(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property Organization &“''HIPU'"A WO 03/046099 A1

International Bureau lm n ikin I,·®/

(43) International Publication Date (10) International Publication Number

5 June 2003 (05.06.2003) PCT W O 03/046099 A l
(51) International Patent Classification7: C09J 131/04, (81) Designated States (national): AE, AG, AL, AM, AT (util­
107/02, 111/02, E04C 2/16, B27N 3/04, C08J 5/18, 7/04 ity model), AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA,
CH, CN, CO, CR, CU, CZ (utility model), CZ, DE (util­
(21) International Application Number: PCT/NZ02/00265 ity model), DE, DK (utility model), DK, DM, DZ, EC, EE
(utility model), EE, ES, FT (utility model), FI, GB, GD, GE,
(22) InternationalFilingDate: 2 December 2002 (02.12.2002) GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ,
LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN,
(25) Filing Language: English MW, MX, MZ, NO, NZ, OM, PH, PL, PT, RO, RU, SC,
SD, SE, SG, SK (utility model), SK, SL, TJ, TM, TN, TR,
(26) Publication Language: English TT, TZ, UA, UG, US, UZ, VC, VN, YU, ZA, ZM, ZW.

(30) Priority Data:
515843 30 November 2001 (30.11.2001)
(71) Applicant (for all designated States except US): AUCK­
LAND UNISERVICES LIMITED [NZ/NZ]; Level 9, 70
Symonds Street, Auckland (NZ).
WO 03/046099 A1 and
(72) Inventors;
(75) Inventors/Applicants (for US only): EASTEAL, Allan,
James [NZ/NZ]; 31 Liverpool Street, Epsom, Auckland
(NZ). DE SILVA, Kaluachchi, Gamage, Karnika [/NZ];
3 Puketutu Rise, Hillsborough, Auckland (NZ).
(74) Agent: BALDWIN SHELSTON WATERS; P.O. Box
852, Wellington (NZ).
WO 03/046099 Al
(84) Designated States (regional): ARIPO patent (GH, GM,
NZ KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW),
Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
European patent (AT, BE, BG, CH, CY, CZ, DE, DK, EE,
ES, FT, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, SI, SK,
TR), OAPI patent (BF, BJ, CF, CO, Cl, CM, GA, GN, GQ,
GW, ML, MR, NE, SN, TD, TG).
Published:
— with international search report
For two-letter codes and other abbreviations, refer to the "Guid­
ance Notes on Codes and Abbreviations" appearing at the begin­
ning o f each regular issue o f the PCT Gazette.

(54) Title: WATER-BASED ADHESIVE COMPOSITIONS

(57) Abstract: A series of aqueous based adhesive compositions including poly(vinyl acetate) with a rubber latex are described. At
least some cross-linking is preferred, and a tackifing agent is also preferred. The adhesives are water-resistant and heat-resistant ad­
hesives suitable for use with (for example) wood, having little coloration in exposed joints. Significant and long-lasting wet strength
is obtained. Versions for use in conjunction with paper products can act as releasable adhesives. Coating versions (in conjunction
with paper and cardboard) are also prepared for the printing and packaging industries.
WO 03/046099 PCT/NZ02/00265

WATER-BASED ADHESIVE COMPOSITIONS

This invention relates to generally to compositions for water based adhesives,

5 and more particularly to compositions including poly(vinyl acetate) and one or
more latex(es).

BACKGROUND

10 An ideal adhesive would include stability and strength properties as well as being
cheap to produce, non-toxic, and easy to use. The ideal strength properties of an
adhesive would result in substrate bonding which is maintained over a long
period depending on the existing physical and chemical environmental factors.
The desired strength of bonding can range from very high, for constructional
15 adhesives to very low, for removable paper labels and the like.

Ideally the materials involved in preparation of the adhesive are cheaply and
readily available, such as renewable materials.

20 Safety issues surrounding an adhesive include the absence of possibly

carcinogenic materials both in the adhesive as manufactured, and in use. For
example the continued slow release of aldehydes from urea-formaldehyde glues
used in particle boards in housing, has been at issue in New Zealand’s "sick
building syndrome". Similarly, the presence of skin cancer promoting substances
25 in isocyanates is a known safety problem. In addition safety can be an issue for
cyanoacrylates if inadvertently splashed into a person's eyes.

Stability of the adhesive prior to use is clearly desirable. For commercial

purposes the adhesive should have a long shelf life. A recognised difficulty with
30 the shelf life of adhesives is seen for example with conventional re-sealable
mailing envelopes, which seal adhesive dries over a relatively short period of
time in storage.

It is therefore an object of the present invention to provide a set of aqueous-

35 based contact adhesive compositions having desirable stability, strength, safety
WO 03/046099 PCT/NZ02/00265

and environmental properties for use in bonding and coating a variety of

substrates such as wood; metal, such as cold-rolled steel, galvanized steel, and
aluminium; fabric; paper; foam; plastic, such as poly(vinyl chloride), polystyrene,
polyethylene, polypropylene, and fibreglass or the like or to at least provide the
5 public with a useful choice.

DEFINITIONS

The following terms used throughout the specification are to be understood in

10 light of their following definitions.

The term “contact adhesive” refers to a film of adhesive which is applied to at

least a portion of a surface of a first substrate and at least a portion of a surface
of a second substrate, the films of adhesive on each substrate then being dried
15 and subsequently brought into contact under pressure so as to form an
immediate, durable bond between the adhesive films of each substrate.

"Water based or aqueous" means that the adhesive comprises a water

component.
20
The term “drying” means the substantial removal of water from the adhesive
composition through evaporation, heating or vacuum drying.

“Substantially water resistant” means that an adhesive bond formed between two
25 contact adhesive films as defined above is substantially resistant to the effects of
boiling water on the strength of the contact adhesive bond.

The term “activator” is the term given to agents that are added to rubbers or
emulsions of rubbers to help initiate their curing.
30
The term “accelerator” is the term given to agents that are added to rubbers or
emulsions of rubbers to accelerate their curing. Such accelerators include an
organic dithiocarbamate, disulphide or thiozole, such as zinc
diethyldithiocarbamate, tetramethyl thiuram disulphide, mercaptobenzothiozole
35 and the like.
WO 03/046099 PCT/NZ02/00265

The term “prevulcanized” is the term used to describe the production of

producing a vulcanised latex or rubber product whereby the latex or rubber is
dried or cured from a liquid state.

5 Abbreviations

The following abbreviations as used throughout the specification are intended to

refer to the following terms

10 NR - Natural Rubber latex

NRx, Ne - Cross-linked natural rubber

PVA - Poly(vinyl acetate) [NB: poly(vinyl alcohol) is not a subject of this

15 specification].

PVA ALK - Poly(vinyl acetate) emulsion, alkalised with 22% aqueous

ammonia solution to give 1.1% ammoniated PVA emulsion.

20 Under the specific examples outlined in the detailed description, codes like
PALK(8)NR(2) mean 8 parts by volume of PVA alk., 2 parts of natural rubber,
and so on, where the following abbreviations are to mean

P - poly(vinyl acetate)
25
NR- Natural Rubber

A - AQL - Polychloroprene latex (Aquastik 1120/ Neoprene 115 from Du

Pont/Dow)
30
R1- Epoxy resin (Europox 710)

R2 - SE 780 (Akzo Nobel Snowtack tackifing agent)

WO 03/046099 PCT/NZ02/00265

R3 - SE 790 (Akzo Nobel Snowtack tackifing agent)

TA- Tetraethylenepentamine

5 NC- crosslinked NR

AC- crosslinked polychloroprene latex (AQL)

PALK - alk. PVA - is a poly(vinyl acetate) emulsion, alkalised with 22% aqueous
10 ammonia solution to give 1.1% ammoniated PVAemuIsion

PC - crosslinked and alkalised PVA

N - alk. NR
15
STATEMENT OF INVENTION

In a first broad aspect this invention provides a water based adhesive

composition, including
20 (a) at least one poly(vinyl acetate); and
(b) at least one latex;
wherein in use the adhesive composition, after drying, is substantially
water-resistant.

25 Preferably the poly(vinyl acetate) adhesive has been subjected to a cross-linking

treatment.

Optionally the composition includes an effective amount of at least one water

based tackifying agent capable of promoting adhesion; preferably in the form of
30 an aqueous dispersion, and selected from a range including rosin acids, rosin
esters, terpene phenolic resins, other hydrocarbon resins, and coumarone indene
resins.

Preferably the tackifying agent is present in an amount of about 1% to about 50%

35 by volume, based on the wet weight of the total adhesive component.
WO 03/046099 PCT/NZ02/00265

More preferably the tackifing agent is used at about 40% by volume based on the
wet weight of the total adhesive component.

5 Preferably the latex of the adhesive composition includes at least one latex
selected from a range including: natural rubber latex; modified natural rubber
latex; compounded natural rubber latex; modified, crosslinked natural rubber
latex; polychloroprene rubber latex and modified polychloroprene rubber latex.

10 Preferred modified rubbers include those having unsaturated chains such as

styrene or methyl methacrylate bonded onto groups such as butadiene including
at the C4 or C l 0 sites.

Preferably the modified natural rubber is compounded, prevulcanized, or grafted

15 natural rubber.

Preferably the compounded natural rubber includes at least one component

suitable to at least partially crosslink natural rubber; the further component being
selected from an activator, an accelerator, an antioxidant and a crosslinking
20 agent; and mixtures thereof.

Preferably the prevulcanized natural rubber includes a component suitable to at

least partially crosslink natural rubber the further component being selected from
an activator, an accelerator, an antioxidant and a crosslinking agent; and
25 mixtures thereof with/without other suitable ingredients before blending with other
latexes.

Preferably, the cross linking agent is a zirconium salt in an alkaline medium, such
as zirconium nitrate.
30
Preferably, the activator is an inorganic oxide, such as zinc oxide.

Preferably, the accelerator is an organic dithiocarbamate, disulphide, thiozole

and the like, such as zinc diethyldithiocarbamate, tetramethyl thiuram disulphide,
35 mercaptobenzothiozole and the like.
WO 03/046099 PCT/NZ02/00265

Preferably, the antioxidant is a phenolic or amine compound or a blend thereof.

More preferably, the antioxidant is Antioxidant 2246, Wingstay L, Vanox MBPC,
Vulkanox BKF, 4020, SKF, MB 2 or SP.
5
Preferably the grafted natural rubber is further modified by the grafting of polar
polymers on to natural rubber to increase polarity. Preferably the polar polymer is
selected from the range including poly(methyl methacrylate) and styrene.

10 Preferably preservatives including biocides are included so that degradation of

the adhesive composition due to bacterial or fungal attack is reduced.

Preferably (in the case of polychloroprene) additional acid acceptors such as zinc
oxide dispersions or aqueous epoxy resins are included so that degradation of
15 the adhesive composition due to release of hydrochloric acid from the
polychloroprene rubber is minimised.

Preferably (in the case of polychloroprene and a natural rubber with poly(vinyl
acetate)), it is preferred that the natural rubber ranging from about 10% to about
20 40% by volume is blended with poly(vinyl acetate) first before polychloroprene is
added.

Preferably the modified poly(vinyl acetate) has become modified by a cross-

linking procedure, and a preferred cross-linking procedure includes use of a
25 zirconium salt; more preferably zirconium nitrate in an alkaline medium.

Preferably the modified polychloroprene has been modified by a cross-linking

procedure and stabilised with zinc oxide or an epoxy resin.

30 Preferably the natural rubber is a stable aqueous emulsion preserved with a low
ammonia biocide composite system, or any other suitable preservative system.

Preferably the adhesive compositions as previously described in this section

further include a tackifing agent, the tackifing agent comprising one or more items
35 selected from a range including a water soluble rosin or modified rosin acid,
WO 03/046099 PCT/NZ02/00265

ester, terpene phenolic resin, other hydrocarbon resin or coumarone indene

resin.

Preferably the water based adhesive has a composition including poly(vinyl

5 acetate), natural rubber, cross-linked polychloroprene rubber, and a tackifing
agent.

More preferably at least one of the PVA and the natural rubber is cross-linked.

10 Even more preferably the invention provides a preferred boiling-resistant, strong

adhesive having the composition of "PC(8)/AC(1)/NC(1 )/R2" according to the
terminology used herein.

In a further aspect the invention provides a method of bonding at least one

15 substrate; the method comprising the steps of:
a) applying a water based adhesive composition as defined above
to at least a portion of a surface of at least one substrate,
b) allowing the adhesive composition to at least partially dry; and
c) contacting the adhesive applied surface of the substrate to
20 another surface.

In a related aspect the invention provides a water based adhesive suitable for
bonding two layers of paper of compositions as previously described in this
section; wherein any one layer of adhesive on a substrate of paper is capable of
25 adhering to a second layer of adhesive on a substrate of paper so that the
adhesive can be used with self-sealing envelopes. In another related aspect the
invention provides a water based adhesive; the adhesive being a removable type
suitable for use with removable paper labels; the adhesive being resistant to
degradation so that a long shelf life can be expected.
30
In a further related aspect the invention provides a water based releasable
adhesive suitable for the manufacture of a range of easily peelable protective
coatings; comprising an outer protective layer selected from a range of materials
including paper, polyethylene, bubble pack, polypropylene and the like, the layer
35 being provided with an inner coating of a releasable composition according to the
WO 03/046099 PCT/NZ02/00265

invention, so that the protective coating may be attached to a delicate surface

such as glass, stainless steel as on televisions, computer screens, microwave
ovens, refrigerators etc in order to protect the surface from scratching during
transport and before use.
5
In a further aspect there is provided a method of applying a water resistant
coating to at least one substrate; the method comprising the steps of:
a) applying a water based adhesive composition as defined
above, to at least a portion of a surface of a substrate, and
10 b) allowing the adhesive composition to dry on the substrate.

Preferably the method further includes the step printing on said adhesive
composition, said composition being capable of accepting printable compositions
while still exhibiting an effective amount of moisture and water transmission
15 resistance. Preferably the composition includes, as a water barrier, at least one
substance selected from a range including silicone, Additive 84, Additive 85, and
Oratan 2001, and preferably the substance is incorporated at up to 20% by
weight. (These are commercial additive samples from Rohm and Haas and Dow
Corning Chemical Companies).
20
In a related aspect the invention provides a water based adhesive composition
suitable for the coating of least one surface of a cardboard including the types of
cardboard known as kraft and corrugated boards with a composition according to
this invention; the composition being capable of accepting printable compositions
25 yet exhibiting an effective amount of moisture and water transmission resistance
between an interior of a box and an exterior.

In a further aspect the invention provides a water-resistant chipboard, the

chipboard being substantially comprised of fragments of wood bonded together
30 with a water based adhesive as previously described in this section, thereby
forming a structural component.

In a still further aspect this invention provides a transparency sheet including a

dye-receptive or printable layer, the dye-receptive layer comprising water based
35 adhesive composition including a poly(vinyl acetate) adhesive together with at
WO 03/046099 PCT/NZ02/00265

least one member of a range including a synthetic latex particularly

polychloroprene latex and natural rubber latex.

Further aspects of the present invention will become apparent from the following
5 detailed description and figures of the invention, which is provided by way of
example and is not to be taken in any way as limiting the scope or extent of the
invention.

Fig 1: shows graphically the performance of trials 90-99 duringa boiling test.
10 (see Example 5, table 8)
Fig 2: shows graphically the performance of trials 120-129 during a boiling test,
(see Example 5, table 8)

DETAILED DESCRIPTION
15
By way of introduction, the invention is based on poly(vinyl acetate) (PVA)
modified natural rubber emulsions providing water-resistant and heat-resistant
adhesives. The invention originated from experiments intended to enhance the
properties of known PVA adhesives. The blends were prepared using
20 commercially available emulsions and other components as follows.

PVA emulsion - Viscopol 6624 (ex Nuplex Chemicals)

Natural rubber latex (NR) (RLA Polymers NZ)
Aquastik 1120 or Neoprene 115 (Dupont Dow or Henkel NZ Ltd).
25 Tackifying Resins Emulsions - SE 780 (R2), and SE 790 (R3) (EKA
Chemicals)
Epoxy Resin - Europox 710

The emulsions were modified and/or crosslinked as stated below before mixing.
30
The invention also provides an adhesive composition including poly(vinyl acetate)
together with modified natural rubber, another synthetic rubber, or their
combinations.
WO 03/046099 PCT/NZ02/00265

10

Such natural and synthetic rubbers include .

(a) those having unsaturated chains attached to units such as butadiene,

wherein examples of such natural and synthetic rubbers have chains such
5 as styrene or methyl methacrylate conjugated at C4 or C l 0 sites on
dienes;

(b) commercially available modified general-purpose latexes, wherein

examples of such natural and synthetic rubbers are commercially
10 available under the tradenames MEGAPOLY latex (rubber latexes grafted
with methyl methacrylate in order to increase the polarity and thereby the
adhesion of the adhesive compositions). MG 30 is a low polarity
compound with 30% PMMA, and MG 49 is a high polarity compound, with
49% PMMA. Other, related compounds can be synthesised. These
15 compositions would give transparent, tough and semi-reinforced films.

Preferred components of the adhesive compositions of the present invention

1 PALK - PVA emulsion was alkalised with 22% industrial grade ammonia
20 solution to give 1.1% ammoniated PVA emulsion.
2 Ammoniated, crosslinked PVA - (denoted as PC in formulations) -
alkalised PVA was crosslinked using a 0.3 m/l aq. Zr(NOg)^ solution. 1.5

ml of this solution was added to 100 ml of alkalised PVA emulsion to

effect crosslinking in the system.
25 3 NR - NR latex (with -45% dry rubber content) was alkalised using 22%
industrial grade aqueous ammonia solution. 4% ammonia solution
(relative to latex) was added to alkaline NR latex.
4 NRx - Crosslinked NR latex. In some instances crosslinked NR with an
antioxidant was used to improve heat resistant properties. The formulation
30 used to crosslink NR was as follows in Table 1.
WO 03/046099 PCT/NZ02/00265

11

Table 1. Formulation of crosslinked NR

Component Parts by weight

NR latex 100
ZDC 0.5
ZnO 0.5
TMTD 0.5
Antioxidant 1

Note: ZDC = zinc diethyldithiocarbamate

5 TMTD = tetramethylthiuram disulphide
Antioxidant = a phenolic or amine antioxidant

5 Polychloroprene (Neoprene 115) (AQL) - AQ latex was modified using

10% epoxy resin, Europox 710.
10 6 Tackifying resins were used without any modification.

Optionally the adhesive composition of the present invention can also contain at
least one water based tackifying agent to promote adhesion, preferably in an
amount of about 1% to about 50% by volume based on the wet weight of the total
15 adhesive component though preferably about 40% by volume based on the wet
weight of the total adhesive component. Suitable tackifing agents for use in the
contact adhesives of the invention include rosin acids, rosin esters, terpene
phenolic resins, hydrocarbon resins, and coumarone indene resins. The tackifier
will generally be used in the form of an aqueous dispersion. One advantage of a
20 tackifing agent is to provide an instant first attachment.

Samples were mixed using simple blending techniques.

EXAMPLE 1:
25 Contact adhesive suitable for use on self-sealing envelopes:

The formulation outlined in Table 2 below allowed the making of paper envelopes
of the type where two lips, each coated with adhesive, are able to form a good
WO 03/046099 PCT/NZ02/00265

12

bond only with other similarly coated lips. The storage life appears to be good.
(Conventional self-seal envelopes lose bond strength in less than a year).

Table 2: Typical formulation of contact adhesive

5

Component Parts by volume

NR 80
PALK. 20
R3 25

Standard 80 gsm photocopy paper was coated with adhesive samples prepared
according to the formulations in Table 3. The strength of the bond produced by
making contact between two such coated papers was determined as the force
10 per unit area of coated paper required to separate the two coated paper surfaces
immediately after the bond was formed, and after ageing. The results are given in
Table 3.

Table 3. Peel strength of adhesives.

15
Sample Composition3 Initial strength/MPa Aged
strengthb/MPa
1 100 N1c 2.7 2.5
2 100 N 5.7 2.2
3 60 N:05 P:1 9.3 5.5
4 60 N1°:05 P:1 4.2 3.0
5 60 N:05 P 4.1 5.3
6 100 N:20 P:1 5.3 8.3

a NR:PVA:tackifing agent (parts by volume); the tackifing agent used was

Snowtack SE 790G from Eka Chemicals (NZ) Ltd.
b after accelerated ageing at 60°C for one week.
20 c Natural rubber latex currently used in manufacture of self-sealing envelopes.
WO 03/046099 PCT/NZ02/00265

13

EXAMPLE 2:

Adhesive for self-sticking note pads similar to the "3M Post-it ™ "type

Adhesive prepared according to the formulation in Table 4 below was applied as

5 a coating to the surface of standard photocopy paper and the coated paper
pressed onto surfaces of paper, glass, wood, plastic and metal. The reversible
performance as self-sticking note pads was assessed qualitatively as at least

equivalent to the performance of "3M Post-it ™ " type note pads. No quantitative
tests were carried out.
10
Table 4: Formulation of adhesive for self-sticking note pads

component parts by volume

NR *
40
PALK *
10
R3 *
50
Triton X-100 *
1
NR 15
water 1

* These components were pre-mixed, before addition of the remaining

15 components.

EXAMPLE 3:
Contact adhesive for bubble wrap-film

20 An adhesive prepared according to the preparation outlined in Table 5 was

coated onto the flat surface of bubble wrap film. The coated film could be stuck
onto a glass surface and peeled away again Iaterwithout leaving a residue on
the glass surface. The coated bubble-wrap film can be used for example to
protect architectural glass, picture frame glass, computer screens, TV screen,
25 stainless steel metal surfaces of refrigerator doors and the like during
transportation, storage, and shipment.
WO 03/046099 PCT/NZ02/00265

14

Table 5: Formulation of adhesive suitable for use as bubble wrap film

component parts by volume

NR 80
PALK. 20
R3 10

5 EXAMPLE 4:
Printable water vapour barrier coating for paper and paperboard

This aspect of the invention is applicable to cardboard boxes and the like where
there is a desire to provide both a barrier against the ingress or egress of water,
10 and to provide a substrate on which printing can be applied. The transparency is
an advantage. This aspect of the invention provides a one-coat system whereas
some prior art sealants require a primer layer to be followed by at least one other.
A typical formulation intended by this aspect is outlined in Table 6 below.

15 Table 6: Typical formulation

component parts by volume

PALK 40
NR 10
AC 10
water 20

The formulations listed in Table 7A were applied as a 10-15 pm thick coating to

standard photocopy paper and the water vapour transmission of the coated
20 paper was determined in accordance with American Society for Testing Materials
standard specification ASTM E96-95 for an exposure time of three days. The
results of the water vapour'transmission properties of these formulations are
given in Table 7A: The abbreviations WVT refers to water vapour transmission
(mass of water vapour transmitted per m2 per day) and WVTR is water vapour
25 transmission rate, which takes into account coating thickness.
WO 03/046099 PCT/NZ02/00265

15

Table 7A: Water vapour transmission data for PVAc/NR emulsion coatings

Sample Formulation WVT/g m"2 d"1 WVTR/g m"1 d"1

1 C l 1 + 25% M2 142.9 26.6

CO
2 339.6 57.4
O
CM

3 N + S4 + water (1:1:1) 516.2 48.1

4 C35 + 15% R6 272.3 47.7

5 C3 + 15% D17 292.4 49.1

6 C3 + 15% D28 253.4 39.9

7 N + S + water (2:1:4) 330.9 53.7

8 C3 240.0 39.7
9 N + S + water (1:1:2) 548.3 78.5
10 C2 diluted 903.3 120.5
- - -

5 1 C l = PC(8)/AC(1)/N(1)/R2
O
M = commercial material (#2200) from Michelman Inc.

3 C2 = PC(8)/AC(1 )/N(1)

4 S = dilutable water repellent silicone emulsion 520 from Dow Corning

5 C3 = PC(8)/AC(1)/N(2)

10 R = commercial material (Oratan 2001) from Rohm & Haas

7 D1 = commercial material (Additive 85) from Dow Corning

8 D2 = commercial material (Additive 84) from Dow-Corning

Parts by volume are in parentheses in Samples 3, 7 and 9.

15

In a further series of experiments the formulations listed in Table 7B were applied

as a 10-15 μιτι thick coating to standard 80 gsm photocopy paper and the water
vapour transmission of the coated paper determined in accordance with standard
specification ASTM E96-95 for an exposure time of three days at 50% relative
20 humidity at 23°C with the results given in Table 7B.
WO 03/046099 PCT/NZ02/00265

16

Table 7B: Water vapour transmission data for PVA/NR emulsion coatings

Sample Formulation _2
Coat weight g m WVT/g m"2 d"1

1 Cl 11 216
2 C2 10 96
3 C3 14 98
4 C4 10 120
5 C5 9 192
6 C6 8 148
7 C7 9 144
8 C8 6 121
9 C9 7 123
10 C10 9 141
- -

5 C l = P(1)/N(5)
C2 = P(1)/N(5)/M(1)
C3 = C l (1 )+ water (0.03)
C4 = P(1)/N(6)
C5 = P(1)/MG1(5)/N(1)
10 C6= P(1)/MG2(5)/N(1)
C7 = C1(1)/APS(0.004)
C8 = C2(1 )/APS(0.004)
C9 = C6(1 )/APS(0.004)
C10 = C4(1)/APS(0.004)/Talc(0.015)
15 MG1 = Poly(methyl methacrylate)-grafted NR latex with 40% total solids
MG2 = Poly(methyl methacrylate)-grafted NR latex with 50% total solids
APS - Ammonium persulphate

Parts by volume are in parentheses.

20

AU of the samples in Table 7B are wax-free except for sample C2 which may
contain some waxy material. AU of the samples except sample C2 show good
printability.
WO 03/046099 PCT/NZ02/00265

17

EXAMPLE 5:
Wood Bonding Performance Tests And Results For PVA Based Emulsion
Adhesives

5 A range of formulations (90-99 and 120-129) was used, as indicated in Tables 8

and 9. Shear strength of wood joints was determined in accordance with the ISO
9020 standard. Wood blocks (at 12 per cent moisture content) were glued at

room temperature (~20°C) and kept under compression (20 kg cm"2) for 24
hours, then left under the same conditions (but without compression) for 3-7
10 days. Their shear strength was evaluated in the dry condition.

Water resistance of adhesives was tested as follows. Glued wood blocks were
immersed in water at room temperature for 6 weeks, then dried in an oven at
60°C for 48 hours prior to shear strength determination. (Note that this procedure
15 does not follow the ISO or ASTM standards)

Boiling water tests were carried out according to the JAS-III Standard: the glued
blocks were immersed in boiling water for three hours, then dried at 60°C for 24
hours. The treatment comprising immersion in boiling water for three hours then
20 drying at 60°C for 24 hours was repeated prior to shear strength determination
for those glued blocks that were intact after the first treatment.

Table 8: Wood Bonding Performance Tests

Dry State Cold water Boiling

Sample Description soak water*
W F W F W F
90 PC(8)/NC(2)/R1 /TA 55.5 0 0 0 22.3 0
91 PC(7)/NC(2)/AC(1)/TA 101.5 0 71.7 0 38.0 0
92 PC(8)/NC(2)/R3 105.5 0 23.5 0 14.6** 0
93 PC(8)/N(2)/R3 108.9 0 69.0 0 55.3** 0
94 P(8)/N(2)/R3 103.3 0 29.0 0 23.2** 0
95 PC(8)/N(2)/R1/TA 52.5 0 27.9 0 32.8** 0
WO 03/046099 PCT/NZ02/00265

18

96 PC(8)/NC(2)/AC(1 )/R3 128.9 20 48.9 0 23.4 0

97 P 148.4 100 37.0 0 - 0
98 PALK 160.8 100 21.0 0 - 0
99 PC(8)/NC(2)/R1/TA/R3 34.9 0 25.8 0 16.7 0
120 PC 155.8 100 58.8 0 - 0
121 PC(8)/NC(2)/R1 58.9 0 14.0 0 11.4** 0
122 PC(8)/NC(2) 164.7 100 95.0 0 40.4 0
123 PC(8)/N(2) 157.9 100 54.3 0 52.3 0
124 PC(8)/AC(1 )/N(1 )/R2 124.7 25 39.0 0 48.5** 5
125 PC(8)/AC(1 )/NC(1 )/R2 107.8 0 74.2 0 62.6** 10
126 PC(8)/AC(1 )/N(1 )/R2 85.6 0 16.4 0 8.5** 0
127 P(8)/N(2) 174.8 100 69.7 0 23.8** 0
128 P(8)/N(2)/R2 67.7 0 48.7 0 54.3** 0
129 PC(8)/N(2)/R2 156.6 100 38.5 0 6.6** 0

Notes
Parts by volume in parentheses in the description column.
O
Columns W = maximum load kg cm ,
5 Columns F = Proportion (%) of wood failure (the glue was stronger than the
wood).
* Samples 91, 96, 99, 122, 123, 124, 125, 128 survived the second treatment
The other samples (except 97, 98 and 120) showed weakening but not complete
separation at the glue line. Samples 97, 98, 120 separated in boiling water within
10 about 1 hour.
** Glue joints weakened upon boiling were pressed together and left in an oven
at 60°C for 48 hrs before testing

By way of interpretation, note that for those samples where the wood, not the
15 glue, gave way, the force involved is about 150-180 kg cm-2. The most promising
compositions appear to be those with the highest remaining strength after boiling.
Samples 91, 96, and 125 were good; with 125 being the "best" according to these
tests.
WO 03/046099 PCT/NZ02/00265

19

EXAMPLE 5A: (see also Fias 1 and 2)

Wood bonding performance tests during extended boiling.

Boiling water test

5
The boiling water test was conducted by continuous boiling of glued wood blocks,,
which gave good relative results for water and heat resistance. The wood blocks
were subjected to two boiling cycles. First the glued wood blocks were boiled for
3 hr, dried in an air circulated oven at 60°C for 48 hr and re-boiled for 4 hr. The
10 results are presented in Table 9 and in bar charts in Figs 1 and 2, where the
height of each bar corresponds to the time to a point of failure. Only a few
samples passed both the 3 and then the 4 hour boiling tests.

Water resistance test

15
The samples were immersed in water at room temperature for 6 weeks with the
following results:

The samples showed excellent resistance to water immersion for 6 weeks.

20 Samples 97, 98, 120, 124 and 125 showed creamy appearance at the joints
within 2- 3 weeks but the joints were intact.

Although uncompounded polychloroprene latex generally has good mechanical

and storage stability, the adhesive composition may require the incorporation of
25 additional acid acceptors such as zinc oxide dispersions or aqueous epoxy resins
to minimize the degradation of the adhesive composition due to release of
hydrochloric acid from the polychloroprene rubber.
WO 03/046099 PCT/NZ02/00265

20

Table 9 - Variants Of Wood Adhesive.

Sample Description tfaii-1/hours tfan-2/hours

90 PC(8)/NC(2)/R1/TA 2.5
91 PC(8)/NC(2)/R3 pass pass
92 PC(8)/NC(2)/R3 1
93 PC(8)/N(2)/R3 1
94 P(8)/N(2)/R3 1.5
95 PC(8)/N(2)/R1/TA 2

96 PC(8)/NC(2)/AC(1 )/R3 pass pass

97 P 0.5
98 PALK 0.75
99 PC(8)/NC(2)/R1/TA/R3 pass 2.5

120 PC 1.5
121 PC(8)/NC(2)/R1/TA 1.5
122 PC(8)/NC(2) pass pass
123 PC(8)/N(2) pass 3
124 P(8)/N(1 )/AC(1 )/R2 pass 1
125 PC(8)/NC(1 )/AC(1 )/R2 pass pass
126 PC(8)/N(1 )/AC(1 )/R2 1.5
127 P(8)/N(2) 2.75
128 P(8)/N(2)/R2 pass 2.5
129 PC(8)/N(2)/R2 1.5

Parts by volume in parentheses.

5 P - Poly(vinyl acetate) NR-NaturaIRubber R1-Epoxy resin (Europox 710)
R2 - SE 780 R3 - SE 790 AC- crosslinked AQL
PC - crosslinked alkalised PVA N C -crosslinked NR A - AQ L-Aquastik 1120/
Neoprene 115
PALK - alkalised PVA N - alkalised NR TA- Tetraethylenepentamine
10
WO 03/046099 PCT/NZ02/00265

21

In Table 9 “pass” in column 3 signifies that the adhesive joint between the wood
blocks remained intact after immersion for three hours in boiling water and drying
at 60°C for 48 hours. “Pass” in column 4 signifies that the adhesive joint
remained intact after subsequent immersion for 4 hours in boiling water. The
5 times recorded in column 3 and column 4 are the times after which the adhesive
joint failed during immersion in boiling water.

Sample 90, sample 95, sample 121 and sample 122 coagulated after standing at
ambient temperature for 1 week.
10
EXAMPLE 6:
Particle Boards Using Natural Rubber/ Pva Adhesives

A number of processes to consume wood chips and convert them into boards
15 rely on forming a matrix of mutually adherent chips set into a solid mass. The
non-toxic and waterproof nature of adhesives according to this invention permit
the manufacture of a water-resistant version of particle board, useful for
bathrooms and shower floors as well as other areas likely to be exposed to
water. In particular, the traditionally employed adhesive in particle board is likely
20 to release trace amounts of potentially toxic formaldehyde over an extended
period and there is a good deal of consumer resistance in some societies to the
risk of exposure to this gas.

EXAMPLE 7:
25 Grafted Natural Rubbers In PVA Adhesives

By way of a yet further variation the present invention also provides adhesive
compositions including modified natural rubber, another synthetic rubber, or their
combinations with PVA. Preferably, such natural and synthetic rubbers have
30 unsaturated chains derived from units such as butadiene or have units derived
from C4 to C10 conjugated dienes, such as styrene or methyl methacrylate.
Natural rubber is commercially available as modified general-purpose latex. For
example, modified latex is available under the tradenames MEGAPOLY latex, as
MG 49, and as MG 30 (rubber latexes grafted with methyl methacrylate to
35 increase the polarity and thereby the adhesion of the adhesive compositions.
WO 03/046099 PCT/NZ02/00265

22

These compositions would give relatively transparent, tough and semireinforced

films.

The adhesive compositions of the present invention provide the following

5 advantages

1 The compositions provide an effective contact adhesive for a variety of

substrates. The compositions provide a user-friendly alternative to existing
adhesives because they are water based and do not employ organic solvents,
10 which may be toxic and expensive.
2 The compositions are inexpensive to produce because they lack exotic
materials.
3 One aspect of the invention provides adhesive compositions suitable to
manufacture self sealing envelopes and self sticking note pads similar to the

15 commercially available and popular "3M Post-it ™ "Note Pads.

4 Another aspect of the invention provides a set of heat and water resistant,
water-based contact adhesive compositions suitable for the outdoor wood
products manufacturing industry.
5 A further aspect of the invention provides coating compositions for
20 application on a variety of films including bubble pack, polyethylene,
polypropylene and the like which may be used as easily peelable removable
protective coatings to prevent scratching or damage of various surfaces including
glass, stainless steel and the like.
6 The invention also provides coating compositions for application on
25 variety of surfaces such as paper and cardboard to provide printable, yet water
and moisture resistant coatings.
7 The waterproof properties, and the transparency of the glue line after
bonding of the compositions of the present invention should allow extensive use
in construction of wood laminates particularly in applications where glue lines are
30 traditionally visible.
8 A longer shelf life than current materials used for resealable envelopes is
an advantage over existing materials.
WO 03/046099 PCT/NZ02/00265

23

9 The capability of the compositions of the present invention to accept ink is

useful in product labelling, and may be extended for example to manufacture of
audiovisual transparencies, as a printable coating over a "Mylar" sheet.
10 The non-toxic and waterproof nature of the adhesive compositions of the
5 present invention permit the manufacture of water-resistant particle board, useful
for bathrooms and shower floors as well as other areas likely to be exposed to
water.

Finally, it will be understood that the scope of this invention as described and/or
10 illustrated within this provisional specification is not limited to the preferred
embodiments described herein for illustrative purposes. Those of skill will
appreciate that various modifications, additions, and substitutions are possible
without departing from the scope and spirit of the invention as set forth.
WO 03/046099 PCT/NZ02/00265

24

CLAIM S

1 A water based adhesive composition, including

(a) at least one poly(vinyl acetate); and
5 (b) at least one latex;
wherein in use the adhesive composition, after drying, is substantially
water-resistant.

2 The composition according to claim 1 wherein the poly(vinyl acetate) is

10 cross linked.

3 The composition according to claim 1 or claim 2 wherein the at least one

latex is selected from one or more of the following; a natural rubber latex,
a modified natural rubber, a compounded natural rubber latex, a modified,
15 cross linked natural rubber latex, a polychloroprene rubber latex and a
modified polychloroprene rubber latex.

4 The composition according to claim 3 wherein the modified natural rubber

includes unsaturated chains.
20
5 The composition according to claim 4 wherein the unsaturated chains of
the modified natural rubber includes styrene or methyl methacrylate
groups.

25 6 The composition according to claim 5 wherein the styrene or methyl

methacrylate groups are further bonded to butadiene groups.

7 The composition according to any one of claims 3 to 6 wherein the

modified natural rubber is a compounded, a prevulcanized, or a grafted
30 natural rubber.

8 The composition according to claim 7 wherein the compounded modified

natural rubber includes one or more further components to at least
partially cross link the natural rubber the further components being
WO 03/046099 PCT/NZ02/00265

25

selected from an activator, an accelerator, an antioxidant and a cross

linking agent.

9 The composition according to claim 7 wherein the prevulcanized natural

5 rubber includes one or more further components adapted to at least
partially cross link the prevulcanized natural rubber the further
components being selected from an activator, an accelerator, an
antioxidant and a cross linking agent.

10 10 The composition according to claim 8 or claim 9 wherein the cross linking

agent is a zirconium salt in an alkaline medium.

11 The composition according to claim 10 wherein the zirconium salt is

zirconium nitrate.
15
12 The composition according to any one of claims 8 to 11 wherein the
activator is an inorganic oxide.

13 The composition according to claim 12 wherein the inorganic oxide is zinc

20 oxide.

14 The composition according to any one of claims 8 to 13 wherein the

accelerator is an organic dithiocarbamate, disulphide, thiozole and the
like.
25
15 The composition according to claim 14 wherein the accelerator is zinc
diethyldithiocarbamate, tetramethyl thiuram disulphide,
mercaptobenzothiozole and the like.

30 16 The composition according to any one of claims 8 to 15 wherein the

antioxidant is a phenolic or amine compound or a blend thereof.

17 The composition according to claim 16 wherein the antioxidant is

Antioxidant 2246, Wingstay L, Vanox MBPC, Vulkanox BKF, 4020, SKF,
35 MB 2 or SP.
WO 03/046099 PCT/NZ02/00265

26

18 The composition according to claim 7 wherein the grafted natural rubber

is further modified by the grafting of one or more polar polymers on to natural
rubber to increase polarity.

5 19 The composition according to claim 18 wherein the polar polymer is

selected from poly(methyl methacrylate) and styrene.

20 The composition according to any one of claims 7 to 19 wherein the

natural rubber is in a stable aqueous emulsion.
10
21 The composition according to claim 19 wherein the aqueous emulsion is
preserved with a biocide.

22 The composition according to any one of claims 3 to 21 wherein the

15 polychloroprene rubber latex and the modified polychloroprene rubber latex
further include one or more acid acceptors to stabilise said composition.

23 The composition according to claim 22 wherein the one or more acid

acceptors is selected from a zinc oxide dispersion or an aqueous epoxy resin.
20
24 The composition according to any one of claims 3 to 23 wherein about
10% to about 40% by volume of the natural rubber latex is blended with the
poly(vinyl acetate).

25 25 The composition according to claim 24 wherein the natural rubber latex is

blended with the poly(vinyl acetate) before any polychloroprene is added to
the composition.

26 The composition according to any one of claims 1 to 25 wherein the

30 composition further includes an effective amount of at least one water based
tackifying agent.

27 The composition according to claim 26 wherein the water based tackifying

agent is an aqueous dispersion.
35
WO 03/046099 PCT/NZ02/00265

27

28 The composition according to claim 26 or claim 27 wherein the water

based tackifying agent is selected from one or more of a rosin acid, a rosin
ester, a terpene phenolic resin, a hydrocarbon resin, and a coumarone
indene resin.
5
29 The composition according to any one of claims 26 to 28 wherein the
tackifying agent is present in an amount of about 1% to about 50% by
volume, based on the weight of the composition.

10 30 The composition according to claim 29 wherein the tackifying agent is

present in an amount of about 40% by volume, based on the weight of the
composition.

31 The composition according to any one of claims 1 to 30 further includes,

15 as a water barrier, at least one substance selected from a range including
silicone, Additive 84, Additive 85, and Oratan 2001.

32 The composition according to claim 31 wherein the water barrier is

present in the composition at up to 20% by weight of the total composition.
20
33 The composition according to any one of claims 1 to 32 further including
at least one preservative.

34 The composition according to claim 33 wherein the preservative is a

25 biocide.

35 The composition according to claim 21 or claim 34 wherein the biocide is

a fungicide or a bactericide.

30 36 A method of bonding at least one substrate; the method comprising the

steps of:
b) applying a water based adhesive composition as defined in any
one of claims 1 to 34, to at least a portion of a surface of at
least one first substrate,
35 b) allowing the adhesive composition to at least partially dry on the
WO 03/046099 PCT/NZ02/00265

28

first substrate;
c) contacting the adhesive applied surface to a second substrate
surface; and
d) forming an adhesive bond between the first and second
substrates.

37 The method according to claim 36 wherein said first substrate is selected

from wood; metal including cold-rolled steel, galvanized steel, and aluminium;
fabric; paper; foam; plastics including poly(vinyl chloride,) polystyrene,
10 polyethylene, polypropylene, and fibreglass.

38 The method according to claim 36 or 37 further including the steps of

applying and at least partially drying an adhesive composition as defined in
any one of claims 1 to 34 to at least a portion of the second surface of a
15 substrate.

39 The method according to claim 36 or claim 37 wherein said adhesive

composition is selected so as to achieve a reversible or releasable adhesive
bond when said first substrate is selected from paper, polyethylene, bubble
20 pack and polypropylene.

40 The method according to claim 39 wherein the second substrate is paper

when the first substrate is paper.

25 41 The method according to claim 36 wherein when the first substrate is

selected from polyethylene, bubble pack and polypropylene and the second
substrate has a delicate surface such as a glass or stainless steel surface,
which is readily scratched.

30 42 A method of applying a water resistant coating to at least one substrate;

the method comprising the steps of:
a) applying a water based adhesive composition as defined in
any one of claims 1 to 34, to at least a portion of a surface of a
substrate, and
35 b) allowing the adhesive composition to dry on the substrate.
WO 03/046099 PCT/NZ02/00265

29

43 The method according to claim 42 wherein said substrate is selected from

wood; metal including cold-rolled steel, galvanized steel, and aluminium;
fabric; paper; paperboard; corrugated boards, kraft cardboard; foam; plastics
including poly(vinyl chloride,) polystyrene, polyethylene, polypropylene, and
5 fibreglass.

44 The method according to claim 43 wherein said substrate is selected from

paperboard, corrugated card and kraft cardboard.

10 45 The method according to any one of claims 42 to 44 further including the

step of printing on the dry water resistant coating on the substrate.

46 A method of bonding at least one first wood substrate to a second wood

substrate; the method comprising the steps of:
15 a) applying a water based adhesive composition as defined in any
one of claims 1 to 34, to at least a portion of a surface of the
first wood substrate,
b) allowing the adhesive composition to at least partially dry on the
first wood substrate;
20 c) contacting the adhesive applied surface to the second wood
substrate surface; and
d) forming a transparent adhesive bond between the first and
second wood substrates.

25 47 The method according to claim 46, wherein the adhesive composition

includes poly(vinyl acetate), natural rubber, cross-linked polychloroprene
rubber, and a tackifing agent.

48 The method according to claim 47 wherein the PVA and the natural
30 rubber is cross-linked.

49 The method according to any one of claims 46 to 48 wherein the

composition includes 8 parts by weight of cross linked poly(vinyl acetate), 1
WO 03/046099 PCT/NZ02/00265

30

part by weight of cross linked polychloroprene latex; 1 part by weight of cross

linked natural rubber and. two parts by weight of a tackifing agent
“(PC(8)/AC(1 )/NC(1 )/R2)”.

5 50 A method of making a water-resistant structural chipboard component, the

chipboard being substantially comprised of fragments of wood bonded
together with a water based adhesive composition including poly(vinyl
acetate), natural rubber, cross-linked polychloroprene rubber, and a tackifing
agent.
10
51 The method according to claim 50 wherein the PVA and the natural
rubber is cross-linked.

52 The method according to claim 50 or claim 51 wherein the composition

15 includes 8 parts by weight of cross linked poly(vinyl acetate), 1 part by weight
of cross linked polychloroprene latex; 1 part by weight of cross linked natural
rubber and two parts by weight of a tackifing agent “(PC(8)/AC(1)/NC(1)/R2)”.

53 A transparency sheet including a dye-receptive or printable layer, the dye-

20 receptive layer comprising a water based adhesive composition including a
poly(vinyl acetate) component together with at least one member selected
from a synthetic latex and/or a natural rubber latex.

54 The transparency sheet according to claim 53 wherein the synthetic latex

25 is polychloroprene latex.
 INTERNATIONAL SEARCH REPORT Intemational application No.
PCT/NZ02/00265

A. CLASSIFICATION OF SUBJECT MATTER

Int. Cl. 7; C09J 131/04, 107/02, 111/02; E04C 2/16; B 27N 3/04; C08J 5/18, 7/04

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
IPC: C09J 131/04, 107/02, 111/02; D 21H 21/18; D 2 I H 21/20; E04C 2/16; B 27N 3/04; C09D; 131/04, 107/02, 111/02;
CO8J 5 /1 8 ,7 /0 4
Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)
D E R W E N T: W P A T , JAPIO

DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to
claim No.

US 5476896 A ( P E R E IR A et a l ) 19 December 1995

X col. 3, lines 42-47; examples 1-5; claims 1-19 1-49
Y 50-54

W O 01/10968 A ( 3 M IN N O V A T IV E PROPERTIES C O M P A N Y ) 15 February 2001

X page 4, lines 7-15; page 8, line 13 - page 10, line 18; claims I, 10, 11, 17-21 1-49

W O 00/35596 A ( A . B. B R O D E U R ) 22 June 2000

X page 3, lines 12-26; example IV ; claims 1-14,16 1-46

X Further documents are listed in the continuation o f Box C X See patent family annex

* Special categories of cited documents:

"A" document defining the general state of the art
which is not considered to be of particular
relevance
"E" earlier application or patent but published on or
after the international filing date
"L" document which may throw doubts on priority
claim(s) or which is cited to establish the
publication date of another citation or other special
reason (as specified)
"O " document referring to an oral disclosure, use,
exhibition or other means
n p ir
document published prior to the international filing
"T" later document published after the international filing date or priority date
and not in conflict with the application but cited to understand the principle
or theory underlying the invention
"X" document of particular relevance; the claimed invention cannot be
considered novel or cannot be considered to involve an inventive step
when the document is taken alone
"Y" document of particular relevance; the claimed invention cannot be
considered to involve an inventive step when the document is combined
with one or more other such documents, such combination being obvious to
a person skilled in the art
document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report
21 February 2003 2 6 FEB 2003
Name and mailing address of the ISA/AU Authorized officer
AUSTRALIAN PATENT OFFICE
PO BOX 200, WODEN ACT 2606, AUSTRALIA
E-mail address: pct@ipaustralia.gov.au DR. A TESSEMA
FacsimileNo. (02)6285 3929 TelephoneNo : (02) 6283 2271

FormPCT/ISA/210 (second sheet) (July 1998)

 INTERNATIONAL SEARCH REPORT International application No.
PCT/NZ02/00265
C (Continuation). D O C U M E N TS CONSIDERED TO BE R ELEV A N T

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to
claim No.

US 5145748 A ( G A ID IS et al. ) 8 September 1992

X col. 3, line 35 - col. 4, line 18; col. 5, line 19 - col. 6, line 14; claims 1-46

US 4299930 A ( BOGGS ) 10 November 1981

X example I; claims 1-46

EP 1008639 A ( IN T E R N A T IO N A L SD H ES IVE S B V ) 14 June 2000

X page 3, line 11 - page 4, line 56; claims 1-17 1-46

DerwentAbstract Accession Number 82-67207E/32, Class A81 G03 (A l8 ), and JP 57-

108174 A (A IK A K O G Y O K K ) 6 July 1982
X abstract 1-46

DerwentAbstractAccessionNumber 81-50653D/28, Class A81 G03 (A 12A 14), and JP

56-059883 A (A IK A K O G Y O K K ) 23 M a y 1981
X abstract 1-46

Derwent Abstract Accession Number 94-018645/03, Class A81 G03 ( A l 8 A 25), and JP
5-320601 A (S E K IS U IC H E M IN D CO L T D ) 3 December 1993
X abstract 1-46

Derwent AbstractAccessionNumber 96-094467/10, Class A81 G03 ( A l 7), and JP 8-

003527 A (M IT S U I D U PO N T P O L Y C H E M IC A L K K ) 9 January 1996
X abstract 1-46

DerwentAbstractAccessionNum ber 81-01074D/02, Class A81 G03 (A17 A 23)), and

JP 55-144042 A (D J K IN T K K ) 10 November 1980
X abstract 1-46

DerwentAbstractAccessionNumber 80-37350C/21, Class A81 G03 (A 18), and JP 55-

050081 A ( K Y O E IK K ) 11 April 1980
X abstract 1-46

Derwent AbstractAccessionNumber 95-252489/33, Class A81 G03 ( A l 8 A 25), and JP

7-157742 A (K A N E B O N SC K K ) 20 June 1995
X abstract 1-46

U S 4804573 A (M c C A R T H Y et a l.) 14 February 1989

X claims 4-8 1-25, 36-45

EP 052938 A ( M IN N E S O T A M IN IN G A N D M A N U F A C T U R IN G C O M P A N Y ) 15
January 1986
X col. 3, lines 34-47; col. 5, lines 16-44; claims 1-8 53
Y 54
U S 5407895 A ( E G A S H IR A et al. ) 18 A pril 1995
Y col. 2, line 59 - col. 3, line 13; examples 1 ,2 5 3 ,5 4

FormPCT/ISA/210 (continuation of Box C) (July 1998)

 INTERNATWiAL SEARCH REPORT ^Remational application No.
Information on patent family members PCT/NZ02/00265

This Annex lists the known "A" publication level patent family members relating to the patent documents cited in the
above-mentioned international search report. The Australian Patent Office is in no way liable for these particulars
which are merely given for the purpose o f information.________________________________________________________

Patent Document Cited in Patent Family Member

Search Report

US 5476896 BR 9401951 CA 2149619

WO 200110968 AU 200020281 BR 9917427 EP 1206502

US 6440259

WO 200035596 US 6187865

us 5145748 AU 57549/90 CA 2017530 EP 403958

GB 2234275 HK 1413/94 NZ 233668

SG 1245/94 TR 27453 ZA 9003738

US 5132183

us 4299930 NONE

EP 1008639 NONE

us 4804573 BE 905477

EP 52938 CA 1184951 JP 57122448

US 5407895 EP 332204 EP 715963 JP 1229689

US 4992413 US 5166127 US 5362701

JP 1229690 JP 1229691 JP 1229695

JP 1229692 JP 1264893 JP 1291985

E N D OF A N N E X

FormPCT/ISA/210 (citation family annex) (July 1998)