3~ -11 :
. , ~
" 3l~6~78 1 described herein which are within the full intended scope of the J ¦ nventlon as deiined in the appended claims.
12~ 1 ] 7 2~1
~1 1 , :: . . . . . , .. . .; . :.
I 1, lC~60~
l a hydro~ypropyl methyl cellulose, both manufactured by Hercules, 2 Inc. Reten ~ i~ a polyacrylamide also manufactured by Hercules, 3 Inc.
7 The following dry-set mortar mix was prepared and 8 tested for necessary properties including sag resistance in 9 accordance ~ith Test Procedure I.
. . Ii 11 381 gm~. of Portland cement 12 5 gms. of methyl hydroxypropyl cellulose*
13 2 gms. of polyvinyl alcohol, 87% hydro~yzed 14 12 gms. of powde~d ~ u~ sul~te ~h ~ waters o 15 ~ 600 8ms of -30 mesh sand hydrati~n 17 To the 1000 gms of mix was added 250 gms of water. The mortar 18 ~howed good bond to ab~orptive and`non-absorptive tile, adequate 19 open time and adjustability, good initial set time and excellent ~ag resis~ance.
22 * ~o~ Chem. Co,, Me~hocel ~ 4000 cps, 90 HG grade.
24 EXAMP~E 8 26 Po~land Cement, Sand together with Clay and Alum 2B A ~ry set mortar mix co~si~ting o equ~l parts o 29 I Por~la~d ce~ent and fi~e sand as well as ~ethocel ~ (4000 cps 30 ¦I go HG, 0,~%) was preparedt Hyd~ted ~lu~inu~ sulfate and finely 25 ~
~. , .
.: , : ~ ' ~ - :' , ~ 960~8 1 divided clay (attapulgite or kaolin) were added and the resultant 2 dry mixture combined with water. The resultan~ mortar was sub- ~
3 mitted to Test Procedure I with the following results: j AMOUNT
5 CEMENT/SAND CLAY AMOUNTAMOUNT OF SA~
AMT. ~ms. METHOCEL ADDITIVE CLAY SALT (gms.) (inche 6 98~8 0.6 Attagel 150 0.6 0.0 F/O
8 98.5 0.6 Attagel 150 0.6 0.3 1/8 98.3 0.6 Attagel lS0 l.l 0.0 l/4 9 98.4 0.6 Georgia 1.0 0.0 5/16 ¦
Kaolin ll 98.1 0.6 Georgia 1.0 0.3 3/32 12 ~ ~aolin 14 EXAMPL~
16 MDM I - Aluminum Salt~
18 MDM I wa~ compounded wilth hydrated aluminum salts and 19 gelatinou~ aluminum hydroxide (prepared in situ) mixed with 20 water and tested for sag resistance in accordance with Tes~ I
21 Procedure II in the proportions set forth below to give the sag re~ults reported in ~he final column.
23 AMOUNT ~DDITIVE S~G
24 ~D~ I (g~ WATER (gm) ADD~TIVE ~gm) (inches 25 98.6 25 A12(SO4)3 1.2 No sag 26 98.28 25 A12(SO4)31.25 No sag 27 Ca (~H2) 0.47 29 In aceordance with the above procedure but where, in place of 301,A12(S04)3 14 H20, there is utilized MnS04H20, Cr2(S04)3, .
l l l l l ~ 26- ! I
`, ...... , ., .. ..... . .. ~, . ..... ..... . .
... . . ... ,.. ;.` .~. . . . ..
2 18 H20, CuS04 5H20, NlS04 6H20, ZnS04 7H~0 Sb2 (S04)3, 3 Fe2(S04~3 9H20. K2S4 A12(S04)3 24H20, Na2~S04)A12 (S04)3 -4 24H20- (NH4)2 S04 A12 (S04) 24H20, NH2Fe (S04)2 12H~O and K2S04Cr2(S04)3 24H20, there are obtain~d similar results.
6 ~ , 9 DSM I - Gelatinous Aluminum Hydroxide.
10 . , I .
11 DSM I was comp~unded with gelatinous aluminum hydroxide,¦
12 mixed with water and te~ted for ~ag resistance in acrordance with 13 Te8~ Procedure I in the proportions set forth below to give the 14 sag resultq reported in the inal column.
.16 DSM I ~gm) WATER (gm~ ADDITIVE AMOUNT ADDITIYE (Inches) 98.2 25 Gelatinous 1.2 0 17 ~l(OH),3 18 .
19 In accordance with the above procedure, bu~ where in place of 20 gel~tinous aluminum hydroxide there is employed a gela~inous l l 21 hydroxide of iron, cobalt~nickel or chromium, similar results are 1, ¦
22 obtai~ed, 23 .
24 E~IPL~
25 .
26 Experimen~s were carxied out using DSM Ib~ a dry set ~or~r m~x of the compo~itlon of Formula~ion I wherein half ~he 29 ~mount o Me~hocel ~ is u~ed and is supplemented with a hydroxy-! alky~ ~ellulose polyme~ and the added sal~ was Al~(S04)3 14H~O.
l ll Ij ~ 27 ~ , .
- ~ . :,, IL09~713 1 DSM I b WATER AMOUNT SALT POLYMER SAG
2 9~.8 - 25 l.Z hydroxy 0 3 propyl cellulose 98.8 25 1.2hydroxy ethyl 4 cellulose 0 8 Latex-containing sag resistant cementi~ious composi-9 tions are obtained using DSM I. Where the latex is a styrene-butadiens latex either a salt or a gelatinous hydroxide is 11 added. With vinyl chloride~based latexes gelatinous hydroxide 12 i~ substantially preferred.
14 A) Styrene-butadiene copolymer latex (aqueous dispersion) 16 DSM I WATER LATEX A12(SO4) ALUM. HYDROXIDE
_ 3 17 100 25 ~- -- F/~
18 98.8 28 1`.2 -- 0 19 ~8.8 27 -- 1.2 0 21 B) Polyvinyl chloride latex ~aqueous dispersion) 22 I .
23 DSM I ATER LATEX ALUM. HYDROXIDE SAG
100 25 26 1.2 0 26 .
2~
29j! Sag resistance is imparted to non-cementitious adhesives 30 ¦i by the addition of ~ gel~tinous met~ hydroxide or lime ~nd a sal~
l l l - 2~ - l l l . . - . . ..
~ ~ 6o~7~3 1 eonvertlble to a ge~atinous or metal hydroxide.
3 Polyvinyl acetate resin based adhesive 4 1.
51 ; A12(S04) GELATINOUS SAG
61 ADHESIVE 14 H20 3 Al(OH)3 (Inches~
7 100 ~ F/O
8 98.75 1.25 -- 1/16 9 98.28 1.25 0.47 1/16 11 EXAMPL~ 14 12 . I j 13A Portland cement-based patching plaster according to 14 thi~ invention i8 prepared using the following ingredients in dry 15 admixture:
.16 .
17 In~xedients Amoun~, % By Weight . I
18 white Portland cement 23.2 19 slaked lime 5.8 20 sanda 69,8 21 aluminum -~u~fate 1.2 22 1.
23a comprising about 95% ~y weight o~ particles havin~ .
a partlcle size of 140 mesh or less, U.S. Standard 24~ieve, and about 5% by weight of particles having 25- a mash ~ize of greater ~han 140 mesh. I
27 ¦Water in the amount of 21,9% by weight, based on the 28 ¦weight of the dry blend, is added to obtain a workable viscosity, 29 ,and the ~esulting aqueou~ compo~itio~ is t~owelled onto a 30~l~ertlcally di~possd glaR~ pla~e be~ween guide strips 1/4 inch I _ ~9 las~7~
1 thick, A Type B t~le, in accorda~ce with American National 2 St~ndart Speclfication A 118.1 (1967), iQ tapped llghtly onto 3 the ~urfa~ o~ the t~o~elled patching plaster immediately after 4 application, The top edge of the tile is accurately marked, and 5 any downwa~d displacement-of the tile two hours after placement 6 ls me~u~d as the sag. No sag i~ ob~erved afte~ ~wo hours.
8 ~y way of comp~ison, fl cont~ol form~lation con~aining 9 ~he same ing~edients in the sa~e ~mounts, but without aluminum sul~ate, 13 te~ed and the tile is obse~ed to sag and fall off 11 the gla~s p:Late within two hours. ,`
14 , ' A plaster of paris-based patching and spackling com-.16 position in accordance with this invention is prepared using the 17 following ingredients in dry admixture:
19 Ingredients Amount, % By Weight 20 plaster of paris 79.0 21 casein glue~ 9.9 22 limestoneb 9 9 23 aluminum sulate 1.2 ~41 Il . . . .
2s,¦ b compr~sing approximately 95% by weight o calcium I carbonate and about 5% by weight of magnesium car- I
26 I bonate, partlcle slze 200 mesh, U.S. Standard Sieve.
28 I Water in the amount of 34.0% by weight, based on the 29 dry blend, ~B added to obtain a workable ViSc09ity and the 30 l reBulting aqueous composition is e~aluated for sag resistance 1~
j - 30 -I
l l . .. . ~ , , , ~ ~ 9 6~7 8 2 uslng the te~t procedure de~cribed ln Example 14. After two 3 hourfl, a ~g of 3/8 inch i~ observed, By way of comparison, a control formulation is pre- l I
S pared u~i~g the same ing~edients and the same amounts, but wi~h- I I
6 out ~luminum sulfate added. The aqueous c~mposition is trowelled:
8 o~o ~ g~a~ plate wlth~ut a lo~d being imposed upon it, i.e., n~ tlle ~8 applied. The control ~ompo~i~ion is observed to sag 9 4 inche~ w~hi~ a period of ~wo hours even withou~ an imposed lo~d, 11 l i 12 . EXAMP~E 16 1 ¦
13 .
14 A Portland cement~based stucco composi~ion according to this invention is prepared uslng the f~llowing ingredients .16 in dry admixSure: ¦
18 Xn~redien~s Amount, % By Weight l9 Portlan~ cement 23.5 1 ' 20 ~nda 70.5 1 11 21 limeston~b ~ 4.8 22 al~minum ~ulfa~e 1.2 ¦
23 ~
24 a `as in ~xample 1 b ~3 in Example 2 27 I Water in ~he amoun~ o~ 20,Qb by ~eig~, based on the 28 ¦dry blend, ls added to obtain a workable ~iscosity, and the 29 laqueou3 composition 1~ evalua~ed for 3~g resistance using the proc~dur~ de~crib~d in ExAmple 14. No s~g i~ observed.
~ - 31 -I , , ~, ,. , ., I
~ 9 6 ~ 3 1 By way of comparison, a control formulation without ¦ ' 2 aluminu~ sulfate is observed to sag and fall off the plate with- I i 3 in two hours even though no load is imposed.
E ~ ~LE 17 7 An organic polymer-based adhesive composition accord-8 ing to this invention is prepared using the following ingredients:
IO Ingredients Amount, % By Weight 11 Vinyl acetate resin 65.38 12 Water 32.93 1 1 13 Aluminum sulfate 1.23 1 ¦-14 Calcium hydroxide 0.46 16 Using the procedure described in Example 14, the compo-17 sition i9 evaluated for sag resistance, and a sag of 1/4 inch 18 within a 2-hour period is observed.
For purposes of comparison, a control composition con- I
21 taining the same ingredients in the same amounts is prepared, ~ I
22 except that aluminum sulfate and calcium hydroxide are not I ¦
23 included. The control composition is evaluated for sag resist-24 ance using the same test procedure, with the result that the 25 tile falls off within 2 hours, indicating complete failure. I
26 I ;`
27 Other modifications and variations of this invention 28 will suggest themselves to those of ordinary skill in the art 29 in the light of the above disclosure. It is to `be understood, therefore, that changes may be made in the particular embodiments - 3~ -11 :
. , ~
" 3l~6~78 1 described herein which are within the full intended scope of the J ¦ nventlon as deiined in the appended claims.
12~ 1 ] 7 2~1
Claims (21)
A-78, A-78A, CLAIMS:
1. A composition capable of admixture with water to form a sag resistant adhesive composition, the composition before said admixture comprising:
(A) an adhesive composition selected from among:
(i) dry-set cementitious mortar compositions comprising an hydraulic cement and at least one water soluble high molecular weight polymer;
(ii) hydraulic non-dry-set compositions comprising an hydraulic cement or plaster of paris; and (iii) non-hydraulic, non-dry-set compositions comprising a room temperature hardening polymer; and (B) at least one, non-fibrous compound selected from the group consisting of gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the compound or compounds being present in an amount at least sufficient to provide the desired sag resistance.
(A) an adhesive composition selected from among:
(i) dry-set cementitious mortar compositions comprising an hydraulic cement and at least one water soluble high molecular weight polymer;
(ii) hydraulic non-dry-set compositions comprising an hydraulic cement or plaster of paris; and (iii) non-hydraulic, non-dry-set compositions comprising a room temperature hardening polymer; and (B) at least one, non-fibrous compound selected from the group consisting of gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the compound or compounds being present in an amount at least sufficient to provide the desired sag resistance.
2. A composition according to Claim 1 in which (A)(i) includes at least one substantially water insoluble polymer.
3. A composition according to Claim 2 in which the substantially water insoluble polymer is in the form of a latex.
4. A composition according to Claim 1 in which com-ponent (B) is present in an amount of at least about 0.2% by weight of the composition.
5. A composition according to Claim 4 in which com-ponent (B) is present in an amount of from about 0.2 to about 5.0% by weight of the composition.
6, A composition according to Claim 1 wherein (A)(i) comprises at least 20% by weight of said hydraulic cement or plaster of paris and at least 0.2% by weight of said water soluble high molecular weight polymer.
7. A composition according to Claim 1 wherein (A)(ii) is present in an amount of from about 20 to about 100% by weight.
8. A composition according to Claim 1 wherein (A)(iii) is present in an amount of from about 5 to about 100% by weight.
9. A composition according to Claim 1 wherein the room temperature hardening polymer of (A)(iii) is present in the form of a resinous liquid or an emulsion, suspension, dispersion, partial solution or total solution.
10. A composition according to Claim 1 wherein com-ponent (B) is a gelatinous metal hydroxide.
11. A composition according to Claim 10 wherein the gelatinous metal hydroxide is aluminum hydroxide.
12, A composition according to Claim 1 wherein com-ponent (B) is a metal salt capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material.
13. A composition according to Claim 12 wherein the metal salt comprises at least one anion and at least one cation, the cationic moieties being selected from among (i) aluminum cations, (ii) cations of the transition elements other than copper of Period 4 of the Periodic Table, (iii) the cations of cerium or antimony, and (iv) the mixed cations of the classifica-tion MIMIII where MI is an alkali metal or ammonium cation and MIII is a trivalent cation of Periods 3 and 4 of the Periodic Table, and the anionic moieties are selected from anions of strong mineral acids and of alkanoic acids having up to 20 carbon atoms in the chain.
14. A composition according to Claim 12 wherein the metal salt is powdered aluminum sulfate.
15. A composition according to Claim 1 wherein the water soluble alkaline material is lime.
16. A composition according to Claim 1 which also comprises an inert filler.
17. A composition according to Claim 16 wherein said inert filler is sand.
18. A sag resistant adhesive compsition which com-prises a composition according to Claim 1 and added water.
19. A method of causing a first covering surfacing having a first surface to adhere to a substrate having a second surface which comprises (a) applying a composition of Claim 1 to said second surface, and (b) pressing said first surface coated with said composition of Claim 1 onto said second surface.
20. In a method of installing floor and wall covering surfaces, the improvement which comprises using a sag resistant adhesive composition comprising in admixture:
(A) an adhesive composition selected from among (i) dry-set cementitious mortar compositions comprising an hydraulic cement and at least one water soluble high molecular weight polymer;
(ii) hydraulic non-dry-set compo-sitions comprising an hydraulic cement or plaster of paris; and (iii) non-hydraulic compositions comprising a room temperature hardening polymer; and (B) at least one non-fibrous compound selected from the group consisting of gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the compound or compounds being present in an amount at least sufficient to provide the desired sag resistance.
(A) an adhesive composition selected from among (i) dry-set cementitious mortar compositions comprising an hydraulic cement and at least one water soluble high molecular weight polymer;
(ii) hydraulic non-dry-set compo-sitions comprising an hydraulic cement or plaster of paris; and (iii) non-hydraulic compositions comprising a room temperature hardening polymer; and (B) at least one non-fibrous compound selected from the group consisting of gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the compound or compounds being present in an amount at least sufficient to provide the desired sag resistance.
21. A method of imparting sag resistance to an adhesive composition selected from among (i) dry-set cementitious mortar compositions comprising an hydraulic cement and at least one water soluble high molecular weight polymer;
(ii) hydraulic non-dry-set compo-sitions comprising an hydraulic cement or plaster of paris; and (iii) non-hydraulic non-dry-set compositions comprising a room temperature hardening polymer, the method comprising adding to said adhesive composition at least one non-fibrous compound selected from the group consist-ing of gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the compound or compounds being present in an amount at least sufficient to provide the desired sag resistance.
(ii) hydraulic non-dry-set compo-sitions comprising an hydraulic cement or plaster of paris; and (iii) non-hydraulic non-dry-set compositions comprising a room temperature hardening polymer, the method comprising adding to said adhesive composition at least one non-fibrous compound selected from the group consist-ing of gelatinous metal hydroxides and metal salts capable of forming a gelatinous or hydrated hydroxide in the presence of a water soluble alkaline material, the compound or compounds being present in an amount at least sufficient to provide the desired sag resistance.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/749,946 US4082563A (en) | 1976-12-20 | 1976-12-20 | Sag resistant mortar compositions |
| US749,946 | 1976-12-20 | ||
| US85780477A | 1977-12-05 | 1977-12-05 | |
| US857,803 | 1977-12-05 | ||
| US857,804 | 1977-12-05 | ||
| US05/857,803 US4142911A (en) | 1976-12-20 | 1977-12-05 | Sag resistant adhesive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1096078A true CA1096078A (en) | 1981-02-17 |
Family
ID=27419394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA293,325A Expired CA1096078A (en) | 1976-12-20 | 1977-12-19 | Sag resistant compositions |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS53104641A (en) |
| CA (1) | CA1096078A (en) |
| CH (1) | CH625773A5 (en) |
| DE (1) | DE2756499A1 (en) |
| FR (1) | FR2374391A1 (en) |
| IT (1) | IT1143790B (en) |
| MX (1) | MX147642A (en) |
| NL (1) | NL7714018A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2938338C2 (en) * | 1979-09-21 | 1982-06-03 | Giulini Chemie Gmbh, 6700 Ludwigshafen | Additive to improve the properties of lightweight concrete and a process for the production of this lightweight concrete |
| CH648272A5 (en) * | 1981-10-12 | 1985-03-15 | Sika Ag | ALKALIF-FREE SETTING AND HARDENING ACCELERATOR AND METHOD FOR ACCELERATING THE SETTING AND HARDENING OF A HYDRAULIC BINDING AGENT. |
| KR101674535B1 (en) * | 2010-01-12 | 2016-11-09 | 롯데정밀화학 주식회사 | Admixture composition for tile cement mortar and tile cement mortar composition having the admixture composition |
| BR112015006145A2 (en) * | 2012-09-19 | 2017-07-04 | Hercules Inc | dry mortars with long opening time and increased water factor |
Family Cites Families (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB191306697A (en) * | 1913-03-18 | 1914-01-22 | Richmond Ettling | Improvements in Artificial Stone, Concrete and the like and Materials therefor. |
| US1865021A (en) * | 1929-11-08 | 1932-06-28 | Yosemite Portland Cement Corp | Cement and process of making |
| US2228539A (en) * | 1938-02-21 | 1941-01-14 | Harold M Stark | Artificial stone |
| US2374562A (en) * | 1939-03-09 | 1945-04-24 | Calvin A Owens | Treatment of hydraulic cement compositions |
| DE711145C (en) * | 1940-02-13 | 1941-09-26 | I G Farbenindustrie Akt Ges | Process for waterproofing building materials |
| US2307270A (en) * | 1940-08-04 | 1943-01-05 | Mellon Inst Of Ind Res | Building material |
| GB560985A (en) * | 1942-08-14 | 1944-05-01 | Calven Arthur Owens | Treatment of hydraulic cement compositions |
| US2390138A (en) * | 1943-06-28 | 1945-12-04 | Coe Lab Inc | Method of conditioning gel molds |
| US2465278A (en) * | 1945-10-25 | 1949-03-22 | Kaspar Winkler & Co | Expansive cement |
| GB680234A (en) * | 1950-01-12 | 1952-10-01 | Sidney George Henderson | Improvements in compositions for improving the hardening time of cement, mortar or concrete mixtures |
| FR1028139A (en) * | 1950-10-31 | 1953-05-19 | Inst Francais Du Petrole | Delayed setting cement for high temperature cementation |
| AT176498B (en) * | 1951-02-14 | 1953-10-26 | Perlmooser Zementwerke Ag | Method of retarding the setting of cements |
| AT255306B (en) * | 1964-04-15 | 1967-06-26 | Stanislaw Dipl Ing Bastian | Cement material and process for its manufacture |
| US3313638A (en) * | 1965-05-17 | 1967-04-11 | Johns Manville | Castable refractory |
| US3429725A (en) * | 1965-10-21 | 1969-02-25 | Grace W R & Co | Cement retarder composition |
| US3429724A (en) * | 1965-10-21 | 1969-02-25 | Grace W R & Co | Cement set retarding composition |
| US3425892A (en) * | 1965-10-22 | 1969-02-04 | Grace W R & Co | Cement set retarder |
| GB1203002A (en) * | 1968-04-23 | 1970-08-26 | T A Materials Inc | Unsintered ceramic products |
| NL7005269A (en) * | 1970-04-13 | 1971-10-15 | ||
| AT303597B (en) * | 1970-05-12 | 1972-11-27 | Kaspar Winkler & Co | Process for the production of cement, mortar or concrete with improved properties |
| US3725088A (en) * | 1971-06-29 | 1973-04-03 | E Penno | Composition for waterproofing concrete and aggregate and improving bonding and strength of aggregate |
| DE2330955B2 (en) * | 1972-06-19 | 1977-11-10 | Japan Synthetic Rubber Co, Ltd.; Chichibu Cement Co, Ltd.; Tokio | PLASTER COMPOUND AND THEIR USES |
| DE2341923C3 (en) * | 1973-08-18 | 1980-01-31 | Bayer Ag, 5090 Leverkusen | Inorganic binding agent mortar, method of making and using the same |
| GB1478299A (en) * | 1973-09-13 | 1977-06-29 | Ass Portland Cement | Hydraulic cement composition |
| FR2306953A1 (en) * | 1975-04-08 | 1976-11-05 | Claustre Georges | Adhesion promoter for resin - for coating granules used in resin concrete; comprises an oxide sulphide or sulphate |
-
1977
- 1977-12-16 NL NL7714018A patent/NL7714018A/en not_active Application Discontinuation
- 1977-12-16 MX MX17181977A patent/MX147642A/en unknown
- 1977-12-19 CA CA293,325A patent/CA1096078A/en not_active Expired
- 1977-12-19 DE DE19772756499 patent/DE2756499A1/en not_active Ceased
- 1977-12-19 CH CH1560177A patent/CH625773A5/en not_active IP Right Cessation
- 1977-12-20 IT IT3099377A patent/IT1143790B/en active
- 1977-12-20 JP JP15499577A patent/JPS53104641A/en active Granted
- 1977-12-20 FR FR7738505A patent/FR2374391A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2756499A1 (en) | 1978-06-22 |
| NL7714018A (en) | 1978-06-22 |
| FR2374391A1 (en) | 1978-07-13 |
| IT1143790B (en) | 1986-10-22 |
| CH625773A5 (en) | 1981-10-15 |
| JPS53104641A (en) | 1978-09-12 |
| JPS5623472B2 (en) | 1981-05-30 |
| MX147642A (en) | 1982-12-30 |
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| MKEX | Expiry |