U.S. patent application number 10/981188 was filed with the patent office on 2005-05-26 for method and compositions for decorating glass.
This patent application is currently assigned to Deco Patents, Inc.. Invention is credited to Hu, Ming, Kamen, Melvin Edwin.
Application Number | 20050113484 10/981188 |
Document ID | / |
Family ID | 25338179 |
Filed Date | 2005-05-26 |
United States Patent
Application |
20050113484 |
Kind Code |
A1 |
Kamen, Melvin Edwin ; et
al. |
May 26, 2005 |
Method and compositions for decorating glass
Abstract
A method for decorating a vitreous article, in particular, a
glass substrate, comprising applying to the glass in a
predetermined design a radiation curable ink composition which is
(i) operable when cured to bond to glass, and (ii) strippable from
the glass upon exposure to alkali, and curing the ink on the glass
by exposing it to the radiation by which it is curable, thereby
bonding the ink to the glass; and related compositions; as well as
a method for stripping the decorative indicia from glass upon
exposure to alkali, and the related compositions.
Inventors: |
Kamen, Melvin Edwin;
(Highlands, NJ) ; Hu, Ming; (Piscataway,
NJ) |
Correspondence
Address: |
JONES DAY
222 EAST 41ST ST
NEW YORK
NY
10017
US
|
Assignee: |
Deco Patents, Inc.
|
Family ID: |
25338179 |
Appl. No.: |
10/981188 |
Filed: |
November 3, 2004 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10981188 |
Nov 3, 2004 |
|
|
|
10002220 |
Nov 15, 2001 |
|
|
|
10002220 |
Nov 15, 2001 |
|
|
|
09479590 |
Jan 7, 2000 |
|
|
|
09479590 |
Jan 7, 2000 |
|
|
|
08868409 |
Jun 3, 1997 |
|
|
|
6093455 |
|
|
|
|
08868409 |
Jun 3, 1997 |
|
|
|
08862304 |
May 23, 1997 |
|
|
|
Current U.S.
Class: |
523/160 |
Current CPC
Class: |
C03C 2217/485 20130101;
C03C 2218/355 20130101; B41M 7/0081 20130101; B41M 7/009 20130101;
C03C 17/007 20130101; C09D 11/101 20130101; B41M 1/34 20130101;
C03C 17/32 20130101 |
Class at
Publication: |
523/160 |
International
Class: |
C09D 011/00 |
Claims
What is claimed is:
1. A method for decorating a vitreous article comprising the steps
of: a) applying to the vitreous article in a predetermined design a
radiation curable ink composition comprising free acid groups which
is (i) operable when cured to bond to the vitreous article, and
(ii) strippable from the vitreous article upon exposure to alkali,
followed by, b) curing the ink on the vitreous article by exposing
it to the radiation by which it is curable, and thereafter, c)
subjecting the decorated vitreous article to an elevated
temperature which is higher than about 90.degree. C. until the ink
is sufficiently adhered to the vitreous article.
2. The method of claim 1 wherein the alkali is an aqueous alkaline
solution.
3. The method of claim 2 wherein the aqueous alkaline solution
comprises 2 to 10% by weight of alkali.
4. The method of claim 3 wherein the alkaline solution is an
aqueous solution of sodium hydroxide or potassium hydroxide.
5. The method of claim 4 wherein the alkaline solution contains 4%
by weight of sodium hydroxide.
6. The method of claim 1 wherein the ink composition is strippable
from the vitreous article upon exposure to an aqueous alkaline
solution for a period of 1 to 60 minutes, wherein said aqueous
alkaline solution has a temperature of 60 to 100.degree. C., and
contains 2 to 20% by weight of the total alkali composition of
alkali.
7. The method of claim 1 wherein the ink composition comprises a
monomer or oligomer having at least one free acidic group.
8. The method of claim 7 wherein the acidic group is a carboxylic
acid group, a phosphoric acid group, or a sulfonic acid group.
9. The method of claim 7 wherein the monomer or oligomer is an
ethylenically unsaturated monomer or oligomer.
10. The method of claim 9 wherein the ethylenically unsaturated
monomer or oligomer is an acrylate or methacrylate.
11. The method of claim 10 wherein the acidic group is a carboxylic
acid group.
12. The method of claim 11 wherein the monomer or oligomer contains
repeating alkylene oxide units.
13. The method of claim 11 wherein the monomer or oligomer is an
aromatic acid anhydride.
14. The method of claim 1 wherein the ink composition comprises, by
weight of the total composition: about 5-95% of a ethylenically
unsaturated monomer or oligomer having at least one free acid
group, and, about 5-95% pigment.
15. The method of claim 14 wherein the ink composition further
comprises about 0.5-25% by weight of the total composition of a
silane adhesion promoter.
16. The method of claim 14 wherein the ink composition further
comprises about 0.01-10% by weight of the total composition of a
polyether defoaming agent.
17. The method of claim 14 wherein the ink composition further
comprises a fluorinated surfactant.
18. The method of claim 1 wherein the ink is curable by exposure to
actinic radiation.
19. The method of claim 1 wherein the ink is curable by exposure to
ultraviolet radiation.
20. The method of claim 1 wherein the vitreous article is
glass.
21. A method for stripping decorative indicia from a glass
substrate decorated with a radiation cured ink composition
containing free acid groups which is (i) operable after radiation
curing and exposure of the decorated vitreous article to an
elevated temperature which is higher than about 90.degree. C. to
bond to glass and, (ii) strippable from the glass upon exposure to
alkali, comprising contacting the glass substrate having the
decorative inidicia thereon, with an aqueous alkaline solution
containing about 2-20% by weight alkali for a period of 1 to 60
minutes.
22. The method of claim 21 wherein the glass substrate having the
decorative indicia thereon is contacted with the aqueous alkaline
solution at a temperature of about 60 to 100.degree. C.
23. The method of claim 21 wherein the radiation cured ink
composition is a polymeric composition formed by the polymerization
of ethylenically unsaturated monomers or oligomers having at least
one free acid group.
24. The method of claim 23 wherein the ethylenically unsaturated
monomers or oligomers are acrylates or methacrylates.
25. The method of claim 23 wherein the acid group is a carboxylic
acid group, a sulfonic acid group, or a phosphoric acid group.
26. The method of claim 25 wherein the acid group is a carboxylic
acid group.
27. The method of claim 1 wherein the length of exposure at the
elevated temperature is between about 0.5 minutes to about 30
minutes.
28. The method of claim 21 wherein the length of exposure at the
elevated temperature is between about 0.5 minutes to about 30
minutes.
Description
[0001] This application is a continuation-in-part of copending U.S.
Patent Application Case Docket No. Rev 97-2, filed May 23, 1997,
entitled "Method and Compositions For Decorating Glass", by
inventors Melvin Edwin Kamen, and Ming Hu, for which a U.S. patent
application Ser. No. ______ is not yet available.
TECHNICAL FIELD
[0002] The invention is in the field of decorating vitreous
articles with radiation curable inks. In particular, the invention
relates to decoration of vitreous articles such as glass, with
radiation curable inks which, to facilitate recycling, are capable
of being chemically removed from the glass upon exposure to alkali
for a ed period of time.
BACKGROUND OF THE INVENTION
[0003] Commercial ceramic and glassware is often decorated by
applying a pattern in colored ink on the surface of the substrate
with screen printing, offset printing, or any other direct
application technique. The glass is then baked at high temperature
to bond the design or indicia to the glass surface. This process,
sometimes referred to as applied ceramic labeling (ACL), exhibits
certain drawbacks. Often, the ink compositions contain heavy metals
and volatile organic solvents (VOC's). Both VOC's and heavy metals
are usable from the environmental point of view. Second, ACL
requires high temperature ovens for the baking step, which results
in considerable energy usage and an increased potential for worker
injury due to the high temperatures at which the process operates.
Moreover, the high temperature ovens are expensive, cumbersome
pieces of equipment which re considerable floor space in
factories.
[0004] The decoration of glass with ultraviolet (UV) radiation
curable organic pigmented inks for the decoration of glass and
ceramic ware is known in the art. Organic inks generally can be
cured by exposure to radiation, such as ultraviolet radiation, thus
obviating the need for high temperature baking. In addition, UV
curable organic inks can be formulated to contain little or no
VOC's or other nonaqueous solvents. Organic inks generally exhibit
excellent adherence to glass.
[0005] In many countries, it is mandatory that beverages such as
beer and soda, be marketed in returnable glass bottles. After the
beverage has been consumed, the glass bottles are returned to the
beverage filler. They are then cleaned, sterilized, refilled,
relabeled, then sold again. Decals and paper labels are most often
used to decorate returnable beverage bottles. Both types of labels
have many drawbacks. For example, both paper labels and decals are
expensive. In addition, they are messy, and can easily come off
upon exposure to water or other materials. In addition, many of the
adhesives used in decals become sticky when subjected to the bottle
cleaning process, and cause machines, drains, etc. to be gummed
up.
[0006] There is a need for a method to decorate returnable beverage
bottles that provides excellent decorative effect. In addition, the
method must be cost competitive when compared to paper labels and
decals. At the same time the decorative indicia applied should be
easily strippable from the glass container between fillings.
SUMMARY OF THE INVENTION
[0007] The invention is directed to a method for decorating a
vitreous article comprising the steps of:
[0008] a) applying to the vitreous article in a predetermined
design a radiation curable ink composition which is (i) operable
when cured to bond to the vitreous article, and (ii) strippable
from the vitreous article upon exposure to alkali,
[0009] b) curing the ink on the vitreous article by exposing it to
the radiation by which it is curable, thereby bonding the ink to
the vitreous article.
[0010] The invention is also directed to a method for stripping
decorative indicia from a vitreous article decorated with a
radiation cured ink composition containing free acid groups which
is (i) operable, when cured, to bond to the vitreous article, and
(ii) strippable from the vitreous article upon exposure to alkali,
comprising containing the vitreous article wish an aqueous alkaline
solution containing 2-20% by weight alkali for a period of
approximately 1 to 120 minutes.
[0011] The invention is directed to a ink composition comprising,
by weight of the total composition:
[0012] 5-95% of an acid functional monomer or oligomer,
[0013] 5-95% of a monomer or oligomer that does not contain free
acid groups,
[0014] 5-95% pigment
DETAILED DESCRIPTION
[0015] All percentages mentioned herein are percentages by weight
unless otherwise indicated.
[0016] The radiation curable ink compositions used in the method of
the invention must be operable, when cured, to bond to the vitreous
article, which is preferably glass. In particular, the ink
compositions must be capable of adhering to glass to a degree
sufficient to permit use as a commercial container used for
beverages or other consumable materials. At the same time, the
polymerized ink compositions must be capable of being readily
stripped or removed from the glass upon exposure of the decorated
glass to alkali. Glass containers are filled; then they are
decorated with the radiation curable ink compositions. After the
beverage in the container is consumed, the container is returned to
the filler. The decorative indicia is stripped from the glass upon
exposure to alkali. The containers are then cleaned, sterilized,
filled, redecorated, and shipped again.
[0017] Generally, strippable ink compositions are made from
radiation curable monomers and/or oligomers having at least one
free acid group. The term "free acid" means an acidic group which
is capable of reacting with alkali. Examples of such acidic groups
are carboxylic acid groups, phosphoric acid groups, sulfonic acid
groups and the like. Preferably, the acid group is a carboxylic
acid group. The resulting polymerized coating contains free acidic
groups which, upon exposure to alkali, react with the alkali to
form a salt. As a result the decorative indicia are much more
readily removable from the glass. It should be noted that in order
for radiation cured glass coatings to be considered "high
performance", decorative indicia must be capable of withstanding
exposure to a concentrated aqueous alkali solution for a period of
two to four hours. In contrast, the radiation cured ink
compositions of the invention must be completely removed from the
glass container upon exposure to aqueous alkali before two hours
has lapsed; after a period of about 1 to 120 minutes, preferably
about 1 to 60 minutes, more preferably about 5 to 30 minutes.
[0018] The Ink Compositions
[0019] The Acid-Functional Monomer and/or Oligomer
[0020] The ink compositions used in the method of the invention,
contain about 5-95%, preferably about 10-85%, more preferably about
15-75% of a monomer, oligomer, or low molecular weight homo- or
copolymer having at least one free acid group. A variety of such
materials are suitable, provided they have at least one free acid
group, such as a carboxylic acid, sulfonic acid, or phosphoric acid
group. The phrase "having at least one free acid group" means that
the monomer unit has at least one free acid group, or the oligomer
contains at least one monomer unit containing a free acid group, or
if a homo- or copolymer, at least one monomer unit thereof contains
at least one free acid group. Preferably the ink composition
contains a monomer or oligomer, in particular an ethylenically
unsaturated monomer or oligomer having at least one free acid
group. Examples of preferred monomers or oligomers include those
having carboxylic acid functional groups such as: 1
[0021] wherein R.sub.1 is H, a C.sub.1-30 straight or branched
chain, substituted or unsubstituted, saturated or unsaturated
alkyl, aryl, aralkyl, a pyrrolidone, or a substituted or
unsubstituted aromatic, alicyclic, or bicyclic ring where the
substitutents are C.sub.1-30 straight or branched chain alkyl, or
halogen. 2
[0022] wherein R.sub.1 is as defined above, and R.sub.2 is X--COOH
wherein X is a C.sub.1-30 straight or branched chain alkyl, aryl,
arylalkyl, or CH.sub.2CH.sub.2--O.paren close-st..sub.nY--COOH or
CH.sub.2CH.sub.2--O).paren close-st..sub.nY--COOH wherein Y is a
C.sub.1-10 straight or branched chain alkyl and n is 1-10,000.
[0023] Preferably the monomer or oligomer is of Formula II wherein
R.sub.1 is H or CH.sub.3, and R.sub.2 is X--COOH wherein X is a
C.sub.1-10 straight or branched chain alkyl, more preferably ethyl.
More preferably R.sub.2 is beta-carboxyethyl, e.g. as in
beta-carboxyethyl acrylate, which is sold under the tradename B-CEA
by UCB Radcure, Inc. B-CEA is a reactive monomer which contains
both acrylate and carboxylic acid functionality, predominantly as
the acrylic acid dimer, and, in particular, is a mixture of about
40% by weight B-carboxyethylacrylate, about 40% by weight higher
homologs of acrylic acid, and about 20% by weight of acrylic acid.
The B-carboxyethylacrylate component of this mixture has the
following formula: 3
[0024] In addition, carboxylic acid functional oligomer, such as
aromatic acid methacrylate half esters and aromatic acid acrylate
half esters are also suitable acid functional oligomers for use in
the method of the invention Examples of such oligomers are partial
esters of anhydride-containing copolymers such as those disclosed
in U.S. Pat. No. 4,722,947, which is hereby incorporated by
reference. These copolymers correspond to the following formula:
4
[0025] wherein R.sub.1 and R.sub.2 are each independently hydrogen,
C.sub.1-20 alkyl, aryl, alkaryl, cycloalkyl, or halogen; R.sub.3,
R.sub.4, and R.sub.5 (see below) are each independently hydrogen,
C.sub.1-20 alkyl, or aryl; and R.sub.6 is the same or different and
is alkyl, aralkyl, or an alkyl substituted alkyl radical containing
about 1 to 20 carbon atoms as well as oxyalkylated derivatives
thereof and the subscripts x, y, z, and p are each whole numbers
such that the sum of x, y, z, and p may range from about 3 to 20;
and x, p, and y are each equal to or greater than 1, and z may be
0; and B is --OAOCOCR.sub.5CH.sub.2 wherein A is a linear or
branched divalent alkylene of from about 1 to 20 carbon atoms, or
an oxyalkylated derivative thereof as described for R.sub.6.
[0026] Particularly preferred aromatic partial esters of anhydride
containing copolymers are those sold by Sartomer, Inc. under the
Sarbox tradename, such as SB-400, SB-500, and SB-600. Particularly
preferred is aromatic acid methacrylate half ester in ethoxylated
trimethylolpropane triacrylate, which is sold by Sartomer, Inc.
under the tradename Sarbox SB500E50.
[0027] Other suitable carboxylic acid functional monomers include
acrylic acid, bisacrylamidoacetic acid,
4,4-bis(4-hydroxphenyl)pentanoic acid, 3-butene-1,2,3-tricarboxylic
acid, 2-carboxyethyl acrylate, itaconic acid, methacrylic acid,
4-vinylbenoic acid, and mixtures of these materials.
[0028] Examples of monomers containing sulfonic acid groups include
2-acrylamido-2-methyl-1-propanesulfonic acid;
2-methyl-2-propene-1-sulfon- ic acid, 2-propene-1-sulfonic acid,
4-styrenesulfonic acid, 2-sulfoethyl methacrylate,
3-sulfopropyldimethyl-3-methacrylamidopropyl ammonium inner salt,
3-sulfopropyl methacrylate, vinylsulfonic acid, and so on.
[0029] Examples of monomers containing phosphoric acid functional
groups include bis(2-methacryloxyethyl)phosphate, monoacryloxyethyl
phosphate, and so on.
[0030] Additional Polymerizable Reactants
[0031] In addition, the ink compositions may contain about 5-95%,
preferably about 10-85%, more preferably about 15-75% of other
polymerizable reactants such as radiation curable monomers,
oligomers, or low molecular weight homo- or copolymers,
terpolymers, or graft or block copolymers which do not contain free
acid groups. Examples of suitable monomers include epoxides,
cycloaliphatic epoxides, vinyl chloride, styrene, ethyl acrylate,
vinyl acetate, difunctional acrylic monomers such as hydroxy alkyl
acrylates, or hydroxy alkyl methacrylates, vinyl butyrate, vinyl
methyl ether, methyl methacrylate, isobornyl acrylate,
acrylonitrile, or mixtures thereof. Suitable polymers include
oligomers, homo- or copolymers, terpolymers, graft copolymers of
the above monomers provided they have a molecular weight of less
than about 50,000, otherwise it is too difficult to effect
polymerization, i.e. curing. Preferred are acrylate homopolymers or
acrylate or methacrylate copolymers, preferably acrylate or
methacrylate copolymers Examples of such acrylate or methacrylate
copolymers include epoxy acrylates, copolymers of propylene glycol
and a dicarboxylic acid, urethane acrylates, and the like.
Preferably, the compositions contain one or more polymerizable
reactants selected from the group consisting of urethane acrylate
copolymers, tripropylene glycol acrylate, epoxy acrylate, and
mixtures thereof.
[0032] Preferably, the radiation curable compositions of the
invention contain about 5-95% by weight of acrylate or methacrylate
monomers, or homo- or copolymers which do nt contain acid
functional groups.
[0033] Pigment
[0034] The compositions used in the invention preferably contain
5-95%, preferably 5-50%, more preferably 8-35% by weight of the
total composition of pigment A wide variety of pigments are
suitable including organic and inorganic pigments. Examples of such
pigments are set forth in U.S. Pat. No. 5,178,952, which is hereby
incorporated by reference. Inorganic pigments include extender
pigments such are baryites, barium sulfate, calcium carbonate,
talc, clay, alumina, titanium dioxide, white carbon, chinese white,
zinc sulfide, lithopone, ultramarine, Prussian blue, cobalt, chrome
oxide, viridian chrome green yellows, oranges, and reds, cadmium,
chromium, iron oxides, carbon black, metallic pigments, aluminum
powder, bronze powder, zinc chromate, strontium chromate, zinc
dust, copper, and so on. Examples of suitable organic pigments
include azo pigments, indolinones, isoindolinones, vat pigments,
the Lakes, pthalocyanine pigments and so on. The preferred pigment
to impart white color to the ink composition is titanium dioxide.
Preferred red and yellow pigments are isoindolinones and
pyrrolopyrrols as disclosed in U.S. Pat. Nos. 4,415,685; 4,579,949;
4,791,204; 4,666,455; 5,074,918; 4,783,540; 4,914,211; 4,585,878;
as well as U.S. Pat. No. 5,571,359 of Kamen, et al., all of which
are hereby incorporated by reference. The pyrrolopyrrols are
genially of the formula: 5
[0035] wherein R.sub.1 and R.sub.2 are each independently alkyl,
arylalkyl, aryl, substituted or unsubstituted isocyclic or
heterocyclic aromatic radicals; R.sub.3 and R.sub.4 are each
independently H, substituted or unsubstituted alkyl,
alkoxycarbonyl, aroyl (e.g. benzoyl), arylalkyl (e.g. benzyl), aryl
(e.g. phenyl), alkanoyl, C.sub.5-6 cycloalkyl, alkenyl, alkynyl,
carbamoyl, alkylcarbamoyl, arylcarbamoyl, or alkoxycarbonyl; and X
is O or S. Preferred is a compound wherein R.sub.1 and R.sub.2 are
each independently phenyl or naphthyl, R.sub.3 and R.sub.4 are
hydrogen, and X is O. Particularly preferred as a red pigment is
pyrrolo 3,4-C pyrrol-1,4-dione, 2,5-dihydro-3,6-di-4-chlorophe- nyl
which has a CAS number 84632-65-5 and is known by the common name
C.I. pigment red 254. This pigment is commercially available from
Ciba-Geigy Pigments Division, Newport, Del., under the tradename
Irgazin DPP Red 80. Other Ciba-Geigy red pigments sold under the
tradename Irgazin are also suitable.
[0036] Suitable isoindolinones are as set forth in U.S. Pat. Nos.
3,884,955, 3,867,404, 4,978,768, 4,400,507, 3,897,439 and 4,262,120
and 5,194,088 all of which are hereby incorporated by reference.
Preferred isoindolinones are tetrachlorocyanobenzoic acid alkyl
esters, particularly benzoic acid,
2,3,4,5-tetrachloro-6-cyano-methyl ester which is reacted with
2-methyl-1,3-benzenediamine and sodium methoxide. This pigment
composition has the common name C.I. Pigment Yellow 109 and is
available commercially from Ciba-Geigy Pigments Division, Newport
Del. under the tradename Irgazin yellow 2GLTE. Other pigments in
the Irgazin Yellow series as manufactured by Ciba-Geigy are also
suitable.
[0037] Particularly suitable are blue pigments marketed by
Ciba-Geigy under the tradename Irgazin Blue X-3367, or by
Whittaker, Clark, & Daniels under the tradename Ultramarine
Blue 5009.
[0038] Defoaming Agent
[0039] The ink compositions used in the invention also preferably
contain about 0.01-10% of a defoaming agent, preferably a
polyether-containing defoaming agent, which will cause the ink to
apply smoothly on the glass substrate without bubbles or
unevenness. A wide variety of defoamers are suitable, but preferred
are defoamers sold by BYK Chemie under the BYK tradename. Examples
of such defoaming agents are alkylvinyl ether polymers set forth in
U.S. Pat. No. 5,187,201, which is hereby incorporated by reference.
Examples of other defoamers include polyethers such as BYK-052,
BYK-053, and BYK-033. BYK-052 and -053 are polyethers such as
polyethylene or polypropylene glycol ethers, and in particular,
polyvinyl ethers. Also suitable is BYK-354 which is a polyacrylate
solution, and BYK-022 which is a mixture of hydrophobic solids and
foam destroying polysiloxanes in polyglycol. Preferably the
polyether defoaming agent is an alkoxylated alkyl phenol more
particularly a mixtures of petroleum distillates and an ethoxylated
alkyl phenol, such as that sold by BYK-Chemie under the tradename
BYK-033.
[0040] Adhesion Promoter
[0041] The ink compositions used in the invention also preferably
contain about 0.01-25%, preferably about 0.05-15%, more preferably
about 0.1-5% of a silane adhesion promoter which will enhance
adhesion of the cured resin to the glass surface. Examples of
silanes are silane esters, vinyl silanes, methacryloxy silanes,
epoxy silanes, sulfur silanes, amino silanes, or isocyanoto
silanes. Suitable silanes include organofunctional silanes of the
formula: 6
[0042] wherein
[0043] n=0-3
[0044] a=0-2 7
[0045] X is each independently CH.sub.3, Cl, OCOCH.sub.3,
OC.sub.2H.sub.4OCH.sub.3,(OC.sub.2H.sub.4).sub.2OCH.sub.3. or --OR,
where R is a C.sub.1-20 straight or branched chain alkyl,
preferably methyl or ethyl
[0046] Silanes having this formula are commercially available under
the Dynasylan trademark from Huls, America, Inc., Piscataway, N.J.
or Osi Specialities Inc. Other organofunctional silanes such as
those disclosed in U.S. Pat. No. 5,221,560, which is hereby
incorporated by reference, are also suitable. Such organosilanes
are acryloxyfunctional silanes including
3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethox-
ysilane, 2-methacryloxyethyltrimethyoxysilane,
2-acryloxyethyltrimethyoxys- ilane,
3-methacryloxypropyltriethoxysilane,
3-acryloxypropyltrimethyoxysil- ane,
3-acryloxypropyltriethoxysilane,
2-methacryloxyethyltriethoxysilane,
2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane,
etc. Suitable glycidoxy silanes include
3-glycidoxypropyltrimethoxysilane,
2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethyl silane,
and so on. Preferred for use in the compositions of the invention
are acryloxy-functional silanes, isocyanato silanes, and amino
silanes. The preferred acryloxy-functional silane is
3-methacryloxypropyl trimethoxy silane, which is sold by Huls
America, Inc. under the tradename DYNASYLAN MEMO. The preferred
amino silane is sold by Huls America, Inc. under the tradename
DYNASYLAN TRIAMO. The preferred isocyanoto silane is sold by Osi
Specialities Inc., under the tradename A-1310. In the preferred ink
compositions of the invention a mixture of three silanes is
preferred, generally 0.01-2% by weight of each.
[0047] Surfactant
[0048] The ink compositions also preferably contain contain
0.01-20%, preferably 0.5-10%, more preferably 1-5% by weight of a
fluorinated surfactant. The term "fluorinated surfactant" means a
fluorine containing compound having at least one liphophilic group
or portion and at least one hydrophilic group or portion. In
particular, fluorocarbon or fluorosilicone surfactants are most
desireable. Suitable surfactants include those set forth in U.S.
Pat. No. 4,961,976 which is hereby incorporated by reference.
Preferred are fluorocarbon surfactants, such as those marketed
under the Fluorad trademark by 3M Company. These fluorochemical
surfactants include fluorinated alkyl esters, fluorinated alkyl
polyoxyethylene ethanols, and the like. Particularly preferred are
nonionic fluorinated alkyl alkoxylates e.g. those marketed by 3M
under the trademark FC-171. Preferred are fluroinated C.sub.1-30
alkyl ethoxylates and propoxylates.
[0049] Photoinitiator
[0050] The ink compositions preferably contain a photoinitiator
which catalyzes the polymerization of the monomers upon exposure to
the radiation by which the monomers are curable. There are
generally two types of photoinitiators: free radical and cationic.
Free radical initiators are more commonly used with ethylenically
unsaturated monomers and oligomers, while cationic photoinitiators
are used with epoxy or vinyl ether functional resins. Preferably,
the compositions used in the invention contain free radical
photoiniators. Suitable free radical-type photoiniators include
carbonyl compounds such as ketones, acetophenones, benzophenones,
and derivatives thereof. Examples of such materials include, for
example, methyl ethyl ketone; benzophenone; benzyl dimethyl ketal;
1-hydroxycyclohexylphenylketone; benzyl-2-N,N-dimethylamino-1,4(4--
morpholinophenyl)-1-butanone; 2,2-dimethoxy-2-phenyl acetophenone;
2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one;
2-hydroxy-2-methyl-1-phenyl-propan-1-one;
4-(2-hydroxyethoxy)phenyl-(2-hy- droxy-2-methylpropyl)ketone; and a
mixture of bis(2,6-dimethyoxybenzoyl)-2- -4-4-trimethylpentyl
phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propa- n-1-one.
Preferred is a mixture of 25% bis(2,6-dimethyoxybenzoyl)-2-4-4-tr-
imethylpentyl phosphine oxide and 75%
2-hydroxy-2-methyl-1-phenyl-propan-1- -one, which is sold under the
tradename Irgacure 1700 by Ciba-Geigy.
[0051] Small amounts of cationically curable monomers or oligomers
may be used in the compositions of the invention, for example less
than about 10%, preferably less than about 5% by weight of the ink
composition. However, cationically cured compositions generally
exhibit a high bond strength to glass, such that if they are used
in substantial amounts in the composition of the invention, the ink
will not be stripped from the glass upon to alkali. If canonically
curable monomers or oligomers are used in the compositions of the
invention, ft is desirable to use cationic photoinitiators. The
term "cationic photoinitiator" means a molecule or ingredient
which, upon excitation, undergoes a photochemical transformation
which efficiently generates a species capable of initiating
cationic polymerization. If the ink composition of the invention is
cured by UV or actinic radiation rather than electron beam it is
desirable to add a cationic photoinitiator which catalyzes
cross-lining of the resin upon exposure to the radiation to which
the resin is sensitive. On the other hand, if the ink compositions
of the invention are cured with electron beam it may be possible to
dispense with the cationic photoinitiator. Various types of
cationic photoinitiators are suitable. Both ionic cationic
photoinitiators such as onium salts or organometallic salts are
suitable as well as non-ionic cationic photoinitiator such as
organosilanes, latent sulphonic acids and the like. Preferred are
photosensitive onium salts, in particular, onium salts such as
those disclosed in U.S. Pat. Nos. 4,058,401, 4,138,255, 4,161,478,
4,175,972, all of which are hereby incorporated by reference.
Triaryl sulphonium salts are most preferred, in particular triaryl
sulphonium salts such as those sold by Union Carbide under the
tradename Cyracure UVI 6990 and 6974. Also suitable are ferrocenium
salts such as those sold under the Irgacure tradename by
Ciba-Geigy, in particular Irgacure 261. Sulphonyloxy ketones and
silyl benzyl ethers are also good cationic photoinitiators. A
detailed analysis of the mechanism of cationic curing is disclosed
in "Photosensitized Epoxides as a Basis for Light-Curable Coatings"
by William R. Watt, American Chemical Society Symposium, Ser. 114,
Epoxy Resin Chemistry, Chapter 2, 1979, and in "Chemistry and
Technology of UV and EB Formulation for Coat Inks, and Paints,"
Volume 3, entitled "Photoinitiators for Free Radical and Cationic
Polymerization, K.K. Dietliker, pages 332-374 (1991), both of which
are hereby incorporated by reference. Photosensitive onium salts
are used as photoinitiators in cationic curing, in particular,
onium salts such as those disclosed in U.S. Pat. Nos. 4,058,401,
4,138,255, 4,161,478, 4,175,972, all of which are hereby
incorporated by reference. Triaryl sulphonium salts are most prefer
in particular triaryl sulphonium salts such as those sold by Union
Carbide under the tradename Cyracure UVI 6990 and 6974. The
photoinitiator is generally present at about 0.1-15%, preferably
about 0.5-12%, more preferably about 0.5-10% by weight of the total
composition.
[0052] The preferred ink compositions used in the invention
comprise:
[0053] 5-95% of an ethylenically unsaturated monomer or oligomer
containing at leas one few acid group,
[0054] 5-95% pigment, and
[0055] 5-95% of a monomer or oligomer free of acid groups.
[0056] More preferably, the ink composition comprises, in addition,
an ingredient selected from the group consisting of about 0.1-25%
of a silane adhesion promoter, about 0.01-10% of a polyether
defoaming agent, about 0.01-20% of a fluorinated surfactant, and
about 0.1-1% of a photoinitiator.
[0057] The Decorating Method
[0058] The term "ceramic" or "vitreous article" when used in
accordance with the invention shall mean glass, ceramic, tile, and
similar vitreous materials. The articles which may be decorated or
printed according to te method of the invention may be in any shape
or form, such as a container, sheet, tile, figurine, or the like.
In the preferred embodiment of the invention the article is made of
glass or ceramic and is a container, such as a cosmetic or beverage
container.
[0059] The ink composition is applied to the article to be
decorated in a predetermined design using a variety of printing
methods including screen printing, offset printing, gravure, hand
painting and the like. After the ink is applied the substrate or
article is irradiated with UV or actinic radiation using a
conventional UV light source. The term "UV" means ultraviolet light
which generally has a wavelength of 4 to 400, preferably 325 to 400
nanometers. The term "actinic" means radiation having a wavelength
of 200 to 600 nanometers. Electron beam may be used instead of a UV
light source. If a UV conveyer is used, it is set up so that the
substrate passes through the beam of radiation for an amount of
time appropriate to completely cure the ink composition and cause
it to adhere to the substrate. If desired, the substrate may be
moved through the conveyer in one or more passes to achieve the
required curing. The pr time varies de on the ink formula, but
generally curing is complete in a period of time ranging from
fractions of a second to 30 minutes. It is preferred, that by the
time the decorated substrate or article is removed from the
conveyer, the ink is completely cured and fused to the substrate
surface. In some cases it may be necessary to subject the newly
screened glass container to slightly elevanted temperature prior to
UV curing the applied ink on the substrate, or to an additional
post-UV cure application of beat to finally polymerize the ink on
the substrate. Preferably, the decorated substrate is subjected to
post-UV cure heating at a temperature of 90 to 200.degree. C.,
preferably 100-200.degree. C. for a period of 0.5 to 30
mintues.
[0060] The ink compositions are well suited for use in automated
systems such as the multiple color printing disclosed in coped
application Ser. No. 432,485, filed May 1, 1995 by Kamen, et al.,
entitled "Apparatus and Method For Screen Printing Radiation
Curable Compostions", or with the methods disclosed in U.S. Pat.
No. 5,562,951, both of which are hereby incorporated by
reference.
[0061] In another embodiment of the invention, it is possible to
make the ink composition of the invention without the pigment and
print it on the glass substrate in predetermined design according
to the methods described above. For example, a substrate such as a
container may be decorated in a pre-determined design by silk
screening the unpigmented ink composition on the substrate and
curing with the appropriate radiation. A layer of hot stamping foil
is then compressed against the substrate with a press which is head
to a temperature sufficient to cause the hot stamping foil to
adhere to the printed ink design but not to the ink-free areas of
the glass. Hot stamping foil is generally a laminate comprised of a
carrier material (often polyester or a similar material capable of
release), a release film between the carrier and a subsequent
decorative coat which is usually color or a metallized coat, most
often aluminum or colored aluminum. The foil may contain other
optional layers such as one or more protective layers, hot melt
adhesive layers, etc. between the metallized layer or layers and
the carrier material. More specifically, hot stamping foil can be
defined as a multilayer web comprised of a backing film carrier, a
release coating, one or more protective top coatings, one or more
color coatings, and a hot melt adhesive in that order. The hot
stamping foil is then compressed aghast the container with the hot
melt adhesive layer being compressed against the substrate. The
compress, which may be a standard hot stamping press or a hand held
press, is heated to a temperature sufficient to cause the hot melt
adhesive layer of the hot stamping foil to adhere to the ink
decorated portion of the squats. Generally this temperature ranges
from about 250 to 400.degree. F. Temperatures higher than this may
cause deterioration of the hot stamping foil. The application of
heat causes the adhesive side of the hot stamping foil to become
adhesively adhered to the ink design but not to the ink-free areas
of the substrate. When the compress is removed, a portion of the
foil laminate adheres to the ink decoration but not to the ink free
areas of the glass. In particular, adhered to the ink design on the
substrate is the hot melt adhesive layer, the color coatings, and
the protective top coatings, in that order, of the hot stamping
foil. Portions of the release coating may or may not be adhered to
the protective top coating because the release coating is designed
to melt upon application of heat and cause the polyester carrier
backing layer to release from the protective top coat layer and
some remnants may remain.
[0062] The resulting hot stamped substrate exhibits a metallic
gold, silver, or colored appearance depending on the color of the
hot stamping foil.
[0063] In yet another embodiment of the invention, it is possible
to provide a decorated substrate which has a two tone effect where
all or a portion of the colored ink on the sure is hot stamped. In
this instance a pigmented ink composition is applied to the
substrate in a predetermined design and cured by exposing it to the
radiation by which it is curable for a time sufficient to effect
complete cure. Hot stamping foil is applied as described above to
either the entire ink design or to only a part (i.e. complete or
partial registration). If the hot stamping foil is applied in
partial registration, or applied to a portion of the pigmented ink
design, a pleasant two tone effect is achieved. Many times it is
more economical to print the entire design on the substrate using
colored ink and then hot stamp over the desired portion of the
design, rather than applying clear ink and hot stamping, and then
printing colored ink in the desired design in a second
application.
[0064] The ink compositions of the invention provide sufficient
adhesion to glass as well as exhibiting sufficient resistance to
scuffing and scratching to make the decorated articles suitable for
use on commercial beverage and cosmetic bottles.
[0065] The Stripping Method
[0066] The ink compositions of the invention can be removed from
glass upon expose of the glass to alkali. In particular, the free
acid groups found in the polymerized ink composition are capable of
reacting with the hydroxyl groups of the base to form a salt which
is easily stripped or removed from the glass.
[0067] The aqueous alkaline solution comprises about 1-20%,
preferably about 2-15%, more preferably about 2-12% by weight
alkali. Suitable akali materials include hydroxides (e.g. alkali
metal and alkaline earth metal hydroxides) such as sodium
hydroxide, potassium hydroxide, calcium hydroxide, and the
like.
[0068] The cured ink compositions should be removed from the glass
upon exposure to the aqueous alkali after a period of about 1 to
120, preferably about 1-60, more preferably about 1-30 minutes. The
glass substrate is generally immersed in the aqueous alkali
solution for the appropriate time period, after which the ink
compositions are removed from the glass surface.
[0069] Preferably the glass container is subjected to the aqueous
alkaline solution at a temperature of 60 to 100.degree. C., more
preferably 70 to 95.degree. C., most preferably 72 to 90.degree.
C.
[0070] In the most preferred embodiment of the invention the ink
composition is removed from the glass containers after exposure of
the glass to a 4% (approximately) aqueous solution of sodium
hydroxide at a temperature of 70 to 100.degree. C., after 1-15
minutes.
[0071] The decorating method and compositions of the invention are
excellent for use on glass containers used in the returnable
beverage market. The decorative indicia applied according to the
invention remains on the glass for the useful commercial life of
the container, yet can be easily removed upon exposure to an
aqueous alkali solution. This eliminates the need for paper labels
and decals, which results in a significant cost savings. Also, the
indicia are much more aesthetically pleasing, similar to the
aesthetics achieved with ACL. Thus, beverage and cosmetic
manufacturers are able to offer glass containers that provide
aesthetics similar to ACL, with indicia that can be easily removed
upon exposure to alkali solutions when the glass container is
returned to the filler.
[0072] The invention will be further described in connection with
the following examples, which are set forth for the purposes of
illustration only.
EXAMPLE 1
[0073] A white ink composition was made as follows:
1 grams wt % Dipentaerythritol pentaacrylate.sup.1 25.0 24.8 Epoxy
acrylate + tripropylene glycol acrylate.sup.2 27.0 26.8 Aromatic
acid methacrylate 1/2 ester 5.0 5.0 in ethoxylated
trimethylolpropane triacrylate.sup.3 Beta carboxyethyl
acrylate.sup.4 10.0 9.9 Aromatic urethane acrylate with 10.0 9.9
polyacrylated polyol diluent.sup.5 Titanium dioxide (pigment) 17.0
16.9 Irgacure 1700.sup.6 3.0 3.0
Gamma-isocyanotopropyltriethoxysilane- .sup.7 0.5 0.5
3-methacryloxypropyl trimethoxysilane.sup.8 0.5 0.5
Trimethoxysilylpropyldiethylene triamine.sup.9 0.5 0.5 Fluorinated
alkyl alkoxylate.sup.10 0.5 0.5 BYK-033.sup.11 1.0 1.0
Modaflow.sup.12 0.8 0.8 .sup.1SR399, Sartomer Company, Inc. (other
polymerizable reactant) .sup.2CN104, Sartomer Company, Inc. (other
polymerizable reactant) .sup.3SB500 E50, Sartomer Company, Inc.
(polymerizable reactant with free acid group) .sup.4B-CEA, UCB
Radcure Inc. (polymerizable reactant with free acid group)
.sup.5EB-220, UCB Radcure Inc. (other polymerizable reactant)
.sup.6Ciba-Geigy Corp. Mixture of 25% by weight
bis(2,6-dimethoxybenzoyl)-2,4-,4-trimethylpentyl phosphine oxide
and 75% by weight 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
(photoinitiator) .sup.7A-1310, Osi Specialities, Inc. (adhesion
promoter) .sup.8DYNASYLAN MEMO, Huls America Inc. (adhesion
promoter) .sup.9DYNASYLAN TRIAMO, Huls America Inc. (adhesion
promoter) .sup.10FC-171, 3 M Company (surfactant) .sup.11BYK-033,
BYK-Chemie. A mixture of 92% by weight of petroleum distillates and
5% by weight ethoxylated alkyl phenol (defoaming agent)
.sup.12Modaflow, Monsanto, Inc. Ethyl acrylate and 2-ethylhexyl
acrylate copolymer (defoaming agent)
[0074] The ink composition was made by combining the ingredients
and mixing well.
EXAMPLE 2
[0075] A blue ink composition was made as follows:
2 grams wt % Dipentaerythritol pentaacrylate.sup.1 25.0 23.9 Epoxy
acrylate + tripropylene glycol acrylate.sup.2 27.0 25.8 Aromatic
acid methacrylate 1/2 ester 5.0 4.8 in ethoxylated
trimethylolpropane triacrylate.sup.3 Beta carboxyethyl
acrylate.sup.4 10.0 9.6 Aromatic urethane acrylate with 10.0 9.6
polyacrylated polyol diluent.sup.5 Ultramarine blue 5009.sup.13
20.0 19.1 Irgazin blue X-3367.sup.14 1.0 0.9 Irgacure 1700.sup.6
3.0 2.9 Gamma-isocyanotopropyltriethoxysilane.sup.7 0.5 0.5
3-methacryloxypropyl trimethoxysilane.sup.8 0.5 0.5
Trimethoxysilylpropyldiethylene triamine.sup.9 0.5 0.5 Fluorinated
alkyl alkoxylate.sup.10 0.5 0.5 BYK-033.sup.11 1.0 1.0
Modaflow.sup.12 0.5 0.4 .sup.1SR399, Sartomer Company, Inc. (other
polymerizable reactant) .sup.2CN104, Sartomer Company, Inc. (other
polymerizable reactant) .sup.3SB500 E50, Sartomer Company, Inc.
(polymerizable reactant with free acid group) .sup.4B-CEA, UCB
Radcure Inc. (polymerizable reactant with free acid group)
.sup.5EB-220, UCB Radcure Inc. (other polymerizable reactant)
.sup.6Ciba-Geigy Corp. Mixture of 25% by weight
bis(2,6-dimethoxybenzoyl)-2,4-,4-trimethylpentyl phosphine oxide
and 75% by weight 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
(photoinitiator) .sup.7A-1310, Osi Specialities, Inc. (adhesion
promoter) .sup.8DYNASYLAN MEMO, Huls America Inc. (adhesion
promoter) .sup.9DYNASYLAN TRIAMO, Huls America Inc. (adhesion
promoter) .sup.10FC-171, 3 M Company (surfactant) .sup.11BYK-033,
BYK-Chemie. A mixture of 92% by weight petroleum distillates and 5%
by weight ethoxylated alkyl phenol (defoaming agent)
.sup.12Monsanto, Inc. Ethyl acrylate and 2-ethylhexyl acrylate
copolymer (defoaming agent) .sup.13Wittaker, Clark, & Daniels
(pigment) .sup.14Ciba Pigment Division
[0076] The ink composition was made by combining the ingredients
and mixing well.
EXAMPLE 3
[0077] A white ink composition was made as follows:
3 grams wt % Aromatic acid methacrylate 1/2 ester 25.0 24.5 in
ethoxylated trimethylolpropane triacrylate Beta carboxyethyl
acrylate.sup.2 35.0 34.2 Monofunctional acrylate resin.sup.3 15.0
14.7 Epoxy acrylate + tripropylene glycol acrylate.sup.4 5.0 4.9
Titanium dioxide 15.0 14.7 Iragacure 1700.sup.5 3.0 2.9
BYK-033.sup.6 1.0 1.0 3-methacryloxypropyl trimethoxysilane.sup.7
0.6 0.6 Gamma-isocyanotopropyltriethoxysil- ane.sup.8 0.6 0.6
Methyl diethanolamine 2.0 1.9 .sup.1SB500 E50, Sartomer Company,
Inc. (polymerizable reactant with free acid group) .sup.2B-CEA, UCB
Radcure Inc. (polymerizable reactant with free acid group)
.sup.3Aromatic oligomer containing pendant carboxy functional
groups, Henkel Corporation (polymerizable reactant with free acid
group) .sup.4CN104, Sartomer Company, Inc. (other polymerizable
reactant) .sup.5Ciba-Geigy Corp. Mixture of 25% by weight
bis(2,6-dimethoxybenzpyl)- -2,4-,4-trimethylpentyl phosphine oxide
and 75% by weight 2-hydroxy-2-methyl-1-phenyl-propan-1-one.
(photoinitiator) .sup.6BYK-Chemie, A mixture of 92% by weight
petroleum distillates and 5% by weight ethoxylated alkyl phenol
(defoaming agent) .sup.7DYNASYLAN MEMO, Huls America Inc. (adhesion
promoter) .sup.8A-1310, Osi Specialities, Inc. (adhesion
promoter)
[0078] The ingredients were combined and mixed well.
EXAMPLE 4
[0079] An ultramarine blue composition was made as follows:
4 grams wt % Aromatic acid methacrylate 1/2 ester 25.0 24.2 in
ethoxylated trimethylolpropane triacrylate.sup.1 Beta carboxyethyl
acylate.sup.2 30.0 29.1 Monofunctional acrylate resin.sup.3 15.0
14.5 Epoxy acrylate + tripropylene glycol acrylate.sup.4 5.0 4.8
Irgazin blue X-3367.sup.3 1.0 1.0 Ultramarine blue 5009.sup.6 20.0
19.4 Iragacure 1700.sup.7 3.0 2.9 BYK-033.sup.8 1.0 1.0
3-methacryloxypropyl trimethoxysilane.sup.9 0.6 0.6
Gamma-isocyanotopropyltriethoxysilane.sup.10 0.6 0.6 Methyl
diethanolamine 2.0 1.9 .sup.1SB500 E50, Sartomer Company, Inc.
(polymerizable reactant with free acid group) .sup.2B-CEA, UCB
Radcure Inc. (polymerizable reactant with free acid group)
.sup.3Aromatic oligomer containing pendant carboxy functional
groups, Henkel Corporation (polymerizable reactant with free acid
group) .sup.4CN104, Sartomer Company, Inc. (other polymerizable
reactant) .sup.5Ciba Pigment Division (pigment) .sup.6Whittaker,
Clark, & Daniels (pigment) .sup.7Ciba-Geigy Corp. Mixture of
25% by weight bis(2,6-dimethoxybenzoyl)- -2,4-,4-trimethylpentyl
phosphine oxide and 75% by weight
2-hydroxy-2-methyl-1-phenyl-propan-1-one. (photoinitiator)
.sup.8BYK-Chemie, A mixture of 92% by weight petroleum distillates
and 5% by weight ethoxylated alkyl phenol (defoaming agent)
.sup.9DYNASYLAN MEMO, Huls America Inc. (adhesion promoter)
.sup.10A-1310, Osi Specialities, Inc. (adhesion promoter)
[0080] The ingredients were combined and mixed well.
EXAMPLE 5
[0081] A white ink composition was made as follows:
5 grams wt % Aromatic acid methacrylate 1/2 ester 25.0 22.8 in
ethoxylated trimethylolpropane triacrylate.sup.1 Epoxy acrylate +
tripropylene glycol acrylate.sup.2 10.0 9.1 Beta-carboxyethyl
acrylate.sup.3 30.0 27.3 Monofunctional acrylate resin.sup.4 15.0
13.7 Polytetrafluoroethylene.sup.5 1.0 0.9 Titanium dioxide 17.0
15.5 Irgacure 1700.sup.6 3.0 2.7 BYK-033.sup.7 1.5 1.4
3-methacryloxypropyl trimethoxysilane.sup.8 0.6 0.5
Gamma-isocyanotopropyldiethylene 0.6 0.5 triamine.sup.9
Monodiethanolamine 3.0 2.8 Benzophenone 3.0 2.8 .sup.1SB500 E50,
Sartomer Company, Inc. (polymerizabe reactant with free acid group)
.sup.2CN104, Sartomer Company, Inc. (other polymerizable reactant)
.sup.3B-CEA, UCB Radcure Inc. (polymerizable reactant with free
acid group) .sup.4Aromatic oligomer containing pendant carboxy
functional groups, Henkel Corporation (polymerizable reactant with
free acid group) .sup.5SST-4, Shamrock Technologies, Inc.
(thickening agent) .sup.6Ciba-Geigy Corp. Mixture of 25% by weight
bis(2,6-dimethoxybenzoyl)-2,4-,4-trimethylpentyl phosphine oxide
and 75% by weight 2-hydroxy-2-methyl-1-phenyl-propan-1-one
(photoinitiating agent) .sup.7BYK-Chemie. A mixture of 92% by
weight petroleum distillates and 5% by weight ethoxylated alkyl
phenol (defoaming agent) .sup.8DYNASYLAN MEMO, Huls America Inc.
(adhesion promoter) .sup.9A-1310, Osi Specialties, Inc. (adhesion
promoter)
[0082] The composition was made by combining the ingredients and
mixing the ingredients well.
EXAMPLE 6
[0083] A blue ink composition was made according to the following
formula:
6 grams wt % Aromatic acid methacrylate 1/2 ester 25.0 24.7 in
ethoxylated trimethylolpropane triacrylate.sup.1 Epoxy acrylate +
tripropylene glycol acrylate.sup.2 10.0 9.9 Beta-carboxyethyl
acrylate.sup.3 25.0 24.7 Monofunctional acrylate resin.sup.4 15.0
14.8 Ultramarine blue 5009.sup.5 15.0 14.8 Irgazin blue
X-3367.sup.6 1.5 1.5 Polytetrafluoroethylene.sup.7 1.0 1.0 Irgacure
1700.sup.8 3.0 3.0 Benzophenone 3.0 3.0 BYK-033.sup.9 1.5 1.4
3-methacryloxypropyl trimethoxysilane.sup.10 0.6 0.5
Gamma-isocyanatopropyltriethoxysi- lane.sup.11 0.6 0.5 .sup.1SB500
E50, Sartomer Company. Inc. (polymerizable reactant with free acid
group) .sup.2CN104, Sartomer Company, Inc. (other polymerizable
reactant) .sup.3B-CEA, UCB Radcure, Inc. (polymerizable reactant
with free acid group) .sup.4Aromatic oligomer containing pendant
carboxy functional groups, Henkel Corporation (polymerizable
reactant with free acid group) .sup.5Whittaker, Clark & Daniels
(pigment) .sup.6Ciba Pigment Division (pigment) .sup.7SST-4,
Shamrock Technologies Inc. (thickening agent) .sup.8Ciba-Geigy
Corp. Mixture of 25% by weight
bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide and
75% by weight 2-hydroxy-2-methyl-1-phenyl-propan-1-on- e.
(photoinitiator) .sup.9BYK-Chemie. A mixture of 92% by weight
petroleum distillates and 5% by weight ethoxylated alkyl phenol
(defoaming agent) .sup.10DYNASYLAN MEMO, Huls America Inc.
(adhesion promoter) .sup.11A-1310, Osi Specialties, Inc. (adhesion
promoter)
[0084] The ingredients were combined and mixed well.
EXAMPLE 7
[0085] The white ink composition of Example 2 was applied to
alcoholic beverage bottles by screen printing with a 230 mesh
screen using an Autoroll M-25 semiautomatic screen printing machine
The ink on the bottle was screened by exposure UV light from a P600
power supply having a 9 mm. D bulb. The curing speed was less then
one second per bottle. Then, the blue ink of Example 2 was screened
onto the bottle in partial registration with the cured white ink.
The ink was cured upon exposure to the UV light source. The bottle
was then subjected to post heat curing at a temperature of
100.degree. C. for 30 minutes. The indicia adhered well to the
bottle and exhibited bright, true coloration.
EXAMPLE 8
[0086] The finished bottles decorated in accordance with Example 7
were immersed in a water bath containing 4% sodium hydroxide at a
temperature of 72.degree. C. The cured inks were completely removed
form the bottles after 4 minutes.
[0087] While the invention has been described in connection with
the preferred embodiment, it is not intended to limit the scope of
the invention to the particular form set forth but, on the
contrary, it is intended to cover such alternatives, modifications,
and equivalents as may be included within the spirit and scope of
the invention as defined by the appended claims.
* * * * *