US010280320B2

(12) United States Patent ( 10 ) Patent No.: US 10 ,280, 320 B2

Romanato et al. (45) Date of Patent: May 7, 2019
(54 ) LAMINATION PRINTING INK COMPRISING (2013. 01); C08G 18 /4238 (2013 .01 ); C08G
AN AQUEOUS DISPERSION COMPRISING 18 /48 ( 2013 .01); C08G 18 /4854 (2013.01 );
POLYURETHANE C08G 18 /6511 ( 2013 .01); C08G 18 /6685
(2013 . 01 ); C08G 18 / 722 ( 2013 .01) ; C08G
(71) Applicant: BASF SE , Ludwigshafen (DE ) 18 / 755 (2013 .01); C08G 18 / 758 ( 2013.01);
C09D 11/037 (2013.01)
( 72 ) Inventors: Paola Romanato , Muttenz (CH ); Karl (58 ) Field of Classification Search
Haeberle , Speyer (DE ); Arjan Thomas CPC .. .. .. .. CO9D 11 / 102 ; CO9D 11/037 ;
Termaten , Assen (NL ); Steven CO8G 18 /4854 ; C08G 18 /6685 ; C08G
Zijlstra , Zwolle (NL ); Wouter 18 /722; C08G 18 / 755 ; C08G 18 /758 ;
Toutenhoofd , Heerenveen (NL ) COSG 18 /0823 ; CO8G 18 /283 ; CONG
( 73 ) Assignee : BASF SE , Ludwigshafen (DE ) 18 /3821; COSG 18 /4018 ; C08G 18 /4238;
CO8G 18 / 48 ; B29C 65/ 48; B29C 65 /72
( * ) Notice: Subject to any disclaimer, the term of this See application file for complete search history.
patent is extended or adjusted under 35
U .S .C . 154 (b ) by 129 days . (56 ) References Cited
U . S . PATENT DOCUMENTS
(21) Appl. No.: 15 /110 ,246
4 , 192 ,937 A 3 / 1980 Noll et al.
(22 ) PCT Filed: Jan . 14, 2015 2005 /0043467
2007 /0203289
A1
A1*
2 /2005
8 /2007
Bruchmann et al.
Bruchmann ... C08G 18 /0828
(86 ) PCT No.: PCT/EP2015/050590 2010 /0010113 A11 /2010 Schwalm et al.
524 /589
$ 371 (c ) ( 1), 2010 /0065209 A1 3 /2010 Burghardt et al.
( 2 ) Date : Jul. 7 , 2016
FOREIGN PATENT DOCUMENTS
(87) PCT Pub. No.: W02015/107078 JP 4 - 178418 A 6 / 1992
PCT Pub. Date: Jul. 23 , 2015 JP
8 -60063
2013 -234214
A 3 / 1996
A 11 /2013
(65 ) Prior Publication Data WO WO 2009 /023520 Al 2 /2009
US 2016 /0326389 A1 Nov. 10 , 2016 OTHER PUBLICATIONS
(30 ) Foreign Application Priority Data International Search Report dated Mar. 30 , 2015 in PCT/EP2015 /
050590 .
Jan . 17 , 2014 ( EP ) ....... ...... 14151664 International Preliminary Report on Patentability and Written Opin
ion of the International Searching Authority dated Jul . 19 , 2016 in
(51) Int. Cl. PCT/ EP2015/050590 filed Jan . 14 , 2015 (submitting English trans
B29C 65 /48 ( 2006 .01) lation ) .
B29C 65 /72 ( 2006 .01)
C08G 18 /08 ( 2006 .01 ) * cited by examiner
C08G 18 / 28 (2006 .01)
C08G 18 / 38 ( 2006 .01 ) Primary Examiner — Patrick D Niland
C08G 18 / 40 ( 2006 .01 ) (74 ) Attorney, Agent, or Firm — Oblon , McClelland,
C08G 18 /42 ( 2006 .01) Maier & Neustadt, L .L . P.
C0SG 18 / 48 ( 2006 .01 )
C08G 18 / 65 (2006 .01) (57) ABSTRACT
C08G 18 / 66 ( 2006 .01 ) The present invention relates to a lamination printing ink
C09D 11 /037 ( 2014 .01) comprising an aqueous polyurethane dispersion binder, pig
C09D 11/ 102 ( 2014 .01) ments, an aqueous carrier and optional additives , wherein
C08G 18 / 72 ( 2006 .01) the polyurethane is made of polyisocyanates , specific poly
CO8G 18 / 75 ( 2006 .01) esterdiols, polytetrahydrofuran diol, monohydroxy -poly
(52) U .S . CI. ( alkylene oxide ), diamino acid compound, polyamine com
CPC ........... . C09D 11 / 102 (2013 . 01) ; B29C 65/48 pound and optionally one or more low molecular weight
(2013 .01 ); B29C 65/ 72 (2013 .01) ; C08G polyols .
18 /0823 (2013 .01); C08G 18 / 283 (2013 .01);
C08G 18 /3821 ( 2013 .01) ; C08G 18 /4018 20 Claims, No Drawings
 US 10 ,280 ,320 B2
LAMINATION PRINTING INK COMPRISING The invention provides a lamination printing ink com
AN AQUEOUS DISPERSION COMPRISING prising at least one binder, at least one pigment , an aqueous
POLYURETHANE carrier and optional additives, wherein at least one binder is
an aqueous dispersion comprising a polyurethane , wherein
The present invention relates to a lamination printing ink 5 the polyurethane is made of components comprising
comprising an aqueous polyurethane dispersion binder , pig a ) at least one polyisocyanate with at least two isocyanate
ments, an aqueous carrier and optional additives , wherein groups,
the polyurethane is made of polyisocyanates, specific poly b ) a combination of diols wherein
esterdiols , polytetrahydrofuran diol, monohydroxy - poly bi) at least one of the diols is a polyesterdiol having a
(alkylene oxide ), diamino acid compound , polyamine com - 10 number average molecular weight of from 500 to
pound and optionally one or more low molecular weight 5000 g/mol, preferably from about 1000 to 3000
polyols. The invention also relates to laminates printed with g /mol and
said ink and methods of making said laminates. b2) at least one of the diols is polytetrahydrofuran
Packagings such as packagings for food often comprise having a number average molecular weight of from
printed film laminates made of two or more polymeric films 15 500 to 5000 g/mol, preferably from about 1000 to
which are laminated together and wherein the printing ink 3000 g/mol,
resides between two laminated films. Typically , when pre c ) at least one monohydroxy -poly(alkylene oxide) com
paring packaging intended to be used to package food pound having a number average molecular weight of
products , a film is printed on one side, adhesive is applied on from 500 to 5000 g /mol, preferably from about 1000 to
top of the printing as well as on the clear areas surrounding 20 3000 g /mol,
the printing, and then the film is laminated to a second film d ) at least one diamino acid compound ,
at a laminating nip . In in - line printing , the adhesive is coated e ) at least one polyamine compound having at least two
on top of the freshly printed ink or the opposite web and amino groups and no acid group, and
immediately thereafter is laminated . In many cases, lami If)) OF
optionally one or more polyol compounds having a
nation is accomplished " out of line,” meaning that a printed 25 number average molecular weight of less than 500
roll is taken to another location for lamination . The adhesive g/mol, preferably from 60 to 490 g /mol.
must bond to the ink as well as to the film without causing Preferably, the polyurethane is made of components com
the ink to bleed , run , delaminate , or generate poor bond prising
strength . a ) 5 to 30 % by weight of the at least one polyisocyanate
Printing inks which are suitable for making printed lami- 30 with at least two isocyanate groups,
nates via roll printing process (hereinafter referred to as b ) 10 to 80 % by weight of the combination of diols
" lamination inks" ) face a variety of desired requirements: wherein polyesterdiols (b1) and polytetrahydrofuran
high compatibility with pigments in the liquid ink diol (b2 ) are preferably in a weight ratio of from 1:2 to
blocking behavior of the printed film as low as possible 2 :1,
high lamination bond strength of the film laminates , also 35 c ) 1 to 20 % by weight of the at least one monohydroxy
in case ofmultiple printing poly ( alkylene oxide ) compound having a number aver
high re -solubility of ink which has temporarily dried on age molecular weight of from 500 to 5000 g/mol
the printing rolls d ) 1 to 10 % by weight of the at least one diamino acid
no volatile bases compound ,
Especially , a coagulation or flocculation of ink ingredients 40 e) 0 ,1 to 10 % by weight at least one polyamine compound
should be avoided . In cases , where lamination is accom having at least two amino groups and no acid group ,
plished " out of line” it is important that a printed film is and
blocking resistant before lamination , i.e . that the printed f) 0 to 10 % by weight of the optional one or more polyol
surface of the film is not sticky and does not adhere to other compounds having a number average molecular weight
printed or non - printed film surface areas . 45 of less than 500 g /mol, preferably from 60 to 490
High lamination bond strength is especially critical and g/mol.
difficult to achieve in multiple print laminate wherein a The polyisocyanates (a ) are preferably used in amounts of
second print or further prints are applied on a first print, e. g . 5 to 30 % by weight, more preferred from 10 to 25 % by
a white print is applied on top of a previous colored , weight. The polyisocyanates (a ) are , in particular, diisocya
non -white print. 50 nates X (NCO ) , where X is an aliphatic hydrocarbon radical
Intended or unintended interruptions can occur during the of 4 to 12 carbons, a cycloaliphatic hydrocarbon radical of
roll printing process . The ink on the printing roll cylinders 6 to 15 carbons or an aromatic hydrocarbon radical of 6 to
can becometouch dry during these interruptions. Therefore , 15 carbons or an araliphatic hydrocarbon radical of 7 to 15
it is important that the dried ink on the printing equipment carbons. Examples of such diisocyanates are tetramethylene
re - dissolves quickly in the liquid printing ink stock when the 55 diisocyanate , hexamethylene diisocyanate (HDI), dodecam
printing process is resumed . ethylene diisocyanate , 1 ,4 -diisocyanatocyclohexane , 1 -iso
For hygiene reasons it is desired to provide printing inks cyanato - 3 , 5 ,5 -trimethyl-5 - isocyanatomethylcyclohexane
with no ammonia and no volatile organic tertiary amines. (IPDI), 2 ,2 - bis (4 - isocyanatocyclohexyl)propane , trimethyl
WO 2009/023520 discloses lamination inks comprising hexane diisocyanate , 1 ,4 - diisocyanatobenzene, 2 ,4 - diiso
aqueous polyurethane binders with good lamination bond 60 cyanatotoluene, 2 ,6 - diisocyanatotoluene, 4 , 4 ' - diisocyanato
strength on various substrates. diphenylmethane , 2 ,4 '-diisocyanatodiphenylmethane,
It is an object of the invention to further optimize lami- p - xylylene diisocyanate , tetramethylxylylene diisocyanate
nation printing inks in respect to one or more of the (TMXDI), the isomers of bis (4 -isocyanatocyclohexyl)meth
above -mentioned requirements , especially concerning ane (HMDI, such as the trans /trans, the cis/ cis and the
improved blocking resistance and improved re -solubility 65 cis/ trans isomer ), and mixtures of these compounds. Par
behaviour without undue impairing one or more of the other ticularly important mixtures of these isocyanates are the
desired requirements. mixtures of the respective structural isomers of diisocyana
 US 10 ,280 ,320 B2
totoluene and diisocyanatodiphenylmethane, especially the of the formula HO — (CH2)2 - COOH ,where z is from 1 to 20
mixture comprising 80 mol % 2 ,4 - diisocyanatotoluene and and one hydrogen of a methylene unit can also be substituted
20 mol % 2,6 -diisocyanatotoluene. In addition , the mixtures by a C1-C4- alkyl. Examples are [ epsilon ]-caprolactone,
of aromatic isocyanates, such as 2 ,4 - diisocyanatotoluene [beta ]-propiolactone , [ gamma]-butyrolactone and /or
and/ or 2 ,6 -diisocyanatotoluene, with aliphatic or cycloali- 5 methyl- Tepsilon -caprolactone, and mixtures thereof.
phatic isocyanates, such as hexamethylene diisocyanate or Examples of suitable starter components are the low
IPDI, are particularly advantageous, the preferred propor molecular mass dihydric alcohols cited above as structural
tion of aliphatic to aromatic isocyanates being from 4 : 1 to components for the polyesterpolyols . The corresponding
1 :4 . In addition to the above mentioned isocyanates, other polymers of [ epsilon ] -caprolactone are particularly pre
isocyanates which can be employed as compounds to syn - 10 ferred . Lower polyesterdiols or polyetherdiols can also be
thesize the polyurethanes are those which carry not only the employed as starters for preparing the lactone polymers .
free isocyanate groups but also further, blocked isocyanate Instead of the polymers of lactones it is also possible to
groups, examples being uretdione groups . Especially pre - employ the corresponding, chemically equivalent polycon
ferred are polyisocyanates (a ) selected from the group densates of the hydroxycarboxylic acids which correspond
consisting of 1- isocyanato -3 ,5 ,5 -trimethyl- 5 - isocyanatom - 15 to the lactones.
ethylcyclohexane (IPDI), tetramethylxylylene diisocyanate Polytetrahydrofuran diol (62 ) is obtainable in particular
( TMXDI), hexamethylene diisocyanate (HDI), bis (4 -isocya - by addition polymerization of tetrahydrofuran with itself , in
natocyclohexyl)-methane (HMDI) or mixtures thereof. the presence , for example , of BF3, or by addition reaction
The combination of diols (b ) is preferably used in onto starter components containing reactive hydrogens, such
amounts of 10 to 80 % by weight, more preferred from 20 to 20 as alcohols or amines, examples being water , ethylene
70 % by weight. The weight ratio of polyesterdiols (bl) and glycol, 1,2 -propanediol, 1, 3 -propanediol, 1 ,2 -bis (4 -hy
polytetrahydrofuran diol (62) is preferably from1: 3 to 3 : 1 droxydiphenyl)propane or aniline. Particular preference is
more preferably from 1: 2 to 2: 1. The polyesterdiols (b1) are , given to polytetrahydrofuran having a number average
in particular, polyesterpolyols which are known , for molecular weight of from 500 to 5000 and , in particular,
example , from Ullmann 's Encyklopädie der technischen 25 from 500 to 4500 or from 1000 to 3000 g/mol.
Chemie , 4th Edition , Vol. 19 , pp . 62 to 65. It is preferred to The at least one monohydroxy -poly (alkylene oxide ) com
employ polyesterpolyols that are obtained by reacting dihy- pound (c ) is preferably used in amounts of 1 to 20 % by
dric alcohols with dibasic carboxylic acids. Instead of the weight, more preferably in amounts of from 2 to 10 % by
free polycarboxylic acids it is also possible to use the weight. Suitable compounds ( c ) are alkanol started poly
corresponding polycarboxylic anhydrides or corresponding 30 alkylene glycols. These compounds have an alkyl group at
polycarboxylic esters of lower alcohols , or mixtures thereof, one terminal end and a hydroxy group at the other terminal
to prepare the polyesterpolyols. The polycarboxylic acids end of the polymer . The alkanol has preferably 2 to 8 or 2
can be aliphatic , cycloaliphatic , araliphatic , aromatic or to 5 carbon atoms such as ethanol, propanol or butanol,
heterocyclic and can be unsubstituted or substituted (by preferably n -butanol. The alkylene group is for example
halogen atoms, for example ), and/ or saturated or unsatu - 35 ethylene, propylene or a mixture thereof, preferably ethyl
rated . Examples are suberic, azelaic , phthalic and ene. The general formula can be HO - CA -On - R with A
isophthalic acid , phthalic, tetrahydrophthalic, hexahy being an alkylene group as mentioned above, R being an
drophthalic , tetrachlorophthalic, endomethylenetetrahy - alkyl group as mentioned above and n being a number from
drophthalic , glutaric and maleic anhydride , maleic acid , 20 to 65. The OH - number of the monohydroxy -poly (alky
fumaric acid and dimeric fatty acids. Preference is given to 40 lene oxide) compound (c ) is preferably from 20 to 56 mg
dicarboxylic acids of the formula HOOC - (CH2)y -COOH , KOH /g .
where y is a number from 1 to 20 , preferably an even number The at least one diamino acid compound (d ) is preferably
from 2 to 20 , examples being succinic , adipic , sebacic and used in amounts of 1 to 10 % by weight , more preferably in
dodecanedicarboxylic acids . amounts of from 1 to 5 % by weight. Suitable diamino acid
Examples of suitable polyhydric alcohols formaking the 45 compounds can be selected from the group consisting of
polyesterdiols (bl) are ethylene glycol, 1, 2 -propanediol, diamino carboxylic acid compounds and diamino sulfonic
1, 3 -propanediol, 1, 3 -butanediol, 1 ,4 - butanediol, 1, 4 -butene - acid compounds. Such compounds conform for example to
diol, 1,4 -butynediol, 1,5 - pentanediol, neopentyl glycol, bis the formula H2N - R1-NH - R2- X where R1 and R2 inde
(hydroxymethyl) cyclohexanes such as 1,4 -bis (hydroxym - pendently of one another are a C1-C6 -alkanediyl, preferably
ethyl)cyclohexane , 2 -methyl- 1,3 -propanediol, 50 ethylene, and X is COOH or SO3H . Particularly preferred
methylpentanediols , and also diethylene glycol, triethylene compounds ( d ) are N - ( 2 -aminoethyl)- 2 - aminoethane car
glycol, tetraethylene glycol, polyethylene glycol, dipropyl boxylic acid and N -(2 -aminoethyl )-2 -aminoethane sulfonic
ene glycol, polypropylene glycol, dibutylene glycol and acid and the corresponding alkali metal salts , Na being the
polybutylene glycols. Preference is given to alcohols of the particularly preferred counterion.
formula HO — (CH2)x -OH , where x is a number from 1 to 55 The at least one polyamine compound (e ) having at least
20 , preferably an even number from 2 to 20 . Examples of two amino groups and no acid group is preferably used in
such alcohols are ethylene glycol, 1 ,4 - butanediol, 1,6 - amounts of 0 .1 to 10 % by weight, more preferably in
hexanediol, 1,8 -octanediol and 1, 12 -dodecanediol. Prefer amounts of from 0 .1 to 2 % by weight. The polyamine
ence extends to neopentyl glycol. compounds (e ) can serve generally for crosslinking or chain
Also suitable are polycarbonatediols , as can be obtained , 60 extension and typically have 2 or more primary and /or
for example , by reaction of phosgene with an excess of the secondary amino groups. Polyamines having 2 or more
low molecular mass alcohols cited above as structural com - primary and /or secondary amino groups are employed in
ponents for the polyesterpolyols . Lactone-based polyester- particular when chain extension and/or crosslinking is to
diols are also suitable , these being homopolymers or copo - take place in the presence ofwater, since amines generally
lymers of lactones, preferably hydroxy -terminal adducts of 65 react more quickly with isocyanates than do alcohols or
lactones with suitable difunctional starter molecules. Suit- water. This is in many cases necessary when the desire is for
able lactones are preferably those derived from compounds aqueous dispersions of crosslinked polyurethanes , or poly
 US 10 ,280 ,320 B2
urethanes of high molar weight. In such cases a procedure is with a functionality ofmore than two. Examples of com
followed in which prepolymers with isocyanate groups are mercial compounds are the isocyanurate or the biuret of
prepared , are rapidly dispersed in water and then are sub hexamethylene diisocyanate .
jected to chain extension or crosslinking by adding com - Polyurethane binders having a particularly good profile of
pounds having two or more isocyanate - reactive amino 5 properties are obtained in particular when the monomers (a )
groups . Amines suitable for this purpose are, in general, employed comprise essentially only aliphatic diisocyanates ,
polyfunctional amines with a molar weight in the range from and /or cycloaliphatic diisocyanates ; and when the monomer
(b1 ) employed essentially comprises only polyesterdiols
32 to 500 g /mol, preferably from 60 to 300 g/mol, having at synthesized
least two amino groups selected from the group consisting of 10 diacids , and from
when
the abovementioned aliphatic diols and
component ( d ), comprises alkali metal
primary and secondary amino groups. Examples are salts of N -( 2 - aminoethyl )- 2 - aminoethane sulfonic acid and/
diamines such as diaminoethane, diaminopropanes, diamin or N -( 2 - aminoethyl)- 2 -aminoethane carboxylic acid ; and
obutanes, diaminohexanes, piperazine , 2,5 -dimethylpipera when component ( d ) is a mixture of DETA / IPDA .
zine, amino - 3 - aminomethyl - 3 ,5 , 5 - trimethyl - cyclohexane In the field of polyurethane chemistry it is generally
( isophoronediamine, IPDA ), 4 , 4 '-diaminodicyclo - hexyl- 15 known how the molecular weight of the polyurethanes can
methane, 1 ,4 - diaminocyclohexane, aminoethyletha - be adjusted by choosing the proportions of the co -reactive
nolamine, hydrazine , hydrazine hydrate or triamines such as monomers and by the arithmetic mean of the number of
diethylenetriamine or 1 ,8 -diamino -4 -aminomethyloctane . It reactive functional groups per molecule. The components
is preferred to use mixtures of diamines and triamines , and their respective molar amounts are normally chosen
especially mixtures of isophoronediamine (IPDA ) and dieth - 20 such that the ratio A : B , where A is the molar amount of
ylenetriamine (DETA ). The polyurethanes contain prefer - isocyanate groups and B is the sum of the molar amount of
ably from 1 to 30 mol % , especially from 4 to 25 mol % , the hydroxyls and the molar amount of the further functional
based on the total amount of polyurethane components , of a groups which are able to react with isocyanates in an
polyamine having at least 2 isocyanate - reactive amino addition reaction , is from 0 .5 : 1 to 2 : 1 , preferably from 0 .8 : 1
groups, as monomers (d ). Preferably, the polyamine com - 25 to 1.5 : 1 and , with particular preference , from 0 . 9: 1 to 1.2 :1 .
pound is selected from the group consisting of isophorone With very particular preference the ratio A : B is as close as
diamine, diethylenetriamine and mixtures thereof. possible to 1: 1 .
The amines can also be employed in blocked form , for usually The components (a ) to (f) employed carry on average
example in the form of the corresponding ketimines , ket from 1 . 5 to 2 .5 , preferably from 1 . 9 to 2 . 1 and , with
for 30 particular
azines or amine salts. Oxazolidines too , as are used , for tional groups preference , 2 .0 isocyanate groups and /or func
example , in U .S . Pat. No. 4 , 192,937 , are capped polyamines addition reaction which are able to react with isocyanates in an
which can be employed to chain extend the prepolymers in .
the preparation of the polyurethanes. When capped prising Preferably , the polyurethane is made of components com
polyamines of this kind are used they are generally mixed 35 a ) 5 to 30 % by weight of at least one polyisocyanate with
with the prepolymers in the absence of water and this at least two isocyanate groups,
mixture is subsequently mixed with the dispersion water or b ) 10 to 80 % by weight of a combination of diols wherein
with a portion thereof so that the corresponding polyamines bl) at least one of the diols is a polyesterdiol having
are liberated by hydrolysis. molecular weight of from 500 to 5000 , and
The hardness and the modulus of elasticity of the poly - 40 b2 ) at least one of the diols is polytetrahydrofuran
urethanes can be raised by employing low molecular mass having a number average molecular weight of from
polyols ( f) (preferably diols ) having a molecular weight of 500 to 5000 g /mol,
less than 500 g /mol, e .g. from about 60 to 490 g /mol, wherein polyesterdiols (b1 ) and polytetrahydrofuran diol
preferably from 62 to 200 g /mol. The amount of low (62) are preferably in a weight ratio of from 1: 2 to 2 : 1 ,
molecular weight polyols ( f ) is preferably 0 to 10 % by 45 c 1 to 20 % by weight of at least one monohydroxy - poly
weight, more preferably from 1 to 8 % by weight. Com ( alkylene oxide ) compound having a number average
pounds employed as polyols (f) are in particular the struc molecular weight of from 500 to 5000 g /mol
tural components of the short- chain alkanediols cited for the d ) 1 to 10 % by weight of the at least one diamino acid
preparation of polyesterdiols , preference being given to the compound,
diols having 2 to 12 carbons, to the unbranched diols having 50 e ) 0 , 1 to 10 % by weight at least one polyamine compound
2 to 12 carbons and an even number of carbons, and to having at least two amino groups and no acid group ,
1,5 -pentanediol, 1,4 - butanediol and neopentyl glycol. and
In one aspect of the invention , the polyurethane is made f) 0 to 10 % by weight of the optional one or more polyol
exclusively from components (a ) to (e ) or exclusively from compounds having a number average molecular weight
components (a ) to (f) as mentioned above . 55 of less than 500 g /mol, preferably from 60 to 490
Optionally, the polyurethane can be made from one or g/mol.
more additional compounds , different from components (a ) The polyaddition of the structural components for the
to (f ), with at least one isocyanate group or with at least one production of the polyurethane preferably takes place at
isocyanate -reactive group . Examples are alcohols having a reaction temperatures of up to 180° C ., with preference up
functionality ofmore than 2 which can be used to establish 60 to 150° C . preferably from 70 to 150° C . at atmospheric
a certain degree of branching or crosslinking, such as pressure or under autogenous pressure . The production of
trimethylolpropane , glycerol and sugars . Also suitable are polyurethanes and of aqueous polyurethane dispersions is
monoalcohols which in addition to the hydroxyl carry a known to the person skilled in the art. The polyurethanes
further isocyanate- reactive group, such as monoalcohols preferably take the form of aqueous dispersions and are used
having one or more primary and/ or secondary amino groups; 65 in this form . The pH of the polymer dispersion is preferably
for example, monoethanolamine. For branching or cross - adjusted to be above 5 , in particular to be between 5 . 5 and
linking purposes it is also possible, to employ isocyanates 9.5 .
 US 10 ,280 ,320 B2
The PU dispersions are usually prepared by one of the The polyurethanes can be film forming upon removal of
followingmethods. In the acetone process an ionic polyure the solvent or water, or may be radiation curable . Unless
thane is prepared from the components in a water -miscible formulated to be electron beam curable , the radiation curable
solvent which boils at below 100° C . under atmospheric compositions will frequently contain a photoinitiator. The
pressure . Water is added until a dispersion is formed in 5 inks include a colorant in addition to the binder and solvent.
which water is the coherent phase. The prepolymer mixing nation The colorant is one or more pigment or possibly a combi
process differs from the acetone process in that rather than of pigment and one or more dyes . The colorant may
a fully reacted (potentially ) ionic polyurethane it is a pre azo dyes ( foror inorganic
be organic . Themost common pigments include
example , Solvent Yellow 14 , Dispersed Yellow
polymer carrying isocyanate groups which is prepared first.
In this case, the components are chosen such that the 10 Solvent 23 , and Metanil Yellow ), anthraquinone dyes (for example ,
Red 1 11, Dispersed Violet 1, Solvent Blue 56 , and
above -defined ratio A : B is greater than 1 .0 to 3 , preferably Solvent Orange 3 ), xanthene dyes (Solvent Green 4 , Acid
1 .05 to 1.5 . The prepolymer is first dispersed in water and Red 52, Basic Red 1 , and Solvent Orange 63 ), azine dyes
then crosslinked , possibly by reacting the isocyanate groups ( for example , Jet Black ), and the like. Major usable organic
with amines which carry more than 2 isocyanate -reactive 15 pigments include diarylide yellow AAOT (for example ,
amino groups, or is chain extended with amines which carry Pigment Yellow 14 CI# 21095 ), diarvlide vellow AAQA (for
2 isocyanate-reactive amino groups. Chain extension also example, Pigment Yellow 12 CI# 21090 ), Phthalocyanine
takes place when no amine is added . In this case , isocyanate Blue ( for example , Pigment Blue 15 ), lithol red ( for
groups are hydrolyzed to amino groups, which react with example , Pigment Red 52 : 1 CI# 15860 : 1 ), toluidine red (for
residual isocyanate groups of the prepolymers and so extend 20 example , Pigment Red 22 CI# 12315 ), dioxazine violet ( for
the chain . If a solvent has been used in preparing the example, Pigment Violet 23 CI# 51319 ), phthalocyanine
polyurethane, it is usual to remove the majority of the green (for example, Pigment Green 7 CI# 74260 ), phthalo
solvent from the dispersion , for example by distillation cyanine blue ( for example , Pigment Blue 15 CI# 74160 ),
under reduced pressure . The dispersions preferably have a naphthoic acid red ( for example , Pigment Red 48 : 2 CI#
solvent content of less than 10 % by weight and are , with 25 15865 : 2 ). Inorganic pigments include titanium dioxide (for
particular preference , free from solvents . The dispersions example , Pigment White 6 CI# 77891 ), carbon black ( for
generally have a solids content of from 10 to 75 , preferably example, Pigment Black 7 CI# 77266 ), iron oxides ( for
from 20 to 65 % by weight and a viscosity of from 10 to 500 example , red , yellow , and brown), ferric oxide black ( for
mPas (measured at 20° C . and at a shear rate of 250 s ). example , Pigment Black 11 CI# 77499 ), chromium oxide
In one aspect of the invention the lamination printing ink 30 (for example, green ), ferric ammonium ferrocyanide ( for
is free of ammonia and volatile organic tertiary amines . The example , blue ), and the like . The colorant is not limited to
term volatile means compounds with boiling points below the foregoing . Thus, the colorant may be any conventional
100° C . organic or inorganic pigment such as Zinc Sulfide , Pigment
The lamination ink preferably comprises 8 to 60 % by White 6 , Pigment Yellow 1, Pigment Yellow 3 , Pigment
weight, preferably 15 to 50 % by weight of binder, 3 to 30 % 35 Yellow 12 , Pigment Yellow 13 , Pigment Yellow 14 , Pigment
by weight, preferably 6 to 30 % by weight of pigments , 15 to Yellow 17 , Pigment Yellow 63, Pigment Yellow 65 , Pigment
60 % by weight, preferably 30 to 60 % by weight of water and Yellow 73 , Pigment Yellow 74 , Pigment Yellow 75 , Pigment
0 ,1 to 5 % by weight of additives such as surfactants, Yellow 83 , Pigment Yellow 97, Pigment Yellow 98 , Pigment
antifoam agents, and waxes . Yellow 106 , Pigment Yellow 114 , Pigment Yellow 121 ,
The binder can be exclusively the polyurethane binder of 40 Pigment Yellow 126 , Pigment Yellow 127 , Pigment Yellow
the invention . Combinations of polyurethane binders 136 , Pigment Yellow 174 , Pigment Yellow 176 , Pigment
according to the invention with other polyurethane or non Yellow 188, Pigment Orange 5 , Pigment Orange 13 , Pig
polyurethane binder resins such as acrylics can also be ment Orange 16 , Pigment Orange 34 , Pigment Red 2 ,
employed . When other binder resins are used , they prefer- Pigment Red 9 , Pigment Red 14 , Pigment Red 17 , Pigment
ably do not exceed about 50 % of the total amount of binder. 45 Red 22, Pigment Red 23 , Pigment Red 37, Pigment Red 38 ,
The inks are preferably free of ammonia ; volatile tertiary Pigment Red 41, Pigment Red 42 , PigmentRed 57 , Pigment
amines, residual isocyanate and tin . Red 112 , Pigment Red 122 , Pigment Red 170 , Pigment Red
The lamination printing ink of this invention may be used 210 , PigmentRed 238 , Pigment Blue 15 , Pigment Blue 15 : 1 ,
in either flexographic or gravure printing by simply making Pigment Blue 15 :2 , Pigment Blue 15 : 3 , Pigment Blue 15 :4 ,
minor adjustments to the formulation concentrations . Thus, 50 Pigment Green 7 , Pigment Green 36 , Pigment Violet 19 ,
the component concentrations may be adjusted for use in Pigment Violet 23 , Pigment Black 7 and the like.
flexography or gravure printing. For example , a gravure ink The lamination printing inks may also contain the usual
or a flexographic ink preferably comprises about 8 to 60 wt. ink additives to adjust flow , surface tension , and gloss of a
% of the binder, about 3 to 30 wt. % of the pigment colorant printed ink . Such additives typically are polymeric disper
and about 15 to 60 wt. % solvent or water . The ink preferably 55 sants , surface active agents , waxes, or a combination
has a viscosity between about 15 seconds to 30 seconds , as thereof. These additives may function as leveling agents ,
measured in a # 2 efflux cup . Efflux cup measurement is the wetting agents , fillers , dispersants , defrothers or deaerators ,
conventional method for measuring ink viscosities and or additional adjuvants may be added to provide a specific
involves timing the flow of a calibrated quantity of ink function . The lamination printing inks may contain a poly
through a calibrated orifice . The lower viscosity inks typi- 60 meric dispersant when the colorant is a pigment to disperse
cally are used in gravure printing and the higher viscosity the pigment during mixing and grinding operations in the
inks typically are used in flexographic printing. Thus , when solvent. All components of the ink may be blended together
the ink has a viscosity of about 28 seconds as measured in and ground to reduce the pigment particles to the desired
a # 2 efflux cup , it is suitable for flexographic printing, and size distribution , typically 10 microns or less, or alterna
when the ink has a viscosity of about 18 seconds as 65 tively the pigment and the polymeric dispersant can be
measured in a # 2 efflux cup, it is suitable for gravure premixed and ground in the solvent to form a " base " which
printing . is subsequently blended with the remaining components of
 US 10 ,280 , 320 B2
10
the ink composition . The ink components may be mixed in EXAMPLES
a high speed mixer until a slurry consistency is reached and Test method for pigment compatibility :
then passed through a media mill until the pigment is A lamination coloured ink is prepared, upon blending 30
reduced to 10 microns or smaller. The wide versatility of the wt % of a resin - based pigment concentrate with 70 % of the
inks of this invention allows them to be prepared without a polyurethane dispersion of the invention .
polymeric dispersant, but preferably they are made with a Typical formulation of a resin -based pigment concentrate :
polymeric dispersant for grinding in , for example , polyvinyl 10 40% %resinorganic
/ 1 %
pigment ( eg PY13 , PR57.1 , PB15 .3 , PB7 )/
surfactant/0 . 5 % antifoam / 48 . 5 % water.
butyral or blending with , for instance , a nitrocellulose base. The viscosity of the ink is measured directly after prepa
Thus, the ink of this invention may contain 0 to about 12 10 ratration of the ink , after one day and after 7 days. Viscosity
parts by weight of the polymeric dispersant. Other useful stability is reported . Ink is diluted to print viscosity (25 sec .
colorants , solvents and adjuvants can be identified by con DIN4 cup ) and is printed on an OPP (oriented polypropyl
sulting The Printing Ink Manual. ene ) film . Visual appearance ( color strength , gloss , trans
parency ) is judged .
The present invention further relates to the printed lami- 15 A lamination white ink is prepared , upon blending 40 % of
nate obtained or obtainable by using the ink according to the a resin -free pigment concentrate with 60 % of the polyure
invention for printing on at least a part of a surface of the thane dispersion according to the invention .
laminate . The printed laminate is made preferably from at Typical formulation of a resin - free pigment concentrate
white :
least two polymer films by laminating the films with a 20 75 % titanium dioxide /3 % surfactant/0 . 5 % antifoam /
lamination adhesive wherein the ink resides between the 21. 5 % water.
laminated films. At least one of the polymer films on which Viscosity of the ink is measured direct after preparation of
surface the ink resides preferably comprises a material the
the ink
ink,, arter
after one day and after 7 days . Viscosity stability is
one day
selected from polypropylene, polyethylene terephthalate , 25 reported and pigment sedimentation is judged . Ink is diluted
to print viscosity ( 25 sec . DIN4 cup ) and is printed on an
polyamide and low density polyethylene . OPP film . Visual appearance (opacity, gloss ) is judged .
The present invention further relates to the method of Test method for viscosity measurement:
making a printed laminate , which method comprises : Prepare 120 g colour (or 150 g white ) according to the test
ink formulation , at an ink temperature of 20º C . Put the ink
applying at least one lamination ink according to the into an efflux cup (eg DIN4 cup ) and register the time
invention to at least a part of a surface of a first polymer films needed to run the cup empty ( until the flow coming from the
by a roll printing process ( such as gravure printing or cup is no longer a continuous flow ). Viscosity is recorded as
flexographic printing) and laminating a printed or unprinted “ seconds DIN4” .
second polymer film to the ink -bearing surface of the first Test method for re- solubility :
polymer film by use of an adhesive . The material of the first* 35 andInkwill
will be diluted to press viscosity (25 sec . DIN4 cup )
be printed in gravure on laboratory press on a
and /or the second polymer film is preferably selected from
polypropylene, polyethylene terephthalate , polyamide and substrate Press
( eg LDPE ).
will be stopped and impression roller will be lifted
low density polyethylene . from the substrate . Press will be stopped for 5 minutes , in
Furthermore, the invention also relates to the use of order to allow the ink to dry into the cells of the gravure
polyurethane dispersions according to the invention for 40 cylinder. After 5 minutes press will be started again and the
water based inks for laminating printed (primary ) substrates amount of cylinder rotations will be counted for the original
to (secondary ) flexible films. These laminates render high printedimage to recover on the printed substrate. The sooner the
lamination bond strengths of preferably > 1. 5 N / 15 mm and ity to reimage will recover, the better the re -solubility ( = abil
- dissolve itself) of the ink is.
most preferably > 2 N /15 mm before and after heat-seal. 45 Typical ink preparation :
Lamination is carried out by procedures well known to a Coloured ink is prepared by blending 30 parts of a
person skilled in the art. Laminates in general are obtained ( resin -based or resin -free ) pigment paste (e . g . PB15 . 3 ) and
for example by an ink according to the invention to the 70 parts of a binder test dispersion . The viscosity of the ink
surface of a plastic substrate .After drying , a coated substrate can bemeasured employing a DIN4 cup . The viscosity of the
ink can be reduced to 20 s DIN4 using a 30 / 70 blend of
is obtained . Subsequently a lamination adhesive is used to 50
fix a second plastic surface to the coated substrate . The pigment paste /water.
plastic substrates are preferably polymer films, especially White ink is prepared by blending 40 parts of a resin - free
lally pigment paste (e.g . PW6 ) and 60 parts of a binder test
transparent polymer films or wherein at least one polymer dispersion . The viscosity of the ink can be measured
film is transparent. employing a DIN4 cup . The viscosity of the ink can be
Differently colored inks of the invention are especially 55 reduced to 20 s DIN4 using a 40 /60 blend of pigment
suited for multiple printing, i.e . a first colored printed inkpaste /water.
Typical Ink application :
layer is covered with at least one further , white or non -white
colored ink layer. Ink was applied on the treated side of coex -OPP
( 30MB400 — Oriented Polypropylene Film which can be
Benefits of the inks of the invention are high compatibility 60 obtained from ExxonMobil Chemical) and on chemically
of the binder with the pigments ; good blocking behavior of treatedtreat polyester (Mylar® 813 which can be obtained from
the printed film before lamination ; high lamination bond DuPont Teijin Films), using a wire -bar 0 (4 um wet ink ).
strength of the film laminates, also in case of multiple Inks were applied as 100 % colour (1 layer ), 200 % colour (2
printing ; high re - solubility of ink which has temporarily lavers ) and 100 % colour plus 100 % white ( 2 lavers ). The
dried on printing rolls ; no volatile bases necessary . 65 resulting prints were dried in an oven for 60 s at 60° C .
The invention is now illustrated by the following non - followed by a further drying period of about 1 hour at room
limiting examples. temperature , before making a laminate .
 US 10 ,280 , 320 B2
12
Typical Lamination procedure: Product Characteristics:
In order to test the lamination bond strengths, the prints on Solid content: 45 %
coex -OPP and chemically treated polyester were laminated
to coex -OPP and standard LDPE (Low -density Polyethyl pH : 9 .5
ene ) with a 2 -component
ent /polyurethane lamination adhesive , 5 Viscosity : ca . 130 mPa .s ( 25° C .)
respectively to give OPP /OPP and PET//LDPE laminates .
Preparation of the 2 component polyurethane lamination
adhesive: Example 2
Liofol® Hardener UR6080 : 8.0 weight parts (obtained
from Henkel Industrial Adhesives )
Liofol® UR7780 : 20 .0 weight parts (obtained from Hen 10 Printing Ink and Printing and Laminating
kel Industrial Adhesives ) Application
Ethyl acetate : 20 .0 weight parts (solvent for ease of
application )
Preparation of the laminate : Coloured Ink :
The freshly prepared adhesive is applied to the secondary 15
(unprinted ) film at a coating weight of 2 .5 g /m² (dry ), and
subsequently dried in the oven for 10 s at 60° C . to evaporate Joncryl ® HPD96 Pigment Concentrate PB15 .3 30 wt %
the solvent. The printed films ( coex -OPP and chemically Polyurethane dispersion (example 1) 70 wt %
treated PET) are next carefully applied with the printed side
to the adhesive side of the secondary films ( coex -OPP and 20
LDPE , respectively ), thereby avoiding creation of air White ink :
bubbles in the laminate , to give OPP //OPP and PET//LDPE
laminate structures . The resulting laminates are stored for 3
days under pressure ( ca 0 . 25 kg / cm ) , in order to allow the T750W Pigment concentrate PW6 40 wt %
adhesive to cure. 25 Polyurethane dispersion (example 1) 60 wt %

Ink viscosity is measured , using DIN4 cup , directly after

Example 1 the ink has been prepared . Same ink is measured for
viscosity after 1 day and after 7 days , as a measure of ink
Polyurethane Dispersion stability . The results are given in table 2 .
TABLE 1
polyurethane dispersion components
Equiv . Amount weight % Equivalent (OH ,
Component MW (g ) (solid PUD ) NCO , NH )
Pre- polyester based on adipic acid,
charge
1020 205.2 32.1 0 . 201
neopentylglycol, 1,6 -hexanediol;
OH number = 56 mg KOH / g
pTHF2000 1000 201. 2 31. 5 0 . 201
n -butanol started polyethylene 2 158 46 .55 7 .3 0 .0216
glycol (monohydric alcohol);
OH number = 26 mg KOH /g
Bismuth neodecanoate cat . 0 . 30 0 .05
(CAS = 34364 - 26 -6 )
Feed 1 Isophorone diisocyanates (IPDI) 111. 1 66 .60 10 . 4 0 . 599
H12 MDI (Desmodur ® W ) 132. 1 79. 13 12 . 4 0 .599
Feed 2 Acetone 109.0
Feed 3 1 , 4 -butanediol 45 .05 21. 34 3. 34 0 . 474
Feed 4 Acetone 468 . 1
Feed 5 40 % solution in H2O of sodium 208.6 30.00 1. 88 0 . 144
N -( 2 -aminoethyl)-beta - alaninate
Feed 6 Water 730. 1
Feed 7 isophoronediamine (IPDA ) 84.37 2 .02 0 .32 0 .0239
Diethylenetriamine 34 .53 4 .14 0.65 0 .120
Water 36 .32
pTHF2000 : poly ( tetrahydrofuran ) with molecular weight about 2000 (1950 - 2050 )

The components of the pre -charge are charged in a reactor TABLE 2

vessel followed by the mixture of isocyanates (Feed 1 ) .
Acetone (Feed 2 ) is added to the mixture and the mixture is Viscosity (seconds DIN4 cup )
heated to reflux until the theoretical NCO value is reached . 60 Viscosity direct Viscosity after 1 day Viscosity after 7 days
1 ,4 -butanediol (Feed 3 ) is added and the reaction is further
stirred at reflux until the desired NCO value is reached . The Colour 35 sec 37 sec 37 sec
mixture is diluted with acetone (Feed 4 ). At an internal White 21 sec 22 sec 22 sec
temperature of 50° C ., Feed 5 is added . The mixture is
dispersed by addition of water (Feed 6 ), followed by addi- 65
tion of the amines mixture and water (Feed 7 ). Acetone is Before being able to print the ink on a substrate , the ink
distilled under vaccum . has to be diluted to press viscosity .
 US 10 ,280 , 320 B2
13 14
Reduce viscosity to 20 sec DIN4, using a blend of 30 % TABLE 4
HPD96 PB15 .3 /70 % water for colour ink Typical example of lamination bond strength measurement result
Reduce viscosity to 20 sec DIN4, using a blend of 40 %
T750W PW6 /60 % water for white ink Lamination bond
La strength
5 Ink Substrate [N /15 mm ]
TABLE 3 100 % coloured ink ex . 2 OPP //OPP 4 .0
100 % white ink ex 2 OPP // OPP 4. 5
Typical example of dilution to print viscosity : 100 % coloured ink ex . 2 + OPP //OPP 4.8
100 % white ink ex 2
Viscosity directD ilution (ink :water ) Print viscosity 10 100 % coloured ink ex. 2 PET//LDPE ?i
100 % white ink ex 2 PET //LDPE
100 % coloured ink ex . 2 + PET//LDPE
Colour 37 sec 100 : 5 20 sec 100 % white ink ex 2
White 22 sec 100 :2 20 sec

15 Blocking resistance:
Ink application : Diluted ink (diluted to a viscosity of 20 sec . DIN4 cup )
Print the ink on coextruded OPP (MB400 , ex ExxonMo- will be printed on the relevant substrate ( eg LDPE , OPP,
bil) and on polyester film (Mylar 813 , ex Teijin -DuPont), PET, Nylon ). Coating weight applied : 1.0 g/m² for colour
using a K -bar 0 (applying 4 micron wet coating weight). and 1. 5 g/m² for white . Printwillbe dried in an oven : 10 sec .
20 at 60° C . After drying , a second layer film ( same specifica
For two layers (colour + white): print the first layer of 20 tion ) will be placed on top of the printed film , with the
colour and dry the print in the oven , then print the second backside of the second film facing the printed side of the
layer of white ink on top of the first layer and dry the print printed film . Films will be placed in a Specac laboratory
again in the oven . press and will be blocked at 5 tons/30° C ./24 hrs (represent
Drying: 25 ing 65 kg /cm²). After removing the samples from the
For one - layer print: put the printed substrate in an air blocking tester, the unprinted layer film will be removed
from the printed layer, and the tendency of the unprinted film
circulated oven , for 10 sec at 60° C . air temperature, then to adhere to the printed film (“ blocking ” ) will be judged and
leave the print for 1 h at room temperature before laminating reported as “ Release” ( tackiness ) and “ Damage” ( ink trans
it to the secondary film . 30 fer to the unprinted film ). Typical example of blocking
30
For two-layers print: print the first colour layer, dry 10 sec resistance measurement results are reported below . The
at 60° C . in an air circulated oven , print the second layer of values go from 1 (bad , blocking ink ) to 5 ( good , blocking
white ink , dry 10 sec at 60° C . and leave the print for 1 h at free ink ).
room temperature , before laminating it to the secondary
film . 35 TABLE 5
Lamination : blocking resistance measurement results
Laminate the printed film (OPP resp . PET) to a secondary Ink Substrate Release Damage
film (OPP resp . LDPE ), using a 2 component laminating
100 % coloured ink ex . 2 PET //LDPE
adhesive , in order to get an OPP //OPP resp . PET/LDPE 100 % white ink ex 2 PET //LDPE 3-4
?i
Vi

laminate : 100 % coloured ink ex . 2 + PET//LDPE 3-4 ?

Prepare lamination adhesive: blend 4 g Henkel Liofol® 100 % white ink ex 2

UR6080 / 10 g Henkel Liofol® UR7780 / 10 g ethyl
acetate and mix homogeneous
Apply lamination adhesive onto the secondary film , using
45 The invention claimed is :
K -bar 1 (6 micron wet coating weight), followed by 1. A lamination printing ink comprising :
subsequent drying ( 10 sec in oven at 60° C .) at least one binder,
at least one pigment,
Apply the printed film onto the secondary film , with the an aqueous carrier, wherein the aqueous carrier is a
printed side facing the adhesive 50 solvent or water, and
Firmly squeeze the laminated construction , by using a 10 optionally , at least one additive ,
kg roller wherein the at least one binder is an aqueous dispersion
comprising a polyurethane ,
Put the laminate under pressure ( 10 kg blocks) and store wherein the polyurethane is made of components com
for 3 days at room temperature 55 prising:
Lamination Bondstrength : a ) at least one polyisocyanate with at least two isocyanate
groups,
For measurement of lamination bond strength (= force b ) a combination of diols, wherein
needed to peel the laminate open ), a strip of 15 mm width bl) at least one of the diols is a polyesterdiol having a
is cut from the cured laminate and bond strength is measured 50 number average molecular weight of from 500 to
using a Lloyd Instruments tensile tester. Measurement is 5 ,000 , and
done at a speed of 150 mm /min . During the measurement, b2) at least one of the diols is polytetrahydrofuran
the laminated strip should be kept under a 90° angle against having a number average molecular weight of from
the film clamps . This test is repeated after the laminated strip 500 to 5 ,000 g /mol,
has been heat- sealed at 140° C / 400N / 1 s using a Brugger 65 c ) at least one monohydroxy - poly ( alkylene oxide) com
heat sealer, in order to simulate heat-seal bond strength . pound having a number average molecular weight of
Lamination bond strength is reported in N / 15 mm . from 500 to 5 ,000 g /mol,
 US 10 ,280 , 320 B2
15 16
d ) at least one diamino acid compound , one additive , wherein the at least one additive is a surfactant ,
e ) at least one polyamine compound having at least two antifoam agent, a wax, other additive, or a combination
amino groups and no acid group, and thereof.
f ) optionally , one or more polyol compounds having a 10 . The lamination printing ink according to claim 1 ,
number average molecular weight of less than 500 5 wherein the at least one polyisocyanate (a ) comprises only
g /mol, an aliphatic diisocyanate , and /or a cycloaliphatic diisocya
wherein the lamination printing ink is a gravure ink or a
flexographic ink comprising from 8 to 60 wt. % of the nate ; and the at least one of the diols (bl ) comprises only at
at least one binder, from 3to 30 wt. % of the at least one least one olyesterdio synthesized from an aliphatic diol and
pigment, and from 15 to 60 wt. % of the aqueous 10 a diacid ; and the at least one diamino acid component (d )
carrier, and comprises an alkali metal salt of N -( 2 -aminoethyl)-2 -amin
wherein the ink has a viscosity suitable for flexographic oethane sulfonic acid and /or N - ( 2 - aminoethyl)- 2 -amino - eth
printing or for gravure printing, wherein the viscosity is ane carboxylic acid ; and the at least one diamino acid
from 15 seconds to 30 seconds, as measured in a No. 2 component ( e ) is a mixture of diethylenetriamine and iso
efflux cup . 15 phoronediamine (DETA / IPDA ) .
2 . The lamination printing ink according to claim 1, 1111 .. AA printed lamin having the ink of claim 1 on at least
printed laminate
wherein the polyisocyanate (a ) is at least one selected from a part of a surface thereof.
the group consisting of 1 -isocyanato - 3 ,5 ,5 -trimethyl- 5 - iso 12 . The printed laminate of claim 11 , wherein the laminate
cyanatomethylcyclo -hexane (IPDI), tetramethylxylylene is made from at least two polymer filmsby laminating the
diisocyanate ( TMXDI), hexamethylene diisocyanate (HDI), 20
films with
bis(4 -isocyanatocyclohexyl)methane (HMDI) and a mixture between the laminated films. a lamination adhesive , wherein the ink resides
thereof.
3. The lamination printing ink according to claim 1, 13. The printed laminate of claim 11 , wherein at least one
wherein the polyesterdiol is made from of the polymer films on which surface the ink resides
at least one dicarboxylic acid of the formula HOOC — 25 comprises at least one material selected from the group
(CH ,), — COOH , where y is a number from 1 to 20 , and consisting of polypropylene, polyethylene terephthalate ,
at least one polyhydric alcohol selected from the group polyamide and low density polyethylene .
consisting of a compound of the formula HO - 14 . A method of making a printed laminate , which com
number from 11 toto 20
(CH ,) , OH , where xx isis aa number 20 ,, prises:
neopentyl glycolhere
, and a mixture thereoffrom
. 30
applying at least one lamination ink of claim 1 to at least
4 . The lamination printing ink according to claim 1 ,
wherein the alkylene in the at least one monohydroxy -poly a part of a surface of a first polymer film by a roll
(alkylene oxide) compound is ethylene and /or propylene. printing process, and
5 . The lamination printing ink according to claim 1 . laminating a printed or unprinted second polymer film to
wherein the at least one diamino acid compound is selected 35 the ink -bearing surface of the first polymer film by use
from the group consisting of a diamino carboxylic acid of an adhesive.
compound and a diamino sulfonic acid compound , corre 15 . The method of claim 14 wherein the material of the
sponding alkali metal salts thereof, and a mixture thereof. first and /or the second polymer film is selected from the
6 . The lamination printing ink according to claim 1 , group consisting of polypropylene, polyethylene terephtha
wherein the at least one polyamine compound is selected 40 late , polyamide, low density polyethylene, and mixtures
from the group consisting of isophoronediamine , diethylen - thereof.
etriamine and a mixture thereof. 16 . The lamination printing ink according to claim 1,
7 . The lamination printing ink according to claim 1 ,
wherein the polyurethane is made of components compris wherein furan
the at least one of the diols b2 ) is polytetrahydro
having a number average molecular weight of from
ing : 45 1 ,000 to 3 ,000 g /mol.
a ) 5 to 30 % by weight of the at least one polyisocyanate 17. The lamination printing ink according to claim 1 that
with at least two isocyanate groups,
b ) 10 to 80 % by weight of the combination of diols, comprises (f) one or more polyol compounds having a
c ) 1 to 20 % by weight of the at least one monohydroxy - number average molecular weight of less than 500 g/mol.
poly (alkylene oxide ) compound having a number aver- 50 18 . The lamination printing ink according to claim 5 ,
age molecular weight of from 500 to 5 , 000 g /mol, wherein the at least one diamino acid compound d ) is
d ) 1 to 10 % by weight of the at least one diamino acid selected from the group consisting of N -( 2 -aminoethyl) -2
compound , aminoethane-sulfonic acid , N -( 2 -aminoethyl)- 2 -aminoeth
e ) 0 . 1 to 10 % by weight at least one polyamine compound anecarboxylic acid , a corresponding alkali metal salt, and a
having at least two amino groups and no acid group , 55 mixture thereof.
and 19 . The lamination printing ink according to claim 7,
f) optionally, 0 to 10 % by weight of one or more polyol wherein a weight ratio of the polyesterdiol in bl) and the
compounds having a number average molecular ar weight
weight polytetrahydrofuran diol in b2 ) is from 1:2 to 2 : 1.
of less than 500 g /mol.
8 . The lamination printing ink according to claim 1, 60 20 . The method of making a printed laminate according to
wherein the ink is free of ammonia and free of volatile nationclaim 14 , which comprises applying the at least one lami
organic tertiary amines . ink to at least a part of a surface of the first polymer
9 . The lamination printing ink according to claim 1 , film by gravure printing or by flexographic printing .
further comprising from 0 .1 to 5 % by weight of the at least * * * *