AU539112B2 - New compositions - Google Patents

Description

al a~ijo uioa

limB alol KUl uxd aJ

zr.6' 'lay s.Lkalvd 01 'I11O VITOSWo 10 4

ISO

1111 I.2 I 4 li 11.6 11111- 1111-12.0

MIICROCOPY RESOLUTION -TEST CHART NATINAL.BUREAUI OF SIANbAFOS*-1963-A

1* V

AUSRA A4 Form 1 P fION F4 (NONCOVN1,) A STRALIAt CP Pat6nts.Act -1952--1973 (a Inser names(s) appilican

34(4) (70 r 0 NVIN 1IR ECT ION SEE EOLI O---L6Lw g Is of Invent

D 'E ETE -14 -L Inset

I name(s) declaranl nset a- o~b)7 Melissa Street, dres~es ofap-REGENTS PARK., New South Wales 2143 Ins* address)c AUSTRALIA of decla,

Insert titlehereby apply for the grant of a Patent for an 1 0

of ~~inventionvtor entitled *...CI*D~ZJ

RECrEIVED ~a'~~aa ta oa

Dae 1 AUG 1979 which is described in the accompanying provisional 0

Rtecelt~~

p oe~arat~n ?y/0ur address for service is: C/o Arthur 44 mien Spec iflcwliofl S. Cave Co., Patent Attorneys, I. Alfred-Street, actual i. tentorf! 45 450 Sydney, 2000, in the State of New South Wales, a 454500 40 a Australia. 45

I ()Insert Icua Insert date DATED t;-his day of AlL4 .t 19 0* a mn;tr(

Form signed. 45 8*

Signature(s) (e)STAYBOND PTY. LTD. of O applicant(s), if aEItPae. co~a~yto be execu- tonys *8 .0 a ao a so ted a manner bin- RH *450 S.CV&CO a ding on: the company (f)ARUS.CV&Co 45 ft upplcam~ (azcord'ing to its Ar- derive(s)t from a.u ticles of Adsoc-iati1or1 00 Inwantari Seal, if any. ES G. SIELY. PaI.P.k..

To, THE COMMISSIONER PATENTS. c ARTHUR S. CAVE 4TENT AND TRADE MARK AfTTORNEYS SYDNEY TEN D

0

.4

'orm Regulation

2 The present :Invention relates to water-based corpositions,

and methods of operation using the water-based compositions.

Whilst initially developed in relation to inks and related (I printing methods, the comnof-i-n nrl msz4-hnI rl F +-hK

Ji,

PATEN(FDECLARATION (NON-CONVENTION) 'Regulation

,T12(l) COMMONWEALTH OF AUSTRALIA PatentsAct 19-52 DEL!AININ SUPPORIT OF AN APPLICATION "FOR A PATENT uportoi (a)lr~rful te Aplcaio n mae y a) M01NOCURE PTY. LIMITED

It) Insert title for a pabtfraniv ni) nild nild of znntion. actfraiheto

IMPROX/EMENTS-IN OR RELATING TO POLYMERIZABLE WATER-BASED COATING COMPOSITIONS AND USES THER~EOF Insert full K Gog ART marne(s) of IKe~ evin Gog ART de lrndec.

Insert of(d) 13 Lucas Avenue, Russell Lea, utai of declarant(s). Au

do solemnly and sincerely declare as follows:- i. I EHnt/We arc the "appli:An(s)f6r tha pttzt.

(Orin the case of an applic ation by a body c_oErjate. Cu00V Insert nari~e I* I am! We tie-authorized by MON OCURE PT. L.IMI .TE.D of I6ody.... oC 0 rporate,

the applicant for the patent to make thids declaration on its behalf.

(Or, where a p eson other than the inventor is the a pjiqcant. (f 1. full Kenneth Stanley JONES and Kevin G~orge..JARRE namve(s) of

0 Insert of) Of 95 Bettington Road, Dundas, N.S.W. 2117, Australia; ftklms~ej f aictual, and 13 Lucas Avenue, Russell Lea, N.S.W. 2046, Australia respectively

are the actual inventor(s) of the invention and the facts upor which the applicant(-- isfa entitt-d to make the application. are as follows:- (h,st t h MONOCURE PTY. LIMITED is the assignee of the said loies il invention from STAYBOND PTY., LIMITED who, in turn,

w~astheassignee of the said invention from the said Ingetefs. inventors,

.Declaredgt Sydney this 9 th day of 198 4

K.G. JARRET q

To: ignatutre of Declarant(g The Commissioner of Patents

ARTHUR S. CAVE CO. PATENT AN6~ TRAD.14MARK ATTORNEYS SYDNdEY k

(12) AUSTRALIAN PATENT ABRIDGMENIT (19) AU (11) AU-B-61909/80

(54) COATING AND CURING METHOD (71) MONOCURE PTY. LIMITED (21) 61909/80 539112 (22) 31.8.79 (23) 29.8.80 (24) 31.V.79 (43) 5.3.81 (44' 13.9.84 3 (51) C08F 2/48 C08F 2/50 C08F 2/54 C08F 2/44 C08J 9/20 C09D 11/10 C09D 3/81 PE 0288, PE 1229 (72) KENNETH STANLEY JONES AND KEVIN GEORGE JARRETT (74) CA (56) 70825/74 485825 47.7-481, 47.7-4 7, 47.7-56 18486/70 449670 09.4-34 67235/65 09.4-35, 09.4-37 47.7-491 (57) Claim

1. A method of coating upon a suitable substrate which

comprises the steps of applying, to a said substrate, a polymerizable water-based coating composition which does not dye-sfu 7'iQme-rf o- pof-ime.ic require air-drying and which comprises a coating compound,

and an aqueous monomer system, the said system comprising at least one water-soluble or water-miscible or water-dispersible

eLhylenically unsaturated monomer and a photo-initiator

catalysb as required; and subjecting the so-applied composition

to curing, in the absence of hceat and without preliminary air-

drying, by UV radiation in the presence of the said photo-

initiator catalyst or by electron beam radiation, the aqueous monomer system being thereby polymerized.

NU AU 34 4

116±16/14

COPMNWEALTE O6F AUSL IAT- Form Reqlation L909/80 PATENTS, ACT, '1952 13 2

COM1PLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE 53> 31.8.79 Short Titlet 3 1 V .79 61909 W8 13 .9 .84 Int., Cl F 2/44

Application Number: Lodged:

0 C 0

00 oComplete Specifica.tion-Lodged: 0000 Accepted: 100

0 C, Upsedt Published: *0000 C. 0 0

O 00~riority: *Po0

0000

whi ch

Related Art: *000 0 0 s not 0 000 0 4000 0000 @0 0 0 0 .2-d, 0*

ng at 00 00 0 0 TO BE COMPLETED BY APPMjCANT 00

ersible 0 0Namie of Applicant: !QU,99TY. LIMITED Y 1 000* 0 00 0* 0 position 'Addessof Applicant:X Melissa Street, Regents Park, N.S.W. 2143, 00 0 00 0 00

:iy ai r- Australia.

Actual Inventor: Kenneth Stanley Jones Kevin George Jarrett q ucous 25 1 Address for Service: ARTHUR S. CAVF &a Patent and Trade Mark Attorneysg 1 Alfred Street, Sydney, New South Wales, Australia, 2000.

~Compete Specification for the invention entitledt

J'14 4 The following statement isa full description of this invention, inluding the best method of performing it known to me-- A

A;c -I- i~) pji, !t4 9

N; The present invention relates to water-based compositions,

and methods of operation using the water-based compositions.

Whilst initially developed in relation to inks and related

printing methods, the composition and method. of the invention

have been found to be equally efficacious in other coating -ai4- i--binding environments.

m Most current coatings and bin& consist of compositions

which form a film or lattice as the carrier therefor evapor-

ates. These compositions generally comprise inert dispersed

4 *1i @o

oc" 10 solids or soluble substances of desired properties,

properties are obtained on evaporation. In which

printing appli- 4000 oo o cations in particular, these properties (viz. film hardness,

o gloss, adhesion) must be achieved rapidly in order for the 0 0 0 o"oo substrate to withstand high substrate velocity through the

press. Thus enormous quantities of energy are required to

I 0 0 b.6 be expended and "fast" organic solvents are used, thereby introducing fire hazard and pollution problems. o The use of water-based inks as a substitute for solvent- o0 **oo based products is not novel per se. Hitherto, such water-

i i oe based inks were in the form of dispersion polymers.

while water-based inks had potential advantages over solvent- However,

o* based inks such as cost savings, elimination of fire hazard,

reduction in air pollution and more importantly the absence

of a hydrocarbon base (hydrocarbons being subject to increas-

ing shortages and subasquent price rises) they also had

numerous disadvantages such as difficulties with pigment

dispersion, gloss, film thickness, curing time and flow

characteristics which difficulties resulted in aqueous inks

2

1'^ 11 O ir

Y r 1-

based on dispersion polymers not being attractive.

Against this background, the principal object of the

invention is seen as the provision of a water-based ink which

obviate, the disadvantages inherent in prior art aqueous

inks as indicated above (without resurrecting the disadvan-

tages associated with solvent-based inks) ard which, at the

same timc, is inexpensive, easy to apply, and devoid of

toxicity. Further objects include the provision of other

water-based coating -ad binding compositions which (as our

o 10 research developed) were found to be superior to such cQ o

compositions of the prior art, and (ii) within the ambit of S our inventive concept. These will be elaborated hereafter. 0 cordingly, in one broad aspezct, the indcntion p-rovideo

a pol rizable water-based composition comprising a primary

cOmponent d an aqueous monomer system, wherein the said

gystem compris at least one water-soluble or water-miscible

(or -dispersible) onomer; t:he composition being curable by

radiation or otherwis

.o In the foregoing sy tem, a reactive monomer is used

which is soltble in a very ec nomical carrier viz. water.

The water carrier imparts a flui *c mobility to the compo-

sition. It is not necessary for thi carrier to be removed

by vaporation for the composition to a ain its desired

physical properties. The composition may b cured to a solid

polymer, with carrier (or proportion thereof) in situ, by

the application of radiation. The radiation may of any

type heat, electron beam, gamma and ther

adiato)whih toini ad utain plymzriation.

3

In the following examples, the compositions and related

methods of the invention are illustrated. As elsewhere, fi-ay"^ irt WA ri-wJ L. T- r i* i, 4 h ii

Accordingly the invention provides a method, as defined A of the below, which utilizes a polymerizable water-based coating

ink which composition which does not require air-drying. The composition V ueous comprises a dyestuff, pigment or polymeric coating compound, a

isadvan- 5 and an aqueous monomer system wherein the said system 5 cc

at the comprises at least one water-soluble ir I: i or water-miscible or

d of cc water-dispersible ethylenically unsaturated monomer and a

other photo-initiator catalyst as required. as The said composition

(as our is adapted to be applied to a substrate and is curable

o such 10 in the absence of heat by UV radiation in the presence of the 0 6 10 1 i ambit of said photo-initiator catalyst or by electron beam radiation. 66

reafter. In the foregoing system, a reactive monomer is used 6a 0 is -i o 0

.oo 0 which is soluble in a very economical carrier viz water. The 06 6 is I, 6 66

a primary 0s 6 water carrier imparts a fluidic mobility to the composition. 6 said 15 It is not necessary for this carrier to be removed by 15 pa

r-miscible evaporation for the composition to attain its desired physical *066 6 Sy

'i *6*0

0 *6 cable by properties. The composition may be ured to a solid polymer, 66 6 de 6 6*1

*600 with carrier in situ, by the application of UV or electron 6 00Q 66 6 00 6066s

E used e0 60 beam radiation, which is able to initiate and sustain ma

qater. 20 polymerization. 20 S'U 60 0 *6 0 06 *90 9 compo- de I The present invention thus provides a method of coating 6 *6 60 6

removed de

3ired A:- 0*r 00 6

00606b' 666

6

6 on a suitable substrate.

steps of applying the above-defined polymerizable Broadly this method comprises the

water-based

:o a solid composition to a said substrate; and subjecting the so applied PC

Itu, by to curing in the absence of heat and without 25 S1] 25 composition of any preliminary air-drying by UV radiation in the presence of a Id ther said photo-initiator catalyst or by electron beam radiation, f

ac whereby the aqueous monomer system reacts to form a hydro-

phobic polymer (the water present being rapidly lost e.g. by Cu i FGAe 0I1 i-i being absorbed into the substrate and/or by evaporation) w u 4 ~i~k?

"i'i Y II

i Continex N326 Compos (carbon black pigment) 7.45 water 60% N-1 40.0

O^E h r, I jj 1 i:

By controlling the rate and ultimate extent of water

release, the resultant coating flexibility can be controlled.

In its coating aspects,, the low viscosity composition, in addition to the aqueous monomer system and the appropriate

coating pigment, dyestuff et al) component will invariably contain a cataly~st to promote curing, and may also contain one or more non-reactive water borne components (such as emulsions, dispersed or dissolved resins, polymers, and the like). The composition will generally be formulated in the 10 light of such factors as the type of coating required and the

u^ type of radiation to be employed. For example, when curing is carried out by means of electron beam radiation, a catalyst

Co is not required.

The especially preferred aqueous monomer system is a one-

part monomer system; however, a two- or three-part monomer

system may also be used. These are described in further

detail below.

The water-soluble or -miscible (or -dispersible) monomer may be selected from any conventional monomer. Examples of such monomers include acrylic and methacrylic acid and derivatives thereof; acrylamide and N-methylol acrylamide and

derivatives thereof; modified acrylamide, especially acryl- amide modified with aldehydes and the like to ultimately form

polymerization-condensation type polymers; and pyrrolidones

such as vinyl pyrrolidones and mixtures thereof.

The photo-initiator catalysts are generally conventional

free radical-producing components which are chosen in

acco 'dance with the type of UV radiation to be employed for

curing. Their purpose is to initiate and/or increase the

L"/y0 rate of reaction. The benzildimethylketal compound known as

I I

"IRGACURE 651" (a registered Trade Mark of Ciba-Geigy) is a

typically suitable compound for promoting (the initiating

effect of) UV radiation. Where curing is effected by electron

beam radiation a catalyst is not required. The catalyst may

be added simultaneously with the monomer. Alternatively, it

may be added subsequently together with other optional

conventional additives (such as fillers), or as prior appli-

cation to the substrate upon which the composition is

subsequently to be applied. o 10 A plasticizer, which functions to improve the flexibility

of the cured composition, preferably a humectant plasticizer

may also be incorporated. Typical examples are calcium and

zinc chloride, sugar, glycerine aid glycols; other examples

include synthetics such as starch and starch derivatives,

polyvinyl alcohol, gum and modified cellulose. The aforesaid

e non-reactive water borne components, which are exemplified by

emulsions or dispersed or dissolved resins or polymers, do not

take part in the polymerization reaction. However, they are

easily dispersed o dissolved in the compositions and

function to improve the end properties.

4 0 t 0 ft

~ih

6

A II *I~LYY(~IIY ii.

0:

u--rr rrn1rvnrC h~ rrrTn'r m2r inr _It cw~~~~rr ~r~

c6nve ional additives (such as fillers), or as prior

applicati to the substrate upon which the composition

is subsequent to be applied.

The plastic er, which functions to improve the flex-

ibility of the cured mposition, is preferably a humectant

plasticizer. Typical exa les are calcium and zinc chloride,

sugar, glycerine and glycols; other examples include

synthetics such as starch and star derivatives, polyvinyl

.org 10 alcohol, gum and modified cellulose. e eforesaid non-- 6 ft reactive water borne components, which are xemplified by P 6~ 0, emulsions or dispersed or dissolved resins or lymers, do 6 P60,00 6 0, not take part in the polymerization reaction. How er, they

are easily dispersed or dissolved in the compositions aod fj;M j:%p :p W 41- n- A 4- A. S-

In the printing ink applications, where the coating

weight is very low, oxygen inhibition can be a performance P6D

ft #0q problem. In one optional form of the invention, we overcome

the problem by externally applying nitrogen to the printed

20 substrate. Alternatively we may add to the system chemicals

which form in situ carbon dioxide or nitrogen during poly- ft ft 6 ft a0 merization, such chemicals being for example latent CO 2

producing alkali basic carbonate for an acidic form-

ulation). In two-part monomeric systems, acid-base reactants

may be used, such as hydrochloric acid and basic carbonate

sodium bicarbonate or ammonium carbonate). In the

one-part monomeric system, a basic carbonate alone may be

used. The monomer system during reaction turns acid and

7

-j

['p

thus subsequet~tly reacts with the carbonate alkali to

ultimately form CO 2

Amplifying in respect of thli monomeric systems, a

'three-part system may comprise a first water-soluble or

-miscible (or-dispersible) monomer part, a second part

including plasticizer a low-cost carbohydrate plasti-

cizer) an acid and a free-radical catalyst, and a third

part comprising a plasticizer, a CO 2inclusive alkali and

a reducing redox couple. The three parts may be mixed and, 4 44 ~A 4 4 10 when so mixed, foaming and polymerization take place. 44 4 #044 4 A two-part monomer system may have one part including 0444 4 4 04 4 a watce-soluble or -miscible (or -dispersible) monomer, a 4 44*44 4 4 plasticizer te.g. a carbohydrate plasticizer), a CO 2 incluasive o 0* 4 4 0044 alkali and a U.V. catalyst, and a second part consisting of

carbohydrate plasticizer sol~ution, and acid (the parts may

04*0 be alternatively constituted as indicated in the detailed 4 4 4044 o4, examples below). When such parts are mixed and cured (e.g. 00 4 0 04 by 'exposure to U.V. light), polymerization, with formation 44 44 0 o 44 of CO2 gas, takes place. The gas so formed produces foaming

and oxygen is sparged. t' 4 .4 4 4 With two- and three-part systems, foanirpg commences 44 4 4 O 00 immediately the components are combined, whereas the poly-

merization reaction takes longer and thus the formed CCO 2

bubbles are prematurely released. These systems are there-

fore not as suit~ible for printing (or other) thin film

applications as a one-part monomer system which is

especially preferred. Such a system may comprise a water-

soluble or -miscible (or -dispersible) mo~nomer, a latent i /22 S

CO 2 producing alkali, a humectant plasticizer and a U.V.

catalyst. Upon exposure to a U.V. light source, polymer-

ization coinmences, wherein an acidic environment is produced

which in turn reacts with the alkali to form CO2. Prior

to gassing commencing, polymerization occurs and formed gas

is entrapped in a viscous polymer mucilage. Q) S

As indicated above, the coating component may be a .1 dyestuff or pigment. These terms encompass water-soluble

dyestuffs, aqueous pigment dispersions, and such materials

o 10 as clays china clay) and whiting. Other additivies a

Sooa such as surfactant(s) (to aid dispersion),plasticizers (as 00 °o 0 S indicated above) and viscosity controllers may also be a ca 01' present as required. A Q *9o* 0 4 Of those specifically mentioned heretofore, the

especially preferred water-soluble or -dispersible monomers

are acrylamide or N-methylol derivatives thereof. The con- *9 0

I a ventional method for producing acrylamide is by hydrating

S1 acrylonitrile in the presence of sulphuric acid and water

at 100 C, thus forming acrylamide sulphate and subsequently

removing the sulphate and recovering pure acrylamide. In

2) the present invention, the acrylamide may be produced by

at c reacting acrylonitrile in the presence of hydrochloric acid

to produce acrylamide chloride. By further addition of

calcium hydroxide, calcium chloride is formed. The production

of calcium chloride in this way is a convenient and inexpensive

means of eliminating an otnh.rwise unwanted by-product.

Acrylamide monomer as such (without further modification)

is suitable as the water-soluble or dispersible monomer.

9

i The claims defining the invention are as follows:

1. i A method of coating upon a s .itable substrate which e13 4 O g 7 r

;i However,, modification of the acrylamide to the N-methylol

derivatives adds even greater latitude to the formulation.

The reaction of acrylaride with various aldehydes will form

the correspondiijg methylol products and then upon polymer-

ization the condensation reaction occurs simultaneously.

Formaldehyde (in the form of paraformaldehyde) is the

particularly preferred reactant. The percentage solids is not

critical. Where the compositions of the invention are used as

alternative coating compositions, such compositions may be roo 10 applied to a substrate using conventional techniques and cured

Q 0, using such methods as described above. Typical substrates 0b~

0-? include paper, board, wood, metal masonry, glass, cloth 0I I

synthetic surfaces and the like.

In the above-mentioned cases, the advantage of the process

lies in the considerable energy savings resulting from the

polymerization reaction which is exothermic.

The above-mentioned carrier(s) can, of course, be

augmented. Thus, plasticizer(s), stabilizer(s), dyestuff(s)

and the like may also be added.

*0 0

O

1 1

i

i= ^acaapef nAlterr*tiv3y, a throe-part cystm may comric

a fir monomer part, a second part incorporating a plasti-

cizer, an ai and a free radical catalyst, and a third part

incorporating plas f izer, :32 inclusive alkali and reducing redox couple. The compon s may be formulated to equal volume and mixed with resultan imultaneous foaming and polymerization. The foam composition t produced (where air may act as a filler material) has use, int alia, in insulation environments and as a protective coating

animai

O oo The invention will now be described, in greater detail,

with reference to specific working examples. The examples illustrate all aspects of the invention. Unless specifically

o indicated to the contrary, parts are by weight. Where implementation of the examples has involved the use of

conventional proprietary compositions which, in the art, are obtainable under, and normally identified by, trade or Soo like names these compositions have been so identified

and in conjunction therewith, have been identified (as far as possible) by reference to their general chemical con-

stitution. Similarly, where known commercial equipment

1 is used as the source of radiation in the specific examples), such equipment is identified in the manner in which it is known in the art.

Example 1

This example illustrates a three-part monomer system.

The first part comprises 100 parts by weight of N-methylol

acrylamide (hereinafter sometimes referred to, for

convenience, simply as The second part was formed

from 50 parts by weight water, 45 parts by weight sugar,

parts by weight hydrochloric acid and 1.5 parts by weight

ammonium persulphate and a third part from 50 parts by

weight water, 45 parts by weight sugar, 1.5 parts by weight

sodium formaldehyde sulphoxylate, and 3.5 parts by weight 00 sodium bicarbonate. The three parts were mixed together in .0 0 000cc equal proportions.

Example 2

2 0n This example illustrates a two-part monomer system. 000

The first part was produced by mixing 37.5 parts by weight *0 0 0 0o water, 52 parts by weight calcium chloride, 2 parts by weight

hydrochloric acid, 8 parts by weight acetone co-solvent,and S0*100

parts by weight of the catalyst known as "IRGACURE 651"

(see heretofore). The second part was produced by 87 parts

by weight 60% 5 parts by weight ammonium hydroxide 0 00

and 8 parts by weight ammonium carbonate and the two parts *0c0O C) 0 0 mixed together. 00aat

Example 3

This example further illustrates a two-part monomer

system. The first part was formed by mixing 66 parts by

weight 60% 28 parts by weight 50% sugar/water solution

0.3 parts by weight "IRGACURE 651" and 5.7 parts by weight

of sodium bicarbonate. The second part was produced by mixing 90 parts by weight 50% sugar/water solution, 9 parts b, weight acetone, 0.3 parts by weight "IRGACURE 651" and

0 .7 parts by weight acetic acid. The two parts were then

mixed together.

ExLamples 4-7

These examples illustrate several one-part monomeric

systems. For convenience, the systems are presented in

tabular form.

4 4 4, 4 4 4 4 4444 44 A 44 4 40 44004 A 0 ~4 44 44 4 440004 4 04 4 4 .4 4 4 4 04 4 0* 0 4 04 4 44 4444 09 0 440 4 004 00 4 4 4 4 000 44 0 ~'4

Ingredients Ear)I Example Example Example 4 15 6 -7

N.M.A. 50.5 70

Acrylamide 44.0 57: 0

Calcium chloride 5.0 16.0

irgacure 651 0.5 0.5 0.2 0.4

Acetone 3.0 5,~0

(NHA) 2 CO3 10.0 4.0 10,.0

P araformaldehyde 24.0

Triethylamine 0~.8

Water 10.0

Glycerine

Amimonia I I I I

c~LPV~

A6. S I 6 6 5

6 66 6 *6 5 6 6

Ingredients Example Example I 4

N,4.A. 50.5 70.5

Acrylamide 44.0

Calcium chloride 5.0 16.0 irgacure 651 0.5

Acetone

(NH4 2 CO3 10.0

Paraformaldehyde

Triethylamine

Water

Glycerine

Ammonia ample Example 6 7

77

0.2 0.4

10.0

0.8 0.0

?CDA, -vu

In the, following examplcs, the compositions and related con wat methods of the invention are illustrated. As elsewhere,

parts are by weight. ExaMples 8 to 13 illustrate the print- Irgi

ing and other coating aspects of the invention. wh44

RiampIco 14 and 16",illasitmate the bladinpg and foaming aspac~ts 5 in

Examrple 8 the -J Gravure ink (black): cured by U.V. radiation. dis

Composition: s trz I N-methylolacrylamide (water-soluble monomer) 52.0 is(

Primal 1-94 (alkali soluble polymer emulsion) 40.0 10 E-kani 0444 0V~ a 4 ~4 4 Continex N326 (carbon black pigment) 5.0 0 a 0 a a a aqueous ammonia 1.0 04 3V radi a 000 a 4*

COin at 0 Irgacure,651 (photoinitiator catalyst) 2.0 a o a 0 4~4 0 The Primal 1-94 is neutralized with aqueous ammonia, a440

and then added slowly, with stirring, to the N.M.A. solution. 1.5 Prin

A transparent solution results. The pigment and photo- Irga

'ear. initiator catalyst are dispersed into this medium, using a a boo acet no 0 *0

a 0 0 bead mill, at a temperature less than 40 0 C. Printing, watel *.a

*0 on a paper substrate, is effected using a rotogravure 4

press. As indicated above, curzng is by lLV. radiation 20 solu

Curing Unit (H type bulb) of Fusion Systems Corp,). is d L~ ~.0r. 0 a a 4 44 a, Exape 9 04 0 c ata *0.0 0 *4 0 C 0 40 00 a Flexographic ink (black) for reclaimed paper: cured spee

by U.V. rad~iation. coat

Composition: 25 Exa Exam, N-methylolacrylamide (water-soluble monomer) 50.0

P.V.P. R-30 (viscosity controller)

alkanate 3SN5 (surfactant) 0 .05 e lec

Is

Continex N326 (carbon black pigment) 7.45

water 40.0

Irgacure 651 (photoinitiator catalyst)

The P.V.P. K-30 (polyvinylpyrrolidone) is dissolved

in the N.M.A. solution, and the surfactant and water are

then added. The pigment and photoinitiator catalyst are

dispersed as in Example 8. Printing upon the paper sub-

strate is effected with a flexographic press. U.V. curing

is carried out as in Example 8.

Example Q Q oq Clear coating for printed paper: cured by U.V.

radiation.

SComposition:

60% N-methylolacrylamide (water-soluble monomer) 30.0

Primal HA-16 (polymer emulsion) 30.0

Irgacure 651 (photoinitiator catalyst)

Ss" acetone

water 34.0

The polymer emulsion is stirred into the N.M.A.

solution and water is added. The photoinitiator catalyst

is dissolved in the acetone, following which the dissolved OO

0I catalyst is slowly added to the N.M.A. solution with high B O

So speed mixing. Coating is effected per medium of a roll

coater with doctor blade. Radiation is carried out as in

Examples 8 and 9.

Example 11

Transparent coating for clay coated paper: cured by

electron beam radiation.

1/

m curing. Their purpose is to initiate and/or increase the rate of reaction. The benzildimethylketal compound known as

5

Composition:

N-methylolacrylamide (water-soluble monomer) 50.0

33% Platamid M1255 (water-soluble copolyamide resin) 48.0

Eriosin blue dye

The polyamide and N.M.A. solutions are mixed, and

the dye is dissolved therein. Coating is effected as in

Example 10. Electrom bean radiation is carried out using

a 250kV electron accelerator.

Example 12

Clay coating for paper: cured by U.V. radiation.

nah Composition: 0*

OOo- 60% N-methylolacrylamide (water-soluble monomer) 48.0

e0 Eckalite clay 50.0

S.O Irgacure 651.

The photoinitiator catalyst is dispersed in N.M.A.

solution, using a bead or sand mill. Thereafter, the clay a no is dispersed in a similar manner. Coating is carried out

as in Examples 10 and 11 (alternatively, the doctor blade

*o can be substituted by an air knife). U-V. radiation is carried

out as in Examples 8 to

Example 13

Glazing upon ceramic tiles: cured by U.V. radiation.

Composition:

N-methylolacrylamide (water-soluble monomer) 35.0

powdered red glazing glass (pigment) 40.0

Sandoray 1000 (photoinitiator catalyst)

acetone

water 10.0

F-

Il

The N.M.A. solution is diluted with water, the photo-

initiator catalyst is dissolved in acetone, and the former Sis added to the latter with vigorous mixing. Into the

resultant medium, the glazing compound is dispersed (with

4 5 continued vigorous mixing). Silk screen printing is effected,

and the UV radiation is performed as above.

In conclusion, it is reiterated that the preceding

Sperformance details, of the ink and other compositions and

the printing and other methods, are not to be limitatively S: 1.0 construed. Thus the individually specified examples (of oI

1 the components and monomers) may be replaced by functional

Sequivalents, the effect of oxygen inhibition need not be 4

old countered, and so on. As long as the basic inventive

kcriteria predicaed upon the novel application of water-

soluble monomers in novol oompocitionc and rclatcd mcthodd

are observed, matters falling therewithin may be varied in

accordance with situational requirements.

4

:I I

18

ulP*-r4e~-~?3ylw~uuar~ur;~

The N.M.A. solution is diluted with water, the photo-

initiator catalyst is dissolved in acetone, and the former

is added to the latter with vigorous mixing. Into the

resultant medium, the glazing compound is dispersed (with

continued vigorous mixing). Silk screen printing is effected,

and the UV radiation is performed as above.

In conclusion, it is reiterated that the preceding

performance details, of the ink and other compositions and

the printing and other methods, are not to be limitatively

SW* 10 construed. Thus the individually specified examples (of

the components and monomers) may be replaced by functional

equivalents, the effect of oxygen inhibition need not be

l countered, and so on. As long as the basic inventive

criteria predicated upon the novel application of water-

soluble monomers in novel omciioijti and rc atcd mothzcx

are observed, matters falling therewithin may be varied in

accordance with situational requirements.

i1 4

At kl i The claims defining the invention are as follows:

1. A method of coating upon a suitable substrate which

comprises the steps of applying, to a said substrate, a polymerizable water-based coating composition which does not

require air-drying and which comprises a\coating compound,

and an aqueous monomer system, the said system comprising at 0 least one water-soluble or water-miscible or water-dispersible

ethylenically unsaturated monomer and a photo-initiator I C, catalyst as required; and subjecting the so-applied composition

to curing, in the absence of heat and without preliminary air-

''o drying, by UV radiation in the presence of the said photo- 0ia 0000 initiator catalyst or by electron beam radiation, the aqueous

0 monomer system being thereby polymerized.

2. A method as claimed in claim 1, wherein the aqueous 0 0* 0o 0a monomer system is a one-part system. 00"S 3. A method as claimed in claim 1 or 2, wherein the .o0 0 monomer is acrylamide or the N-methylol derivative thereof. 4

4, A method as claimed in any one of the preceding

0 0 claims wherein the substrate is selected from paper, board,

wood, metal masonry, glass, and cloth synthetic surfaces.

A method of coating as claimed in claim 1 and

substantially as herein described with reference to any one

of the foregoing examples thereof.

DATED this 10th day of July 1984.

MONOCURE PTY. LIMITED

By Its Patent Attorneys

ARTHUR S. CAVE CO.

'N p ~NT0 19