Water soluble triazole derivative embossing inhibitor and the use thereof

This invention provides an aromatic or cycloaliphatic triazole-based chemical embossing inhibitor which is completely soluble in water and compatible with water-based printing inks for use in producing textured foamed plastic surfaces. The triazoles comprise a general class of mono- and multi-functional 1-N substituted aminomethyl derivatives which are rendered soluble in water by the presence of at least one polyethyleneoxide (PEO) oligomer chain, or polypropylene (PPO)-polyethyleneoxide copolymer oligomer chain or PPO/PEO/PPO triblock oligomer chain with a sufficiently high PEO/PPO ratio for water solubility. Preferably the triazole derivative has at least six polyethylene oxide monomer moieties per triazole moiety.

FIELD OF THE INVENTION 
The invention relates to blowing agent inhibitors and their use. In 
particular, the invention is directed to water soluble triazole 
derivatives, and more particularly to water soluble triazole derivatives 
having a plurality of polyethylene oxide monomer moieties, preferably at 
least one polyethylene oxide (PEO) chain, which derivatives are effective 
blowing agent inhibitors. 
BACKGROUND OF THE INVENTION 
It is well known to those skilled in the art that foamed plastic surfaces 
may be textured by the process commonly referred to as "chemical 
embossing", wherein the surface of a foamable polymer composition is 
printed with an ink composition containing an agent which inhibits foaming 
in the printed areas when the surface is subsequently subjected to a heat 
treatment. The areas which have not been printed over thus expand normally 
on heating while expansion in the printed areas containing the inhibitor 
is retarded, resulting in a textured surface with depressions in those 
areas printed with the inhibited ink. 
A wide range of compounds have been claimed to act as inhibitors for 
chemical embossing of floor and wall covering surfaces. Carboxylic acid 
anhydrides such as trimellitic anhydride (TMA), disclosed in Nairn et al. 
U.S. Pat. No. 3,293,094, being among the most commonly used industrially. 
However, compounds such as TMA, while suitable for solvent-based printing 
inks, are hydrolytically unstable and thus are not readily usable in the 
aqueous ink formulations rapidly gaining in importance in large scale 
printing operations due to environmental concerns over VOC emission from 
solvent-based inks. 
Triazole compounds such as benzotriazole (BTA) and tolyltriazole (TTA) are 
also widely used in solvent-based inks for chemical embossing. These 
compounds do not hydrolyze to inactive form on contact with water as do 
carboxylic acid anhydrides like TMA. However their use in aqueous ink 
systems is hindered by a lack of substantial water solubility. 
The excellent embossing characteristics, stability and low toxicity of the 
aromatic triazoles have prompted considerable research into ways that 
these compounds could be successfully adapted to aqueous ink systems. The 
prior art, specifically Hamilton U.S. Pat. No. 4,083,907 and Hamilton U.S. 
Pat. No. 4,191,581, has established that sufficient BTA or aminotriazole 
for acceptable embossing can be solubilized into an aqueous ink by 
addition of a water soluble alcohol and buffering agents to raise the pH 
of the ink formulation to between 8-12. 
Certain carboxylic acids, acid anhydrides and acid halides have also been 
claimed to act as foam-expansion inhibitors in aqueous ink formulations 
where the acidic species have been neutralized and the formulation pH 
adjusted to the same 8-12 range (Brixius U.S. Pat. No. 4,369,065 and 
Brixius U.S. Pat. No. 4,421,561). 
Benzotriazole and other inhibitor species have also been solubilized in 
alcohol-containing aqueous inks where the system pH is in the acidic range 
from 3-5 (Sherman et al. U.S. Pat. No. 5,169,435). 
Modified aromatic triazole derivatives have also been cited as 
foam-expansion inhibitors. These compounds are substituted on the 1-N of 
the triazole ring with dialkylaminomethyl groups of varying structure and 
are claimed to be easily incorporated into aqueous inks which contain 
alcohols or other water soluble organic solvents, and do not require the 
use of a pH regulator (Hauser et al. U.S. Pat. No. 4,407,882). Compounds 
of this general structure in which the alkyl groups of the aminomethyl 
substituent are simple hydrocarbons (D'Errico U.S. Pat. No. 4,522,785) and 
perfluoroalkyls (Clark et al. U.S. Pat. No. 4,788,292) have also been 
claimed as corrosion inhibitors. 
Insoluble aromatic and cycloaliphatic azole-based chemical embossing 
inhibitors are disclosed in Sideman et al. U.S. Pat. No. 5,441,563 and 
Remar et al. U.S. patent application Ser. No. 515,110, filed Aug. 14, 
1995. 
In order to enhance the solubility of such derivatives in a wide range of 
functional fluids of varying polarity, a dialkylaminomethyl benzotriazole 
corrosion inhibitor has also been claimed (Poplewell et al. U.K. Patent 
No. 1,466,558) wherein one of the aminomethyl alkyl groups may be a short 
polyethyleneoxide chain of 1-4 repeat units. 
As the triazole-based foam-expansion inhibitors established in the patent 
literature to date are not soluble in water unless alcohols or other 
suitably water-miscible organic co-solvents are also present, there 
continues to exist a need in the art for a water-soluble triazole-based 
inhibitor which does not require such co-solvents, in order to reduce VOC 
emissions during the printing and drying process. 
SUMMARY OF THE INVENTION 
The dialkylaminomethyltriazole derivatives cited previously as 
foam-expansion inhibitors and corrosion inhibitors are readily prepared by 
the known reaction of the starting triazole with a secondary amine and 
formaldehyde in a suitable solvent at varying temperatures. It has also 
been established that if the alkylamine which is to be incorporated as the 
aminomethyl group is primary rather than secondary, and a suitable ratio 
of triazole to amine is used, the product will have two methyltriazoyl 
groups on the original amine nitrogen (Frankenfeld et al. U.S. Pat. No. 
5,076,946). 
In the present invention, by using primary or secondary mono- or diamines 
in which at least one of the substituents is a polyethylene oxide (PEO) 
oligomer of sufficient molecular weight, or a polypropylene oxide 
(PPO)/PEO/PPO triblock oligomer with a sufficiently high PEO/PPO ratio, 
the resulting aminomethyltriazole will be completely soluble in water 
without the need for alcohol or other water-miscible organic co-solvents. 
The PPO/PEO/PPO triblock oligomer has the general formula PPO.sub.x 
PEO.sub.y PPO.sub.z, where x, y and z are positive integers. 
The number of PEO repeat units required to confer water solubility to the 
molecule is related to the number of aminomethyltriazole moieties attached 
to the molecule. The triazole derivatives of the present invention will be 
soluble in water if the ratio of polyethylene oxide monomer moieties to 
triazole moieties is at least six and preferably at least eight. The 
chemical embossing inhibitors embodied in this invention have the 
advantage that they are inherently soluble in water and can be completely 
dissolved in aqueous ink formulations without the necessity of added 
alcohols or other water-soluble co-solvents, or surfactants. However, such 
co-solvents or surfactants can be added without destroying the present 
invention. 
Accordingly, it is the object of the present invention to provide a 
printing ink composition for the production of textured foamed surface, 
which composition comprises a resin, water, and as inhibitor for 
preventing the foaming of a foamable material containing a blowing agent, 
a PEO or PEO/PPO substituted triazole derivative of the formula 
##STR1## 
R.sup.2 =--(C.sub.1 -C.sub.4) alkyl, --(CH.sub.2 CH.sub.2 O).sub.m 
CH.sub.3, --(CH.sub.2 CH.sub.2 O).sub.m CH.sub.2 CH.sub.3, or --R.sup.1 ; 
R.sup.3 =--CH.sub.2 CH.sub.2 --, --CH(R.sup.6)CH.sub.2 --, or --CH.sub.2 
CH(R.sup.6)--; 
R.sup.4 =--(C.sub.1 -C.sub.4) alkyl, or 
##STR2## 
R.sup.5 =--H or --(C.sub.1 -C.sub.4) alkyl; R.sup.6 =--(C.sub.1 -C.sub.4) 
alkyl; 
n=3-45; 
m=1-6; and 
Each of R.sup.1, R.sup.2, R.sup.3, R.sup.5, and R.sup.6 may be the same or 
different. 
R.sup.3 is preferably --CH.sub.2 CH.sub.2 --, --CH(CH.sub.3)CH.sub.2 --, or 
--CH.sub.2 CH(CH.sub.3)--. R.sup.5 is preferably --H or --CH.sub.3. 
When R.sup.4 is --R.sup.3 N(R.sup.1)alkyl, n is preferably 10 to 25. When 
R.sup.4 is --R.sup.3 N(R.sup.1).sub.2, n is preferably 20 to 45, more 
preferably 20 to 35, and most preferably 20 to 30. 
When R.sup.2 is R.sup.1 and R.sup.4 is --(C.sub.1 -C.sub.4)alkyl, n is 
preferably 10 to 30, and more preferably 15 to 25. When R.sup.2 is not 
R.sup.1 and R.sup.4 is --(C.sub.1 -C.sub.4) alkyl, n is preferably 5 to 
25, and more preferably 7 to 25. 
Another object of the invention is to provide a water soluble triazole 
derivative which includes a plurality of polyethylene oxide monomer 
moieties, preferably a ratio of polyethylene oxide monomer moieties to 
triazole moieties of at least six, and more preferably a ratio of 
polyethylene oxide monomer moieties to triazole moieties of at least 
eight. 
A further object of the invention is to provide a PEO or PEO/PPO 
substituted triazole derivative of Formula (1), except n=5-45. 
A still further object of the invention is to provide a method of embossing 
a heat-foamable resinous material by applying the printing ink composition 
of the present invention to selected areas of the surface of a 
heat-foamable resinous material, which material contains a blowing agent, 
and subsequently heating the material to at least the decomposition 
temperature of the blowing agent. 
DETAILED DESCRIPTION OF THE INVENTION 
Structures for some representative examples of the water soluble triazole 
derivatives of the present invention are shown in the following Tables I 
and II in which the substituents of Formula (1) are identified. R.sup.1 is 
identified as aromatic to indicate the first moiety set forth for R.sup.1, 
supra, or cyclohexyl to indicate the second moiety set forth for R.sup.1, 
supra. R.sup.2 is sometimes identified in the same manner. The 
parenthetical numbers following the moieties of R.sup.3 indicate the 
average number of the OR.sup.3 moieties in the compound. The average 
number of polyethylene oxide monomer moieties and polypropylene oxide 
monomer moieties is one greater than n. 
TABLE I 
__________________________________________________________________________ 
Mono- and Vicinal Di-substituted Derivatives 
Cmpd 
R.sup.1 
R.sup.5 
R.sup.4 
R.sup.2 R.sup.3 n 
__________________________________________________________________________ 
1 Aromatic 
--CH.sub.3 
--CH.sub.3 
--CH.sub.2 CH.sub.2 OCH.sub.3 
--CH.sub.2 CH.sub.2 -- 
3-9 
2 Aromatic 
--CH.sub.3 
--CH.sub.3 
Aromatic 
--CH.sub.2 CH.sub.2 -- (19), 
22 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 CH(CH.sub.3 
)-- (4) 
3 Aromatic 
--CH.sub.3 
--CH.sub.3 
Aromatic 
--CH.sub.2 CH.sub.2 -- (13), 
15 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 CH(CH.sub.3 
)-- (3) 
4 Aromatic 
--H --CH.sub.3 
Aromatic 
--CH.sub.2 CH.sub.2 -- (13), 
15 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 CH(CH.sub.3 
)-- (3) 
5 Cyclohexyl 
--CH.sub.3 
--CH.sub.3 
Aromatic 
--CH.sub.2 CH.sub.2 -- (13), 
15 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 CH(CH.sub.3 
)-- (3) 
6 Aromatic 
--CH.sub.3 
--CH.sub.3 
--CH.sub.3 
--CH.sub.2 CH.sub.2 -- (13), 
15 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 CH(CH.sub.2 
)-- (3) 
__________________________________________________________________________ 
TABLE II 
__________________________________________________________________________ 
Symmetrical Di- and Tetra-substituted Derivatives 
Cmpd 
R.sup.1 
R.sup.5 
R.sup.2 
R.sup.4 R.sup.3 n 
__________________________________________________________________________ 
7 Aromatic 
--CH.sub.3 
--CH.sub.3 
--CH.sub.2 CH(CH.sub.3)NR.sup.1 R.sup.2 
--CH.sub.2 CH.sub.2 -- (15.5) 
18 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 
CH(CH.sub.3)-- (3.5) 
8 Aromatic 
--H --CH.sub.3 
--CH.sub.2 CH(CH.sub.3)NR.sup.1 R.sup.2 
--CH.sub.2 CH.sub.2 -- (15.5) 
18 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 
CH(CH.sub.3)-- (3.5) 
9 Cyclohexyl 
--CH.sub.3 
--CH.sub.3 
--CH.sub.2 CH(CH.sub.3)NR.sup.1 R.sup.2 
--CH.sub.2 CH.sub.2 -- (15.5) 
18 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 
CH(CH.sub.3)-- (3.5) 
10 Aromatic 
--CH.sub.3 
Aromatic 
--CH.sub.2 CH(CH.sub.3)NR.sup.1 R.sup.2 
--CH.sub.2 CH.sub.2 -- (39.5) 
42 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 
CH(CH.sub.3)-- (3.5) 
11 Aromatic 
--H Aromatic 
--CH.sub.2 CH(CH.sub.3)NR.sup.1 R.sup.2 
--CH.sub.2 CH.sub.2 -- (39.5) 
42 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 
CH(CH.sub.3)-- (3.5) 
12 Cyclohexyl 
--CH.sub.3 
Cyclohexyl 
--CH.sub.2 CH(CH.sub.3)NR.sup.1 R.sup.2 
--CH.sub.2 CH.sub.2 -- (39.5) 
42 
--CH(CH.sub.3)CH.sub.2 --/--CH.sub.2 
CH(CH.sub.3)-- (3.5) 
__________________________________________________________________________ 
For acceptable processing, it is advantageous to use 5 to 25 parts by 
weight of the polyalkyleneoxide-derivatized aminomethyltriazoles in the 
aqueous printing ink composition. Those skilled in the art will recognize 
that a very wide range of printing ink compositions exist with varying 
combinations of solubilized and/or dispersible binders, pigments, and 
rheology-control additives. The pigments are optional, since it may be 
desirable to use a colorless, inhibitor containing printing ink. The 
water-soluble triazoles of the present invention are potentially useful in 
many other aqueous ink formulations not specifically outlined in the 
Examples as to their exact composition. 
Those skilled in the art will also recognize that varying amounts of water 
will be required to adjust the viscosity of the ink composition to a range 
suitable for typical rotogravure printing. Other methods of printing the 
ink composition onto the foamable plastic surface, such as screen 
printing, relief printing, or planographic printing, may also be used with 
these ink compositions. 
Although this invention is primarily concerned with polyvinylchloride-based 
plastisol compositions thermally blown with azodicarbonamide as the 
printing substrate, there likewise exists a wide range of thermoplastic 
resins which can be thermally foamed with azodicarbonamide and thus are 
potential substrates for aqueous inhibitor printing ink compositions of 
the type claimed. Such other compositions include polyvinylacetate, 
copolymers of vinyl chloride and vinyl acetate, polyacrylate, 
polymethacrylate, polyethylene. polystyrene, butadiene/styrene copolymers, 
butadiene/acrylonitrile copolymers, and natural or synthetic rubbers. 
The specific combinations of PVC, other thermoplastic resins, filler, 
stabilizers, liquid plasticizer and chemical blowing agent that make up a 
typical foamable plastisol substrate vary widely within certain limits and 
those skilled in the art can reasonably anticipate systems which would be 
encompassed by the scope of this invention. 
The invention is illustrated by the following examples related to synthesis 
of the water-soluble triazole derivatives, preparation of the aqueous 
printing ink formulations and demonstration of the chemical embossing 
behavior of the claimed compounds. Unless otherwise stated, all amounts 
and percentages given in the Examples are on a weight basis.

EXAMPLE 1 
Synthesis of Compound 1 
1-N-(2-Methoxyethylmethoxypolyethyleneoxy)aminomethyl!tolyltriazole 
Sixteen and one-half parts of commercial tolyltriazole (TT100, an isomer 
mixture from PMC Specialties) and 50.4 parts of the PEO-substituted 
secondary amine (laboratory prepared) were combined in 150 parts methanol 
and cooled to zero degrees Centigrade. While holding the reaction mixture 
at this temperature, 10.1 parts of commercial 37% aqueous formaldehyde 
solution was added slowly over several hours with continual agitation. The 
reaction mixture was allowed to warm to ambient temperature and worked up 
after 18 hours by removing the solvent under moderate heat/vacuum. The 
resulting oil was then vacuum stripped at higher temperature to remove any 
residual water, unreacted formaldehyde or other volatiles. The final 
product was 67.1 parts (quantitative yield) of a clear, mobile reddish oil 
which was identified by standard spectroscopic techniques as the expected 
Compound 1, 
1-N-(2-methoxyethylmethoxypolyethyleneoxy)aminomethyl!tolyltriazole. The 
compound was found to be completely miscible with water in all 
proportions. 
EXAMPLE 2 
Synthesis of Compound 2 
N,N-Bis(1-N-Tolytriazoylmethyl)polyethylene-Co-Polypropyleneoxyamine 
Twenty-six and seven-tenths parts of commercial tolyltriazole and 100.0 
parts of the PEO/PPO-substituted primary amine (JEFFAMINE M1000 from 
Texaco Chemical Co.) were combined in 150 parts methanol and cooled to 
zero degrees Centigrade. While holding the reaction mixture at this 
temperature, 16.3 parts of commercial 37% aqueous formaldehyde solution 
was added slowly over several hours with continual agitation. The reaction 
mixture was allowed to warm to ambient temperature and worked up after 18 
hours by removing the solvent under moderate heat/vacuum. The resulting 
oil was then vacuum stripped at higher temperature to remove any residual 
water, unreacted formaldehyde or other volatiles. The final product was 
128.7 parts (quantitative yield) of a clear, mobile reddish oil which was 
identified by standard spectroscopic techniques as the expected Compound 
2, N,N-bis(1-N-tolytriazoylmethyl)polyethylene-co-polypropyleneoxyamine. 
The compound was found to be completely miscible with water in all 
proportions. 
EXAMPLE 3 
Synthesis of Compound 3 
N,N-Bis(1-N-Tolytriazoylmethyl)polyethylene-Co-Polypropyleneoxyamine 
Thirty-seven and three-tenths parts of commercial tolyltriazole and 100.0 
parts of the PEO/PPO-substituted primary amine (JEFFAMINE M715 from Texaco 
Chemical Co.) were combined in 150 parts methanol and cooled to zero 
degrees Centigrade. While holding the reaction mixture at this 
temperature, 22.7 parts of commercial 37% aqueous formaldehyde solution 
was added slowly over several hours with continual agitation. The reaction 
mixture was allowed to warm to ambient temperature and worked up after 18 
hours by removing the solvent under moderate heat/vacuum. The resulting 
oil was then vacuum stripped at higher temperature to remove any residual 
water, unreacted formaldehyde or other volatiles. The final product was 
163.9 parts (quantitative yield) of a clear, mobile reddish oil which was 
identified by standard spectroscopic techniques as the expected Compound 
3. This compound differed from Compound 2 only in the number of repeat 
units in the PEO/PPO chain and was also found to be completely miscible 
with water in all proportions. 
EXAMPLE 4 
Synthesis of Compound 4 
N,N-Bis(1-N-Benzotriazoylmethyl)polyethylene-Co-Polypropyleneoxyamine 
Twenty-three and eight tenths parts of commercial benzotriazole and 71.5 
parts of the PEO/PPO-substituted primary amine (JEFFAMINE M715 from Texaco 
Chemical Co.) were combined in 100 parts of methanol and cooled to zero 
degrees Centigrade. While holding the reaction mixture at this 
temperature, 16.2 parts of commercial 37% aqueous formaldehyde solution 
was added slowly over several hours with continual agitation. The reaction 
mixture was allowed to warm to ambient temperature and worked up after 18 
hours by removing the solvent under moderate heat/vacuum. The resulting 
oil was then vacuum stripped at higher temperature to remove any residual 
water, unreacted formaldehyde or other volatiles. The final product was 
97.0 parts (99.3% yield) of a clear, mobile oil, slightly yellow in color, 
which was identified by standard spectroscopic techniques as the expected 
Compound 4, 
N,N-bis(1-N-benzotriazoylmethyl)polyethylene-co-polypropyleneoxyamine. The 
compound was found to be completely miscible with water in all 
proportions. 
EXAMPLE 5 
Synthesis of Compound 5 
N,N-Bis(1-N-Methylcyclohexyltriazoylmethyl)polyethylene-Co-Polypropylene-Ox 
yamine 
Forty and four-tenths parts of hydrogenated tolyltriazole (Cobratec 911 
from PMC Specialties) and 103.8 parts of the PEO/PPO-substituted primary 
amine (JEFFAMINE M715 from Texaco Chemical Co.) were combined in 150 parts 
of methanol and cooled to zero degrees Centigrade. While holding the 
reaction mixture at this temperature, 23.5 parts of commercial 37% aqueous 
formaldehyde solution was added slowly over several hours with continual 
agitation. The reaction mixture was allowed to warm to ambient temperature 
and worked up after 18 hours by removing the solvent under moderate 
heat/vacuum. The resulting oil was then vacuum stripped at higher 
temperature to remove any residual water, unreacted formaldehyde or other 
volatiles. The final product was 146.8 parts (quantitative yield) of a 
clear, mobile oil, slightly yellow in color, which was identified by 
standard spectroscopic techniques as the expected Compound 5, 
N,N-bis(l-N-methylcyclohexyltriazoylmethyl)polyethylene-co-polypropylene-o 
xyamine. The compound was found to be completely miscible with water in all 
proportions. 
EXAMPLE 6 
Synthesis of Compound 10 
N,N,N',N'-Tetra(1-N-Tolyltriazoylmethyl)polyethylene-Co-PolypropyleneOxydia 
mine 
Twenty-six and seven-tenths parts of commercial tolyltriazole and 100.0 
parts of the PEO/PPO-substituted primary diamine (JEFFAMINE ED-2001 from 
Texaco Chemical Co.) were combined in 150 parts of methanol and cooled to 
zero degrees Centigrade. While holding the reaction mixture at this 
temperature, 16.3 parts of commercial 37% aqueous formaldehyde solution 
was added slowly over several hours with continual agitation. The reaction 
mixture was allowed to warm to ambient temperature and worked up after 18 
hours by removing the solvent under moderate heat/vacuum. The resulting 
oil was then vacuum stripped at higher temperature to remove any residual 
water, unreacted formaldehyde or other volatiles. The final product was 
128.6 parts (99.6% yield) of a clear, mobile oil, slightly yellow in 
color, which was identified by standard spectroscopic techniques as the 
expected Compound 10, 
N,N,N',N'-tetra(1-N-tolyltriazoylmethyl)polyethylene-co-polypropylene-oxyd 
iamine. The compound was found to be completely miscible with water in all 
proportions. 
EXAMPLES 7 TO 10 
Preparation and Testing of Inks (10% Concentration) 
Four inks were made using the compounds from Examples 1, 2, 3 and 6. These 
compounds were added directly to Sicpa's anionic water-based ink extender 
694550 at a concentration of 10% active inhibitor. These compounds readily 
solubilized into the ink extender without any adverse reactions. Two 
controls were evaluated at the same time (i.e., 10% Benzotriazole and 8% 
Trimellitic anhydride) in a solvent-base extender. 
All five inks were printed into 9 mils of an expandable plastisol coated on 
flooring felt and on 7 mils of an expandable plastisol coated onto a 
saturated glass mat. The plastisol formulation coated on the flooring felt 
was 100 parts by weight PVC resin, 50 parts plasticizer, 30 parts 
limestone filler, 7.0 parts titanium dioxide pigment, 3.0 parts mineral 
spirits viscosity modifier, 2.1 parts stabilizers, 2.0 parts 
azodicarbonamide blowing agent and 0.6 parts zinc oxide blowing agent 
activator. The printing was done on a flat-bed gravure proof press using a 
100 line screen step-wedge engraved plate. The steps ranged from a deep 
shadow tone to a shallow highlight tone. 
The printed samples were coated with 10 mils of a clear plastisol 
wearlayer, and fused and expanded in a Werner Mathis oven. The clear 
wearlayer was 100 parts by weight PVC resin, 40 parts plasticizer, 4.0 
parts stabilizers and 4.0 parts mineral spirits. The felt backed structure 
was heated for 1.3.+-.0.1 minutes at an air temperature of 
201.degree..+-.1.degree. C. to a blow ratio of about 2.8 to 1. 
The plastisol formulation coated on the glass mat was 100 parts by weight 
PVC resin, 55 parts plasticizer, 30 parts limestone filler, 5.0 parts 
titanium dioxide pigment, 3.0 parts mineral spirits viscosity modifier, 
2.0 parts azodicarbonamide blowing agent and 0.5 parts zinc oxide blowing 
agent activator. The printing was done on a flat-bed gravure proof press 
using a 100 line screen step-wedge engraved plate. The steps ranged from a 
deep shadow tone to a shallow highlight tone. 
The printed samples were coated with 10 mils of a clear plastisol 
wearlayer, and fused and expanded in a Werner Mathis oven. The clear 
wearlayer was 100 parts by weight PVC resin, 50 parts plasticizer and 2.0 
parts stabilizers. The glass backed structure was heated for 1.9.+-.0.1 
minutes at an air temperature of 185.degree..+-.2.degree. C. to a blow 
ratio of about 2.0 to 1. 
The thickness of the printed areas (i.e., restricted area) was measured in 
mils and compared to the thickness of the unprinted expanded surrounding 
areas. This difference is reported as the depth of chemical embossing and 
is shown in Table III. 
TABLE III 
______________________________________ 
DEPTH OF DEPTH OF 
WEIGHT EMBOSSING EMBOSSING 
PERCENT FOR FELT FOR GLASS 
OF COMPOUND STRUCTURE STRUCTURE 
INHIBITOR 
IN INK in mils in mils 
______________________________________ 
Example 7 
10% 5.7 4.7 
(Compound 1) 
Example 8 
10% 4.4 2.9 
(Compound 2) 
Example 9 
10% 5.5 3.9 
(Compound 3) 
Example 10 
10% 3.0 3.2 
(Compound 10) 
BTA 10% 11.8 3.5 
TMA 8% 8.6 5.9 
______________________________________ 
EXAMPLES 11 TO 13 
Preparation and Testing of Inks (15% Concentration) 
The following three inks were made using compounds from Examples 3, 4 and 
5. They were mixed with Sicpa's anionic water-based ink extender 694556 at 
a concentration of 15% by weight, without any problems. A 10% 
Benzotriazole solvent-based ink control was used for this evaluation. 
These inks were printed on the same felt backed and glass backed 
structures used in Table III and evaluated by the same method for the 
depth of chemical embossing (see Table IV). 
TABLE IV 
______________________________________ 
DEPTH OF DEPTH OF 
WEIGHT EMBOSSING EMBOSSING 
PERCENT FOR FELT FOR GLASS 
OF COMPOUND STRUCTURE STRUCTURE 
INHIBITOR 
IN INK in mils in mils 
______________________________________ 
Example 11 
15% 6.8 4.9 
(Compound 3) 
Example 12 
15% 8.6 4.8 
(Compound 4) 
Example 13 
15% 8.9 4.3 
(Compound 5) 
BTA 10% 11.7 3.9 
______________________________________ 
EXAMPLES 14 TO 16 
Preparation and Testing of Compound 3 Inks 
(10%, 15% & 20% Concentration) 
Example 3 (Compound 3) was evaluated at three concentrations to see if the 
depth of chemical embossing would improve with higher concentrations. This 
compound was added to Siopa's anionic water-based ink extender 694556 at 
three concentrations (i.e., 10%, 15% and 20%). A 10% Benzotriazole 
solvent-based ink control was used on the same felt backed structure 
coated with 9 mils of expandable plastisol The same method used previously 
was used to evaluate the chemical embossing depth (see Table V). 
TABLE V 
______________________________________ 
DEPTH OF EMBOSSING 
WEIGHT PERCENT OF 
FOR FELT STRUCTURE 
INHIBITOR COMPOUND IN INK 
in mils 
______________________________________ 
Example 14 
10% 5.7 
(Compound 3) 
Example 15 
15% 8.1 
(Compound 3) 
Example 16 
20% 10.0 
(Compound 3) 
BTA 10% 13.1 
______________________________________