Note: Descriptions are shown in the official language in which they were submitted.
26 .
27 B~CKGROU~D `OF ~TH$ ~NVE~T.~ON
28
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.
21
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
27
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.
18
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. .
28
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 ¦
19
' (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,
27
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.
13
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.
23
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.
26
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 ¦
22
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
-- 11 --
~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.
29
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. ¦ !
13
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.
16
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.
27
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: . .
607E3
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.
11 FORMULATION I
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).
19
The dry set Portland cemen~ mortar dry mix designated
21 herein below as DSM II has the following formulation:
22
23 2,000 grams Type I Portland cement
24 20 ~rams Methocel ~ (65 HG) ~ I
. I `
26 FORMULATION II
27 ll
28 The Portland cement mortar dry mix designated MDMI,
29 for use between two water impervious surfaces, has the following
formulation:
- 16 -
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)
4 TEST PROCEDURE I
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
22
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.
27 /
28 /
29
- 17 -
.
~09~iO7
1 , ~, I
2 EXAMPLE 1
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
9 DSM I DSM II WATER ADDITIVE ADDITIVE SAG
10400 ~m~, 100 gms. -- -- F/O
11400 gms. 100 gms. asbestos 2 g N/S
12
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
22
400 100Aluminum
23 Sulfate 500 g N/S
24
26 EXAMPLE 2
27 DSM I & II - Aluminum Salts.
.......
28
29
DSM I & II were compounded with hydrated and anhydrous
- 18 -
.. 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
12
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,
- 19 -
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
9 EXAMPLE 3
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.
18
AMOUNT ADDITIVE SAG
19 DSM I (gm~ W TER (gm) ADDITI~E (gm) _ (inches)
99.5 25 AlCl 0.5 F/0
21 6 H320
22 99,0 25 A1~13 1.0 7/16
23 6 H20
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
14 5 H2O
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
24 25 9 H2O 3/32
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
- 21 -
~ 36~7~
2 XAMPLE 5
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.)
211 AMOUNT ADDITIYE SAG
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.
14 AMOUNT ADDITIVE SAG
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
24 H20
- 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 )
8 24 H20 5/32
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
17 EXAMPLE 6
18
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.
EXAMPLE 7
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
16
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.
23
24 EXAMP~E 8
26 Po~land Cement, Sand together with Clay and Alum
27
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.
22
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
28
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
`,
...... , ., .. ..... . .. ~, . ..... ..... . .
... . . ... ,.. ;.` .~. . . . ..
9607B
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 ~ ,
7 EXAMPLE 10
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
6 EXAMPLE 12
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.
13
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
24 100 25 26 -- F/O
100 25 26 1.2 0
26 .
27 EXAMPLE 13
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
26
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. ,`
12
13 EXAMPLE 15
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:
18
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.
27
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: ¦
17
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
26
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.
19
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
26
28
29
