Note: Descriptions are shown in the official language in which they were submitted.
I
1 AN ADHESIVE CONSISTING ESSENTIALLY OF
A RICINOLEATE URETHANE POLYOL AND A
2 CHLORINATED POLYVINYL CHLORIDE
3 BACKGROUND OF Lowe INVENTION
-
4 Ricinoleate urethane polyols are well known in the art
S for use in the formulation of adhesives and coatings as
6 plasticizers, pigment dispersing agents and tackifiers as
7 well as a reactive ingredient.
8 Ricinoleate urethane polyols themselves vary in consistency
9 from high viscosity oils to greases and, while they have some
tack, they lack cohesive strength. Thus, they are not employed
11 alone as pressure sensitive adhesives or contact cement nor
12 do they impart cohesive strength to adhesives when used as
13 tackifiers.
14 Two-package urethane adhesives which cure by the reaction
of the hydroxyl groups of the ricinoleate urethane polyol
16 with an isocyanate are strong adhesives when cured but exhibit
17 very little green strength. "Green strength" as used herein
18 means the ability to hold two surfaces together when first
19 contacted and before the adhesive develops its ultimate
bonding properties when fully cured.
21 The degree of green strength exhibited by an adhesive
22 is vital to many applications. High green strength tends to
23
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1 prevent wrinkling and slippage of films during lamination.
2 In panel assembly and packaging, it permits Easter handling
3 and wrapping. When Jan adhesive is applied to a vertical surface,
4 a sufficiently high green strength prevents a mechanically us-
supported, bonded member from slipping under the influence
off gravity. When employed for flocking, high green strength
7 holds fibers in place while the adhesive cures and in the laying
8 of carpet or synthetic flooring it resists curling due to the
9 shape-memory thereof acquired when stored in a roll.
Two-package urethane coatings which cure by the same reaction
as set forth above with respect to adhesives have good flexibility
12 and toughness but develop film hardness slowly. It is preferable
13 that floor coatings develop hardness sufficient to accept traffic
14 rapidly to minimize down-time whether the coating be used on
15 new construction or existing sites.
16 Additionally, when urethane coatings and adhesives are
17 applied to concrete, it is currently necessary to acid-etch
I the concrete prior to application. While acid-etching of the
19 concrete is a prerequisite for excellent adhesion, a higher
I degree of adhesion to concrete that has not been acid-etched
21 is always desirable by virtue of the fact that when large
I areas are acid-etched frequently portions thereof are either
23 missed or inadequately etched resulting in poor adhesion.
24 In accordance with the present invention, it has been found
25 that a mixture of ricinoleate urethane polyol and chlorinated
26 polyvinyl chloride (CPVC) exhibits a unique combination of
27 properties which are not achievable if either product is
28 employed lone or if either product were omitted from certain
29 formulations containing other ingredients. Chlorinated
30 polyvinyl chloride is known for its excellent adhesion to
1 rigid polyvinyl chloride, high tensile strength and inherent
2 flexibility but not as a product known to convert a ricinoleate
3 urethane polyol from a product with little tack and cohesiveness
4 to one that is tenacious as claimed in the present invention.
A chlorinated polyvinyl chloride/ricinoleate urethane
polyol mixture in accordance with the present invention is
7 useful in the formulation of pressure sensitive and curable
8 adhesives, contact cements, protective coatings, curable
9 urethanes and curable coatings. Such mixtures are also useful
10 as tackifying additives, anti-slip additives, flexibilizing
agents, cross-linking agents, adhesion improvers and the like.
1 The term "adhesive" as used herein is intended to include
13 broadly, adhesives, coatings and all other uses to which the
14 combination of chlorinated polyvinyl chloride and ricinoleate
lo urethane polyol may be employed.
16
17 SUMMARY OF THE INVENTION
_
18 An adhesive composition consisting essentially of a
19 solution in a suitable solvent of a ricinoleate urethane polyol
20 and a chlorinated polyvinyl chloride with the chlorinated
21 polyvinyl chloride appearing in quantities no greater than
22 approximately 90% by weight of the combined polyol and
23 chlorinated polyvinyl chloride.
I
25 PREFERRED EMBODIMENT OF THE INVENTION
26 The aforesaid objects and advantages may be achieved from
27 a mixture of chlorinated polyvinyl chloride and a ricinoleate
28 urethane polyol preferred embodiments of which follow.
29 The chlorinated polyvinyl chloride may be made by post
I chlorinating polyvinyl chloride resin. Merely by way of
: i
,
1 example, the following chlorinated polyvinyl chlorides may be
* *
2 employed in this invention: GENCLOR S, GENCLOR T manufactured
3 by Imperial Chemical Industries lid, London, England and
4 marketed in the USA by ICY United States, Inc., Wilmington,
5 Delaware and GOON 625X560, GOON 623X560 manufactured my
6 B. F. Goodrich Chemical Group, Cleveland, Ohio.
7 The chlorinated polyvinyl chloride content by weight should
8 not be more than approximately 90% of the chlorinated polyvinyl
9 chloride/ricinoleate urethane polyol blend. This percentage
10 excludes changes resulting from adding plasticizers, solvents,
11 fillers and the like.
12 The ricinoleate urethane polyol of this invention is made
13 by reacting an isocyanate having an average functionality of two
14 or greater with a ricinoleate polyol having an average hydroxyl
lo functionality of two or greater at an isocyanate/hydroxyl
16 (NCO/OH) ratio of no greater than 0.9/1Ø The ricinoleate
17 urethane polyol resulting from this reaction substantially has
18 no reactive isocyanate groups but does have residual unrequited
19 hydroxyl groups. The methods of preparation of polyol/isocyanate
20 adduces such as the ricinoleate urethane polyol above are well
21 known in the art and need no further explanation.
22 Both aromatic and aliphatic polyisocyanates can be employed
I to react with the ricinoleate polyol to make the ricinoleate
24 urethane polyol of this invention. The preferred isocyanates
are Tulane diisocyanate (TDI) and diphenylmethane diisocyanate
I (MID). Illustrative of other suitable polyisocyanates are
27 the following: Isophorone diisocyanate (IPDI), 4~4'4"
28 triphenylmethane triisocyanate, polyethylene polyphenyl
29 isocyanate m-phenylene, l-chlorophenylene 2,4 diisocyanates,
30 methylene-bis (4-cyclohexylisocyanate) and their equivalents.
* Tracemari;
1 The chlorinated polyvinyl chloride may be combined with the
2 ricinoleate urethane polyol by several methods. Merely by way
3 of illustration and without limiting the scope of the claims
4 hereof, some of the methods are: (a) the chlorinated polyvinyl
5 is dissolve d in the components employed in the preparation of
6 the ricinoleate urethane polyol prior to or during the reaction
7 process; by the chlorinated polyvinyl chloride is dissolved
8 in the finished ricinoleate urethane polyol; and (c) the
chlorinated polyvinyl chloride is added Jo the ricinoleate
10 urethane polyol as a solution of chlorinated polyvinyl chloride
dissolved in a solvent, or dissolved in a non-reactive resin or
12 a non-reactive plasticizer or combination of the same; (d) a
13 chlorinated polyvinyl chloride is added to the ricinoleate
14 urethane polyol by first dissolving in isocyanates, in blocked
15 isocyanates,in reactive phenolics, in melamine-formaldehyde,
16 in urea-formaldehyde or other resins that will chemically react
17 with the ricinoleate urethane polyol. In some cases when adding
the chlorinated polyvinyl chloride by this method the chlorinated
lo polyvinyl chloride would be in to part of a two-package system
20 which reacts with the other part which is the ricinoleate
21 urethane polyol.
22 The following examples are illustrative of the adhesives
23 and coatings claimed herein:
24 EXAMPLE I
This example discloses the formulation, properties,
26 performance and testing of a two-package curing urethane
27 adhesive in accordance with the invention claimed herein. The
28 adhesive cures by the reaction of the hydroxyl groups on the
29 ricinoleate urethane polyol with the isocyanate terminated
30 prepolymer.
'
1 FORMULA Wt. Wt. Wt.
.
2 Par t A A B C
3 Ricinoleate urethane polyol~'; 35 35 35
4 CPVC solution (20% by weight
solids* -- 325 --
6 Methyl Ethyl Kitten 35 Jo Jo
7 Gaston oil/TDI adduce (88/12 by weight having
8 2.1% by weight available hydroxyl expressed as Levi
by weight solids; with a viscosity of 90,000 cups.
`
ISSUE Genclor-S dissolved in ME.
11 Part B
12
13 Isocyanate Terminated urethane
14 prepolymer'~ * 45.3 45.3 45.3
CPVC solution (20% by weight
solids Jo 325.0
16
17 Castro old prepolymer having 4.1% by weight
8 available isocyanates as a 70% by weight solids
1 solution in methyl ethyl kitten.
19 *-'ISSUE Genclor-S dissolved in ME.
Those formulas of Parts A and B which contain CPVC,
21 when mixed result in the same composition.
22 Performance - The data in Table I illustrates the improvement in
23 green strength between the control and the adhesive of this
24 example.
Table 1
26 Genclor-S (V/o by weight of ricinoleate urethane
polyol) 0 65
27
28 Genclor-S (% by weight of prepolymer) 0 67
29 Genclor-S (% by weight of total solids) 0 49
Finger Tack Oily Tacky, legs
1 Green Strength (finger) Poor Fair
2 Green Strength*** 0.2 6.5
3 Bond Strength (7 days)*'** 6 10
4 assay determined by a Scott Pendulum Type Tensile Tester
the readings being employed for comparative purposes.
6 Mixing and Test Procedure - The data listed in Table was
7 determined in the following manner:
8 (A) Part A and B were mixed and allowed to stand at ambient
9 temperature for thirty minutes before beginning to make test
10 samples-
11 (B) Finger Tack - An 8 mill wet film was cast on glass using
12 a draw down blade. The film was given approximately a live
13 minute open time to allow the solvent to evaporate. An index
14 finger was pressed into the adhesive, withdrawn slowly, and
15 based on its "feel" was rated us oily or tacky. In the latter
16 case, a material rated as tacky not only had tack but also had
17 a high green strength, legs and grab.
18 (C) Green Strength (Finger Test) - An 8 mill wet film was
19 cast on glass using a draw down blade. The film was given
approximately five minutes open time in order to allow the
21 solvent to evaporate The relative green strength was determined
22 subjectively by pressing an index finger into the adhesive and
I removing it slowly. A green strength rating of ] or poor
24 indicates that little force was necessary to remove one's finger
and a rating of 10 or excellent means that a very high force was
26 required to pull away from the glass.
27 (D) Green Strength (Scott Pendulum Type Tensile Tester) -
28 A 5 mill wet film, 1" wide and 3" long, was cast on an aluminum
29 panel using a draw down blade. After five minutes open time to
allow the solvent to evaporate, a piece of natural cotton fabric
1, 1
1 was pressed into the adhesive and rolled using a 2 pound weight.
2 The relative green strength of this lamination was determined
3 by immediately placing it in the Scott Pendulum Type Tensile
4 Tester and pulling the aluminum and fabric in opposite directions
(shear adhesion). The numbers recorded were direct readings from
6 the tester with the lowest numbers being the poorest green
7 strength and the highest numbers being the strongest.
8 (E) Bond Strength - The solution was applied to two pipes
9 of Al wide natural cotton fabric using a paint brush. After a
10 five minute open time to allow the solvent to evaporate, the two
11 coated pieces of fabric were then pressed together like contact
I cement. After curing, the samples were subjected to a 90 Peel
13 Strength Test using the Scott Pendulum Type Tensile Tester by
14 pulling apart at a rate of about 2 inches/minute. The numbers
15 shown are the direct readings from the tester with the lowest
16 number being the weakest bond and the highest number being the
17 strongest peel strength.
18 EXAMPLE II
19 The principal difference between the two-package curing
20 urethane adhesive of this example and that of Example I is
21 that a different isocyanate terminated prepolymer was employed.
22 The test procedures were the same as in Example I.
23 FURL Wt. We. i
_
24 Part A A B
I Ricinoleate urethane polyol* 780 780
26 CPVC solution (23% by weight solids -- 178
27 Dibutyltin dilaurate catalyst
28 Tulane 205 68
29 *Castor oil/TDI adduce: having 2.1% by weight available
hydroxyl expressed as 100% by weight solids with a
viscosity of 90,000 cups.
1 8.
ICY Genclor-S dissolved in methyl ethyl kitten (ME).
2 Par B
3 Isocyanate terminated urethane
prepolymer*~'~* 325 325
mob Chemical Mender I 75: Trimethylol preappointed
prepolymer having 13.0% by molecular weight available
6isocyanate as a 75D~ by weight solids solution in
methyl acetate by weight.
8 Performance - The data in Table II illustrates the improvement in
9 Green strength ennui the adhesive of the control and that of
10 this example-
llTable II
12 Genclor-S, (% by weight ricinoleate
urethane polyol) 0 5.0
13
14 Genclor-S, (% by weight total solids) 0 3,9
Finger Tack Oily Tacky legs
16 Green Strength (finger) Poor Good
17 Green Strength to 0.2 0.6
18 Bond Strength (48 his 5 5
lo As determined by a Scott Pendulum Type Tensile Tester;
the readings being employed for comparative purposes.
EXAMPLE III
_ _
I The principal difference between the adhesive of this
23 ex~nple and that of Example II is that the ricinoleate urethane
polyol in this example was made from the reaction of castor oil/
25 IT whereas in Example II, it was made from castor oll/TDI. The
26 test procedures were the same as in Example I.
27 FURL Wt. Wt.
I Part A A B_
29 Ricinoleate urethane polyol* 1084 1084
30 CPVC solution (23% by weight solids)** -- 124
* Trademark
I3ibutyltin dilaurate catalyst 1. 0 1. 0
2 'castor old ~90/10) adduce: having Lyle by weight
3 theoretically available hydroxyl as a 50% by weight
solids solution in methyl ethyl kitten.
4 ICY Genclor-S dissolved in EKE.
S Part B
6 Isocyanate terminated urethane 325 325
prepolymer~
8 'mob Chemical Mondur_CB 75: Trimethylol preappointed
prepolymer having 13.0% by weight mailable isocyanate
9 as a ~5~/0 by weight solids solution in ethyl acetate
lo by weight.
11 Performance - the data in Table III illustrates the difference
12 in green strength between the adhesive of the control and that
13 of this example.
14 Table III
Genclor-S, (% by weight of ricinoleate 0 5.0
16 Genclor-S, (% by weight of total solids) O 3.9
17 Finger Tack Oily Tacky legs
18 Green Strength finger) Poor Good
lo Green Strength';* 0.0 0.4
Bond Strength (7 days)*';-;'; 12.0 12.5
byway determined by a Scot Pendul~ Type Tensile Tester;
Thea readings being employed for comparative purposes.
EXAMPLE IV
Lucy example discloses the formulation, properties, per-
pheromones and testing of a non-curing pressure sensitive adhesive
26 in accordance with this invention. It develops its Properties
I when the solvent evaporates and without undergoing further
28 chemical reaction whereas in Examples I, II, and III the adhesives
29 cure by reaction.
10.
DO
1 FORMULA White. Wt.
2 A B
3 Ricinoleate Urania polyol (50% by
weight solids)* 180.0 180.0
CPVC solution (23% by weight solids 43.4
6 Castro oil/MDL ~84.5/15.5) adduce having 0~8% by weight
7 theoretically available hydroxyl as a 50% by weight
solids solution in ME.
8 **Genclor-S dissolved in ME.
9 Performance - The data in Table IV illustrates the difference
.
in bond strength between the adhesive of the control and that
11 of this example.
Table_IV
13 Genclor-S, (% by weight of total solids) 0 10
14 Bond Strength 0.1 I
(Paper tears)
16 'Casey determined by a Scott Pendulum Type Tensile Tester;
the readings being employed for comparative purposes.
18 Test Procedure - An 8 mill wet film was cast on clay coated paper
lo using a draw down blade. It was then dried for ten minutes at
20 ambient temperature and for an additional five minutes at 138F.
21 to drive off all of the solvent. After cooling to room
22 temperature a l inch wide piece was pressed on a piece of cold
23 rolled steel. The samples were subjected to a 180 Peel Strength
24 Test using the Scott Pendulum Type Tensile Tester by pulling at
25 a rate of about 12 inches/minute. The numbers shown are direct
26 readings from ye tester with the lower numbers being the weaker
27 bond and the higher numbers being the stronger bond.
I EXAMPLE V
29 The principal difference between the pressure-sensitive
30 adhesive of this example and that of Example IV is that in this
11 .
1 example the ricinoleate urethane polyol was made from an aliphatic
2 isocyanate whereas in Example IV an aromatic isocyanate was
3 employed. me test procedures were the same as Example IV.
4 FORMULA
s Wt._ Wt.
6 Ricinoleate urethane polyol* 170 170
7 CPVC solution (20% by weight
solids)~iJ~ 75
9 Caesar oil/IPDI (86~14) adduce hiving 1.1% by weight
theoretically available hydroxyl as a 50% by weight
I solids solution in methyl ethyl kitten and Tulane
11 at 1:1 by weight.
12 *ISSUE Genclor-S dissolved in ME.
13 Performance - The data in Table V illustrates the difference
14 between the control and the adhesive of this example.
Table
16 Genclor~S, (% by weight of total solids) 0 15
17 Finger Tack Oily Moderate
18 Bond Strength*** 0 1.5
Lucy determined by a Scott Pendulum Type Tensile Tester,
Thea readings being employed for comparative purposes.
EXAMPLE VI
thus example discloses a one-package, thermoplastic coating
23 that dries by solvent evaporation. The principal difference
24 between the coating of this example and that of Example VII is
25 that in Example VII the coating is a two-package system that
26 cures by reaction instead ox remaining thermoplastic.
27 FORMULA Wt.
__
28Ricinoleate urethane polyol'~ 30
2~CPVC solution (23% by weight solids'; 87
12,
... . . . . . . . . . .
l *Castor oil/TDI adduce having owe by weight
available hydroxyl as a 100% by weight solids
2 solution with a viscosity of 90,000 cups.
3 ISSUE Genclor-S dissolved in ME.
4 Performance - The data in Table VI illustrates that composition
of this invention can be employed to make a one-package thermos
6 plastic coating that dries by solvent evaporation.
7 Table VI
Genclor-S, (% by weight solids) 40
g Hardness (Sword Rocker 24 hour drycXx 4
Water spot test A
if 95% ethyl alcohol Spot test~X`x`~b A
12 Test Procedure - 7':J;~XAn 8 mill wet film was cast on glass using
13 a draw down blade. After an overnight dry, the sword hardness
14 was determined. Resistance to attack from splashing chemicals
15 was determined by putting two drops of the liquid test solution
16 on the film and rubbing lightly with a finger. If there was no
17 noticeable softening or change in appearance, the film was
18 rated "A" for acceptable.
19 EXAMPLE VII
I The principal difference between the two-package system of
21 this example and Example II is that in this example the formula-
Sheehan is evaluated as a coating whereas Example II was evaluated
23 as an adhesive.
24 FORMULA Wt. Wt. Wit
_ _ _ _ _ _
Part A A B C
_. _ _ _ _ _
26 Ricinoleate urethane polyol~ 780 780 780
27 CPVC solution (23% by weight
solids)** -- 1453 2260
28
29 Tulane 1170 -- --
Dibutyltin dilaurate catalyst 1.0 1.0 1.0
13.
I Lo
l Castro oil/TDI adduce having 2.1% by weight available
hydroxyl as a 100% by weight solids solution with a
2 viscosity of 90,Q00 cups.
3 **ICY Genclor-S dissolved in ME.
4 Part B
Isocyanate terminated 325 325 325
prepolymer~
7 -I Moray Chemical Mender CB_75: Trimethylol preappointed
prepolymer having owe by weight available isocyanate
8 as a 75% by weight solids solution in ethyl acetate
9 by weight.
10 Performance - The data in Table VII illustrates the improvement
if in film hardness and improvement in concrete adhesion of the
12 coating of this example as compared to that of the control.
13 Table VII
14 Genclor-S 7 (% by weight of
ricinoleate urethane polyol) 0 30 60
16 Genclor-S, (% by weight of total
17 solids) 0 25 34
18 Hardness (Sword Rocker), 4 hours 0 3 6
19 Hardness (Sword Wrecker hours 4 8 18
Wet concrete adhesion Poor Fair Fair
21 icing and Test Procedure - The data listed in Table VII was
22 determined in the following manner:
23 (A) Part A and Part B were mixed and allowed to stand at
I ambient temperature for approximately thirty minutes before
25 beginning to make test samples.
26 (B) Hardness - An 8 mill wet film was cast on glass using
27 a draw down blade. After allowing an air dry for the time
28 indicated in the table, the hardness was determined using a
29 Sword Rocker; the higher the number the greater the hardness.
14-
I
l (C) Wet Concrete adhesion - m e solution was brushed on a
2 block of concrete and allowed to cure at room temperature for
3 3 days. The block was then immersed in water for 24 hours.
4 The adhesion was determined subjectively by picking at it with
5 a knife point.
6 EXAMPLE VIII
7 The principal difference between the coatings of this
8 example and that of Example VI is that the chlorinated polyvinyl
9 chlorides of this example are from another manufacturer.
10 FORMULA Wt. White.
11 A
12 Ricinoleate urethane polyol (50% by
weight solids)* 20 20
13
14 CPVC solution (20% by weight solids'; 116 --
CPVC solution (20% by weight solids 116
Castro oil/TDI adduce having 2.1% by weight available
17hydroxyl as a 100% by weight solids solution with a
viscosity of 90,000 cups. mixed with tetrahydrofuran (THY).
18
19*~';B. F. Goodrich coon 625X560 dissolved in tetrahydrofuran
(THY).
21*~';*B. F. Goodrich coon 623X560 dissolved in tetrahydrofuran
(THY).
I
23 Performance - The data in Table VIII are additional illustrations
24 ox compositions of this invention that can be employed as one-
25 package thermoplastic coatings that dry by solvent evaporation.
tubule VIII
27 CPVC solution (% by weight solids) 70 70
28 Hardness (Sword Rocker), 24 hour dry '; 30 30
29 Water spot test '; A A
95% ethyl alcohol spot Taoist'; A A
31 20% hydrochloric acid spot Taoist';* A A
15,
****The test procedure was the same as Example VI.
It will be understood by those skilled in the art
that many modifications and variations of the present invention
may be made without departing from the spirit and the scope
thereof.
aye
