Note: Descriptions are shown in the official language in which they were submitted.
~ ~27~23 l l
Preparalion o~ such laminates generally involves the use of one or
more shee-ts Or corestock in combination with a decorative or print sheet
and, if desir ed, a top sheet or overlay. The corestock, if corestock is
employed, usually comprises an unbleached krart paper which has been
impregnated with a rela-~ive1y inexpensive thermosetting resin such as a
phenolic resin, a polyester resin, and the lil<e, which is eàsily cross-
linked upon the application of heat and pressure during consolidation.
The decorative or print sheet and the overlay (if used) are both
impregnated with a "noble" thermosetting resin (i.e. a resin which is
also cross-lin~kable upon the application of the heat and pressure durins~
consolidation, but which exhibits lit~le or no color deterioration upon
the application of such heat and pressure and which prevents any strike-
through or "bleeding" of the thermosetting resin wsed in the corestock).
Two of the most common "noble" thermosetting resins used to impregnate
the decorative or print sheet employed in the preparation of such laminates
are urea-formaldehyde resin condensates and melamine-formaldehyde resin
condensates, although other resins such as polyester res7ns have also
besn employed as "noble" thermosetting resins for the impregnation oF
such sheets.
After consolidation, in those applications where the resulting
laminate is intended to be used in a structural application, rather than
merely for its decorative effect, the laminate is usually bonded to a
substrate material such as plywood, hardboard, particle board, cement-
asbestos board, and the like, to give it adclitional strength and rigidity
for its intended structural use.
As indicated above, the various laminae employed to îorm the
ultimate laminate are consolidated through the simultaneous application
of heat and pressure between heated pressure platens. Such presses
generally consist of two heavy, heated platens on the top and bottom of
the press, with additional heated platens in between to provide the
~ -2-
~Z7~;23 1 !
numl~er of oper1in~s clesired in the press. Each openil19 typically inclucles
the following ~lem~nts in the following order: a) a heated platen, b)
one or more sheets of caul-stock, which are primarily intended to distribute
pressure uniformly over the surface of the caul plate, c) a metal caul
plate, d) -the opening itself, e) another metal caul plate, f~ one or
more sheets of caul stock, and g) another heated platen. The various
laminae which will form a laminate are placed together in the oper-ing,
sometimes alone and sometimes as a "book" or "pack" of laminates.
In order to prevent the decorative sheet or overlay sheet from
adhering to the caul plate, and in some cases to also irnpart desired
gtoss or surface texture to the decorative sheet or overlay shee-t, it is
customary to employ a release sheet or liner between the print sheet or
overlay sheet and the caul plate. The laminae material which is placed
against the release sheet is typically an uncured amine for maldehyde
resin, such as melamine formaldehyde resin condensate or urea formaldehyde
resin condensate. Such materials have a strong tendency to react with
and/or adhere to the surface of the release sheet, placing tough requlrements
upon the release sheet, which must resist adhering to the laminate.
This ~ifficult requirement is further complicated by the fact that
differ ent manufacturers use different laminate materials and difFerent
press temperatures and pressures. Furthermore, the variation in heating
and cooling cycles occurring from laminate to laminate and edge to
center in each laminate, even in a single pressing operation can result'
in variable release results.
A particularly satisfactory prior art release coating and release
sheet for use with platen pressing of decorative laminates is disclosed
in U.S. Patent No. 3,946,135, issued to John O. H. Peterson on March 23,
B 1976. This patent, ~ hi~i~hePei~ cor~ at-ed ~-by~ reference, discloses
a release coa'ting fa'rmùlation 'comprising a release agent, a monomeric
30 polyhydric alcohol and a cross~linkable thermosetting resin. The
.
I -3- l
~12~U23
monomeric polyhydric alcohol cross-links with the cross-link-
able thermosetting resin to form a particularly stable surface
having a low level of reactance with and/or adhe~ence to
laminates used in panel pressing. Elowever, the relea.se
sheets coated from the above-described formula are sometimes
not entirely satisfactory from a release standpoint for use
with all varieties of laminate materials and press conditions.
Also, the release coating formulation, which is coated as an
aqueous solution onto a paper substrate, is sometimes difficult
to coat because of its low viscosity. Attempts to increase
the viscosity by adding conventional thickener materials
have generally been unsatisfactory because of their tendency
to rapidly cross-link with the other materials in the formulat-
ion to increase the coating viscosity very quickly beyond
that which is coatable, resulting in an unacceptably short
pot life.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention there
is provided a release sheet comprising a substrate having
on at least one of its outer surfaces a dried and cured
coating composition comprising, in effective amounts
for release, a release agPnt, a cross-linkable thermo-
setting resin, and a water dispersible organic compound
containing polyoxyethylene block having more than 14
repeating units, polyoxypropylene block having more than
4 repeating units; or a block copoiymer of polyoxyethylene
and polyoxypropylene.
In accordanc~ with another aspect of this invention
there is provided a coating composition comprising, by dry
weight per 100 parts of coating, from about 3 to about 30
,~ 4
parts by dry weight of a release agent, from about 20 parts
to abou~ 60 parts by dry weigh-t of a cxoss-linkable thermo-
setting resin, and from about 4 parts to about 30 parts by
dry weight of a water dispersible organic compound containing
S polyoxyethylene, polyoxypropylene, or a block copolymer of
polyoxyethylene and polyoxypropylene.
In accordance with another aspect of this invention
there is provided in a method of consolidating a plurality of
laminae impregnated with thermosetting resin by simultaneously
heating and pressing the laminae, the improvement wherein at
least one o~ the outer laminae is pressed against ~ release
surface of a dried and cured coating composition comprising,
in eff~ctive amounts for release, a release agent, a cross-
linkable thermosetting resin, and a water dispersible organic
compound containing polyoxyethylene, polyoxypropylene, or a
block copolymer of polyoxyethylene and polyoxypropylene.
In accordance with another aspect of this invention
there is provided in a method of forming a film of resinous
material which includes the steps of coating the ilm of
resinous material in a flowable state onto a rel~ase surface,
drying the resinous film material, and stripping it from the
release surface, the improvement wherein the release surface
is provided by a dried and cured coating composition compris-
ing, in effective amounts for release, a release agent, a
cross-linkable thermosetting resin, and a water dispersible
organic compound containing polyoxyethylene, polyoxypropylene,
or a block copolymer of polyoxyethylene and polyoxypropylene.
By way of added explanation, the present invention in
one respect relates to a coating composition for use in the
- 4a -
preparation o a release coating and release sheet which is
particularly useful for panel pressing applications wh~rein
decorative laminates are consolidated under heat and pxessure.
In some embodiments, the invention is an improved ~orm of the
release coating described and claimed in U.S. Patent No.
3,946,135. The coating composition of the present invention
comprises a release agent, a cross-linkable thermosetting
resin, and a water dispersible organic compound containing
polyoxyethylene, polyoxypropylene or block copolymers of
polyoxyethylene and polyoxypropylene. The coating composition
is applied to the substrate in an aqueous form, so the organic
compound must be water dispersible, and is preferably water
soluble. A monomeric polyhydric alcohol is-preferably includ-
ed in the coating composition to cross-link with the thermo-
setting resin. However, it can be left out in cases wherethe organic compound provides the same function.
- 4b -
l~ ~ ~
~L~27~3
The water dispersible organic compound is preferably chosen frorn
either
Class A -polyoxyethylenated polyoxypropylena-ted ethyler1e diarnine,
such as -thc materials sold under the trademark Tetronics; or
Class B.-a compound having the formula:
~1 1 ~CH2 C~l O~Cll2-c~l-o~cF
where R1 iS hydrogen or an organic hydrophobe;
R;" R3, and ~ are independently selected from H or CH3-, and where
R2, R3, and R4 are all H, more than 50% of the molecular weight of the
compound is provided by polyoxyethylene;
X is 0, S, or N;
n = 1 where X is 0 or S, n = 2 where X is N; and
a, b, and c are zero or integers, and the sum of a, b, and c is
greater than 1. : - ?i
One Class B type of organic compound is the type in whiçh R1~ R2~
~/~ R3, and R4 is H, and X is 0 (polyoxyethylene), preferably where a + b +
c is greater than 14 (mol. wt. = 634).
Another Class B type of organic compound is the type in which R1 iS
20 H; R2, R3, R4 is CH3-(polyoxypropylene), and a ~ b + c Is pre~erably
less than 25 (mol. wt. ~ 1468), and more preferably greater that 4 (mol.
wt. = 250).
Another Class B type of organic compound is the type in which R1 '
R2 and R4 is H; X is 0; R3 is CH3-; and a; b and c are all integers
25 (block copolymers of polyoxyethylene-polyoxypropylene-polyoxyethylene),
preferably where 300 > a ~ c > 9 and 72 > b > 17.
Another Class B type of organic compound is the type in which R1 '
R3 is H; R2, R4 is CH3-; X i~ 0 and a, b, c are all integers (block
copolymers of polyoxypt opylene-polyoxyethylene-polyoxypropylene), preFerably
where 55 > a + c > 17 and 250 > b > 74.
1~ s
~ 7n23 ll
i Another Class B type of organic compou~cl is the type in which R1 is
E~ ¦ an organic hydrol~. Examples of such compounds include, but are not
iimited to, long-chain carboxylic acid esters of glycerol, polyoxyethylenated
long-chain carboxylic acid esters of sorbitol or sor bitan, polyoxyethylt3natecl
S fatty acids, polyoxyethylenated polyoxypropylenatecl fatty acids, polyoxye-thyl-
enated alkylphenols, and polyoxye-thylenated alcohols.
Some of the above named materials will be recognized as conventional
surfactants. The addition of surfactants to release coatings does no-t
~ usually improve release, and in many case is detrimental to release.
10 Furthermore, it will be ,~ ecognized that the quantities desirable for
improving release in the present invention are much higher than those
quantities normally used in surfactant applications. When used as
surfactants, their function is to cause emulsification, lowering of
surface tension and the like of aqueous systems, and they are ty,cically
15 used in an amount of about 1%. When they are used in the present invention
to improve releas~ characteristics, they are used in a quantity of about
4% to 30% of the coating compound, and as such comprise a substantial
art of the coating structure. It should be recognized that some of the
above-named materials are commercially obtainable or can be prepared as
20 mixtures of each other and of the same type in varying molecular weights.
Such mixtures are within the scope of the invention.
Thè resulting release sheet is highly useful in panel pressing
release applications wherein decorat~ve laminates are consolidated.
They provide significantly improved release under a wide variety of
25 conditions. The coating compositions of the invention exhibit excellent .
stability and pot life. The release sheets prepared therefrom provide
very easy release in the pressing of laminates, includ;ng laminates of
amine formaldehyde resins, under a wide varie-ty of conditions. These
release sheets may be reusablè,`''and they permit excellent control over
30 the gloss and surface texture of the laminates being pressed. Addi~ionally,
6-
1 ~;27;~3 1 ~
the water dispersible oryanic compound provi~les excell~nt viscosity
control over the coating mixture wi-thout excessive build up o-f viscosi~y
This ;s believed to be due to -the materials having only a few reactive
sites even though they are in polymeric ~orm. The present invention is
5 also useful for release coatings u,con which are cast urethanes and
polyvinyl chloride resins.
. .
DESCRIPT10N OF THE PREFERRED EMBODIMENTS
_
The coating compositions of the invention are aqueous coating
compositions comprising a release agent, a cross-linkable thermosetting
10 resin, and a water dispersible organic compound containing polyoxyethylene
andjor polyoxypropylene. Illustrative of the types of release agents
which have been found useful in the coating compositions of the invention
- are the Werner type chromiutn complexes of a fatty acid, such as those
sold under the trade name "QUILON" by E. 1. duPont de Nemours & Company
Inc. of Wiltnir,gton/ Delaware (e.g., QUILON S-the stearic acid complex/
QUILON M or H-the myristic acid complex) and those sold under the tradename
"KROMPLEX 75" (a myristic acid chrome chloride complex) by Sun Chemical
Co. '
.Illustrative of the types of cross-linkable thermosetting res7ns
20 which are useful in the coating compositions of this invention are urea-
ormaldehyde resin condensates, melamine-formaldehyde resin condensates,
phenolic resins, and the like. Iilustrative of the types of monotneric,
polyhydric alcohols which are used in the preferred embodiments of the
present invention are pentaerythritvl, glycerine (glycerol), 1,6 hexanediol,
25 tris-hydroxymethyl nitromethane, tat taric acid (dihydroxysuccinic acid)
and the like, alone or in combination with each other.
The amounts of the various components used in the coating composi-
tions of this invention are not narrowly critical, as long as they are
sufficient to effectively provide release, and preferably range frorn
~ 7
Z;~ ~
about 3 parts by weight (dry) to about 30 parts by weight (dry) of
release agent per 1100 parts by weight (dry) of coating, from about 5
parts by weight (dry) to about 50 parts by weight (dry~ of monorneric
polyhydric alcohol per 100 parts by weight (clry) o-f coa-l:ing ~if -the
5 r~onomeric polyhydric alcohol is to be included), from about 20 parts by
weight (dry) ta about 60 parts by weight (dry) of cross-linkable thermosetting
resin per 100 parts ~y weight (dry) of coating, and from about 4 parts,
preferably 5 or more, by weight (dry) to about 30 parts by weight (dry)
of the water dispersible organic compound per 100 parts by weight (dry)
10 of coating.
In addition to the essential components set forth above, the
coating compositions of the present invention may also contain other
components such as anti-foam agents, dyes, colorants, and the like.
Release sheets are prepared from the coating compositions of this
15 invention by coating the composition on a suitable base and then heating
the resulting coated base until the release coating thereon has been
dried and cured. The principal requirement for the substrate or base to
be suitable is that it have a relatively smooth surface which resists
substantial penetration of the aqueous coating composition into the
20 base. In the case of a cellulosic fibrous substrate such as paper, this
requirement is typically met by providing the paper with a base coating
which comprises a mineral pigment (e . g . clay) and adhesive (or binder) .
In the case of a metal foil, no base coating will be necessary.
The following examples are intended to further illustrate the
25 invention disclosed and claimed herein, but they are not intended to
limit the scope thereof. The release coating formulation of each
example was coated with a Meyer rod on a ~3 Ibs . per 3, 300 square feet
ream base paper sheet that had been previously coated on both sides with
S Ibs. per ream of a convent^nal clay-binder dispersion and further
30 coated on the side upon which the release coating formulation was to be
. ., .
l~ Z3
applied witl- 8 Ibs. per rearn of another convenlional clay-binder
dispersion. In each example except where otherwise indicatcd,
the release coating was applied within 15 minu-tes after mixing
and was dried in a circulatin~ air oven for 1 minute at 15~-
5 160C. to yield a release coating of approximately 3 Ibs. per3,300 square feet ream.
The general formula for each of the examples was:
Component Parts by Weight (Wet~
. Pentaerythritol at 5.6% (~`o /~ ~7 C'o~Ce~,0~14.3 g.
B lo Resimene 735 (an 80% solution in
isopropyl alcohol of a methylated
melamine-formaldehyde resin condensate
sold by Monsanto Company of St. Louis,
Missouri~ 6.0 g.
`p 15 Quilon H (a 50% solution in
~)3l?1 isopropyl alcohol
/~/7~ of a Werner-type chr,mic .
chloride complex with myristic acid
sold by E. I. DuPont de Nemours and
20 Company, Inc. of Wilmington, Delaware~ 2.4 g.
isopropyl alcohol 0.6 g.
2-ethylhexanol 0.6 g.
Additive water soluble organic
compound material under test ~ x
Each of the coated and dried examples was tested by the following
procedure. A 12 by 12 inch platen press at 280F. and 1200 psi was used
for pressing for 10 minutes. The configuration of the stack of materials
in the press was, from top to bottom:
1. Hol: platen
2. Conventional release sheet, face down
3. 2-phenolic sheets
4. Melamine-formaldehyde pre-pre~3 sheet
5. The release sheet of the example being tested, face up
6. 1/8 inch thick aluminum caul plate
3a 7. 3/4 inch thick pressed board
After pressing, the consolidated ~ larninates were stripped from the
release sheet of the example beincl lested and ra1ed as follows:
r6~e ~ J~
~. ~ ~ ~
~Z7~?Z3
Release Value Observed
Perfect peeling-type release
B Sticking in small spots one or more
¦ corners
5 ¦ C Corner sti~king
D Severe corner sticking exterlded alon~
edges
¦ E Total edge and corner sticking
¦ F Partial release only in a few spots
10 ¦ G . Total bonding, no release whatsoever
¦ The test procedure was purposely designed to be sufficiently stringent
¦ to result in very low ratings for the prior art release sheet (the
¦ control) to enable better evaluation of the improved release sheets.
¦ Althouyh the control release sheet performed poorly under this test, it
~5 ¦ is saticfactory for many commercial applications.
¦Example . Amt.g. Releas
~J~ 7 I No - Additive Material ~Wet Wt.) Value
V l G
¦ 1. CONTROL --NO ADDITIVE -- F
¦ 2. Polyoxyethylene (Polyox WSR-80 ) .8 A ,
I mol. wt. = 200,000
¦ 3. Polyoxyethylene (Po~lyox WSR N-101) .8 A
. ~ol. wt. = 100,000 1
¦ 4. Polyoxyethylene (Polyox WSR N-10 ) 1.6 A
I mol. wt. = 100,000
25 5. Polyoxyethylene (Polyox WSR N-101) 3.2 A
mol. wt. = 100,000
6. Polyoxyethylene (POE 2002) mol..8 F
wt. = 200
7. Polyoxyethylene (POE 200 ~ mol.1.6 D
wt. = 200
8. Polyoxyethylene (Carbowax~6001)O4 F
mol. wt. = 600
9. Polyoxyethylene (Carbowax 6001).8 . F
mol. wt. = 600
35 10. Polyoxyethylene (Carbowax 6001)1.6 A-B
. mol. wt. = 600
11. Po].yoxyethylene (Carbowax 40001) .~ F
mol. wt. = 4000
~ t~J~ ,~J~k 10- ` ~
l ~ ~
~ 7
I
¦ 12. Polyoxyc~hylene (Carbowax ~o001)
.8
l mol. wt. = 4000
¦ 13. Polyoxyethylene (Carbowax L~oQol)
1.6 A
I mol. wt. = 4000
5 ¦ 14. Polyoxyethylene (Polyox POE 20Ml)
.4 A
I mol. wt. - 20l000
¦ 15. Polyoxyethylene (Polyox PO~ 20M1)
.g A
mol. wt. = 20,000
I 16. Tetraethylene ~lycol, mol. wt. ~ 176
.4 F
10¦ 17. Tetraethylene glycol, mol. wt. = 176 .g F
18. Polyoxyethylenated po~yoxypropylene .4 A
D I glycol (Pluronic~E-35 ) mol. wt. of
PPO = 950, + 20 moles EO
l 19. Polyoxyethylenated po~yoxypropylene .8 A
15 1 glycol (Pluronic L-35 ) mol. wt. of
PPO = 950, ~ 20 moles EO
20. Polyoxyethylenated po~yoxypropylene .4 A
glycol (Pluronic L-31 ) mol. wt. of
I PPO = 950, + 3 moles EO
20 ¦ 21. Polyoxyethylenated po~yoxypropylene .8 C
l glycol (P]uronic L-31 ) mol. wt. of
¦ PPO = 950, + 3 moles EO
22. Polyoxyethylenated po~yoxypropylene 1.6 D
l glycol (Pluronic L-31 ) mol. wt. of
25 ~ PPO = 950, ~ 3 moles EO
¦ 23. Polyoxyethylenated pol~oxypropylene .4 D
, glycol ~Pluronic F-108 ) mol. wt~
I of PPO = 3250, ~ 300 moles EO
¦ 24. Polyoxyethylenated pol~oxypropylene .8 A
30 I glycol (Pluronic F-108 ) mol. wt.
¦ of PPO = 3250, + 300 moles EO
25. Polyoxypropylenated p~lyoxyethylene .4
l glycol (Pluronic 10R5 ) mol. wt.
¦ of PPO = 1000, + 23 moles of EO
35 ¦ 26. Polyoxypropylenated p~lyoxyethylene .8 A
glycol (Pluronic 10R5 ) mol. wt.
of PPO = 1000, ~ 23 moles of EO
27. Polyoxypropylenated p~lyoxyethylene .4 D
l glycol (Pluronic 17R2 ) mol. wt.
40 ¦ of PPO = 1700, ~ 10 moles EO
28. Polyoxypropylenated p~]yoxye~hylene .8 A
glycol (Pluronic 17R2 ) mol. wt.
of PPO = 1700 ~ 10 n;ol~s EO
l f~ k ~
~.r~ ~t~3?~c!~o:i3~'~.~:;t~U~.~,~.~.. '7~.7~ r5`.X~ r~.'n`~3~ 3i~.~L~~^.'3~=C~ r~
~127~Z3
29. Polyoxypropylenated p~lyoxyethylene .4 ~ li
glycol (Pluronic lOK8 ~ mol. wt.
of PPO = 1000, -~ 91 moles EO
30. Polyoxypropylenated p~lyoxyethylene .8 A
glycol (Pluronic lOR8 ) mol. wt.
of PPO = 1000, ~ 91 moles EO
31. Polyo~ypropylenated p~ly~xyethylene .4 D
glycol (Pluronic 25R5 ) mol. w~
2500 PPO, 57 moles EO
32. Polyoxypropylenated p~lyoxyethylene .8 A
glycol (Pluronic 25R5 ) mol. wt.
2500 PPO, 57 moles EO
33. N,N'-Po]yoxypropylenated .4 D
ethylenediamine mol. wt., i~
2501-3000 + 1~-17 moles EO
(Tetronic~702 )
34. N,N'-Polyoxypropylenated .8 A
ethylenediamine mol. wt.
2501-3000 ~ 17 moles EO
tTetronic 702 )
35. ~N'-Polyoxypropylenated .4 E
ethylenediamine mol. wt.
3501-4000 + 53-61 moles EO
(Tetronic 904~) - -
~5 3~. N,N'-Polyoxypropylenated .8 A
ethylenediamine mol. wt.
3501-4000 ~ 5~-61 moles EO
~Tetronic 9~4 )
37. N~N'-Polyoxypropylenated .4 C
, ethylenediamine mol. wt.
3501-4000 + 3~8-363 moles EO
(Tetronic 908 )
38. N,N'-Polyoxypropylenated .8 A
ethylenediamine mol. wt.
3501-4000 + 3~8-363 moles EO
~Tetronic 908 )
7 39. Polyox~propylene ~Polyglycol .4 B
P-1200 ~ mol. wt. 1200
.
40. Polyoxypropylene (Polyglycol 2002) .~ F
mol. wt. 200
41. Polyoxypropylene (Polyglycol 2002) 1.6 D
~ol. wt. 200
42. Polyoxyethylenat~d castor oil .4 C
(~mulphor~EL-719 ) ~0 moles EO
~5 43. Polyoxyethylenated so~bitan .4
monolaurate (Tween~20 ) 20
moles EO
r~ eff
~ ~ ;~
~L~;Z7~Z3
:~
44. Polyoxyethylellat:ed so~i.tan .8
monolaurate ('rween 20 ) 20
moles EO
45. Polyoxycthylerlated sorb~an ,4
monopalmitate (Tween ~0 ) 20
moles EO
46. ~olyoxyethylenated sorb~tan .~ A
monopalmitate (Tween 40
20 moles EO
47. Polyoxyethylenated sgrbitan .4 A
mollooleate (Tween 80 ) 20
moles EO
48. Polyoxyethylenated sgrbitan .8 A
monooleate (Tween 80 )
20 moles EO
49. Polyoxyethylenated sgrbitan .4 B
monooleate (Tween 81 )
5 moles EO
50. Polyoxyethylenated sgrbitan .8 A
monooleate (Tween 81 ) 5
moles EO
Sl. Polyoxyethylena5ed sorbitol . .4
laurate (&-1045 ) .
.. 52. Polyoxyethylena~ed sorbitol .8 A-B
laurate (G-1045 )
53. Polyoxyethylenated sor~itol- .4 B
lanolin esters (G-1471 )
54. Polyoxyethylenated sor~itol- .8 A
lanolin esters (G-1471 ~
- 30 55. Polyoxyethylenated so~bitol- .4 B
beeswax ester (G-1726 )
56. Polyoxyethylenated so~bitol ,8 B
beeswax ester (G-1726 ) .
57. Polyoxyethylenated .4 A
polyoxypropy~.enated stearic
acid (G-2162 )
58. Polyoxyethylenated .8 A
polyoxypropy~enated stearic
acid ~G-2162 )
59. Polyoxyethyle~ated stearic .4 B
B acid ~Myrj~45 ) 8 moles EO
60. Polyoxyethyle~ated stearic .8 A
acid (Myrj 45~) 8 moles EO .
~r,~,te ,~7,d,~/C
-13-
. . I ~ ~ ~
~27~3
. 3
. I
ol7? 61. Polyo~yethyl.ella~ed ~teari.c .4
/7~ acid (~iyrj 525) 40 moles EO
62. Polyoxyethylc~ated stearic .8 h
acid (~Iyrj S2J) 40 moles EO
63. Polyoxyethylena~ed nonylphenol .~ C
(Tergit:olXNP~ moles EO
64. Polyoxyethylencl~cd nonylphenol .8 D
(Tergi.tol NP-14 ) ~ moles EO
65. Polyo~yethylena~ed nonylphenol .4 D
(Tergitol NP-27 ) 7 moles EO
66. Polyoxyethylena~ed nonylphenol .8 B
. ~Tergitol NP-27 ) 7 moles EO
67. Polyoxyethylena~ed nonylphenol .4 C
(Tergitol NP-35 ) 15 moles EO
68~ Polyoxyethylena~ed nonylphenol .8 A
(Tergitol NP-35 ) 15 moles EO
69. Polyoxyethylena~ed nonylphenol .4 C
(Tergitol NP-40 ) 20 moles EO
70. Polyoxyethylena~ed nonylphenol .8 A
(Tergitol NP-40 ) 20 moles EO
71. Polyoxye~hylenated lauryl alcohol .4 A . .
. ~Brij~35 ) 2~ moles EO
72. Polyoxye~hylenated lauryl alcohol .8 A
~Brij 35 ) 23 moles EO .
73. Polyoxye~hylenated stearyl alcohol .8 B
, (Brij 76 ) 10 moles EO
74. Polyoxye,thyle~ated tert-octylphenol .4 A
~~~ (Triton~X-100 ) 9-10 moles EO
75. Same as Ex. No. 2, except Quilon ~ .8 G
~-~w 3~ was replaced with 3.0 g. of Volan
(a chrome complex of methacryIic
acid)
76. Same as Ex. No. 2,.except Quilon H .8 G
was replaced with p-toluene sulfonic
acid
77. Same as Ex. No. 12, except7Quilon H .8
was replaced with Quilon S (a 30%
solution in isopropyl alcohol of a
. Werner type chromic chloride complex
with stearic acid)
78. Same as Ex. No. 2~ e~cept Resimglle .8 C
735 was replaced with Cymel~303
, ~ f~ ,),0,~
-14-
Z7~;:3
79. Same as Ex. No. 12, except Resimene.8 C
735 was repl~ce~ with ~.8 g. of
Resimene 975' (urea formaldehyde
resin condensate)
S 80. Same as Ex. No. 12, except Resimene.8 A
735 was replased wi~h 4.8 g. o~
Resimene X980 (urea fvrma]dehyde
resin condensate)
81. Same as Ex. No. 2, except 2-ethyl .8 A
hexanol was replaced with an ,
additional 0.9 g. of isopropyl
alcohol
82. Same as Ex. No. 2, except isopropyl.8 B
alcohol was replaced with an
1~ adclitional 0.9 g. of 2-ethyl
hexanol
83. Same as Ex. No. 2, except isopropyl.8 B
. and 2-ethyl hexanol were left out .
84. Same as Ex. No. 12, except .8 A
pentaerythritol was replaced with
tris-hydroxymethyl nitromethane
85. Same as Ex. No. 12, except .8 A
. pentaerythritol was replaced with -
1.6 gms. of 1,6 hexanediol
86. Same as Ex. No. 12, except .8 A
pentaerythritol was left out
87. ~oating of all Polyox WSR-801 G
88. Same as Ex~ No. 1, except Resimene 0 F
735 was replaced with Resimene 9759
89. Same as Ex. No. 1, except Resimene g 0 . F
735 was replaced with Resimene X980
90. Same as Ex. 85, except carbowax 4000 0 F
was left out
91. Same as Ex. No. 2, except Resimene.8 G
735 was left out
92. Same as Ex. No. 20, except coated .4
2 hours after mixing
93. Same as Ex. No. 21, except coated .8 A
2 hours after mixing
94. Same as Ex. No. 22, except coated1.6 . A
2 hours after mixing
. .... ; . l
_ _
1 - Manufactured by Union Carbicle Corp. of N.Y., NoY~
~ @~
llZ7~Z3
2 - Manufactur~d by Dow Ch~m:ical Co. of Midland, MichiKarl
3 - Manufacturcd by Wyandotte Chemical Corp. of Wy~ndotte,
Michigan
4 - Ma~ufactured by G~F Corp. o N.Y., N.~.
S - Manufactured by Atlas Chemical Industri.es, Lnc. of
Wilming~on, D~laware
6 - Manu~actured by Rohm and ~laas Company of Philadelphia,
Pennsylv~nia
7 - Manu~actured by E. I. duPont de Nemours ~ Co. of
Wilmington, Delaware
8 - M~nufactured by American Cyanimide
9 - Manufactured by Monsanto Company of St. Louis, Missouri
. lll
From the above examples it can be seen that a wide variety oF
compounds containing polyoxyethylene and/or- polyoxypropylene significantly
15 improve the release values of the release coating described in ll.S.
Patent No. 3,946,135. For illustration, compare Example No 1 (which
represents the release coating of U.S. Patent No. ~,9~,145) with
Examples Nos. 2 - 74. As can be seen from the examptes, some materials
need be- used in a larger quantity than others to provide the most
20 improved release, and some of the materials are more effective at lower
concentration ~see Exs. 43, 47, 57 and 71). Also, it can be seen that
higher molecular weights of polyoxyethylene, for exampie 600 or more,
provide a greater improvement to release than lower molecular weights.
~See Examples 2-17. ) .41so, it can be seen that examptes of higher
25 molecular weight polyoxypropylene provide greater improvements to release
than lower molecular weight examples. However, polyoxypropylene at
higher molecular weight becomes water insoluble. Therefore, only a
narrow molecular weight range of polyoxypropylene is preferred in the
invention, from a molecular weight of about 200 to about 1200, for
30 example. (See Examples 39 - 41;)
-Examples 75 - 91 illustrate the results from varying other materiais
in the coating formula. Example 86 indicates the ability to leave out
. . I ~ ~
l ~ Z3
the monomeric polyhyclric alcohol of ~he formulcl discloscd anci claimecJ in
0.S. Patent No. 3,9~16,135, when using the additive material of the
present invention. Coating formulations of the present invention have
varying release characteristics dependin0 upon how loncg after beincJ
mixed they were coa-ted on the paper. Examples 92 - 9" illustrate the
improvement over the coatin~ mixture of examples 20 - 22 when coatinl 2
hours after mixing.
While the invention has been particularly shown and describecl with
reference to preferred embodiments thereof, it is understood that a
10 number of variations and modifica-tions will occur to a person skilled in
the art without departincJ from -the spirit and scope of the invention as
defined in the appended claims.
,~
