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

(19) World Intellectual Property Organization

International Bureau

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

29 January 2009 (29.01.2009) PCT WO 2009/012545 Al
(51) International Patent Classification: MIGUEL, Rovido, Ubirajara [BR/BR]; Rua Alhambra,
C09J 111/00 (2006.01) C08K 5/00 (2006.01) 25, Jardim Europa, 09172-120 Sao Paulo - SP (BR).

(21) International Application Number: (74) Agent: MOMSEN, LEONARDOS & CIA.; Rua Teofilo
PCT/BR2008/000174 Otoni 63, 10th floor, 20090-080 Rio de Janeiro - RJ (BR).

(22) International Filing Date: 23 June 2008 (23.06.2008)
(25) Filing Language: English
(26) Publication Language: English
(30) Priority Data:
PI0703285-4 26 July 2007 (26.07.2007) BR
(71) Applicant (for all designated States except US): OX-
ITENO S.A. INDUSTRIA E COMERCIO [BR/BR];
Av. Brigadeiro Luis Antonio, 1343, 7° andar, BeIa Vista,
01317-001 Sao Paulo - SP (BR).
(72) Inventors; and
(75) Inventors/Applicants (for US only): DA SILVA,Andre,
Luis, Conde [BR/BR]; Rua Virginia Ferni, n. 501, apt
41A, 08253-000 Sao Paulo - SP (BR). TOMASSINI,
Carlos, Roberto [BR/BR]; Rua Cruzeiro, 103, 09060-080
Santo Andre - SP (BR). ROSA, Fabio [BR/BR]; Rua
Santo Andre, 55, apt 41, Bloco A, 09020-230 Santo Andre
- SP (BR). SABIO, Airton, Antonio [BR/BR]; Rua Aruja,
353, Vila Curuca, 09291-250 Santo Andre - SP (BR).
(81) Designated States (unless otherwise indicated, for every
kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA,
CH, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE,
EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID,
IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC,
LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN,
MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH,
PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV,
SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN,
ZA, ZM, ZW
(84) Designated States (unless otherwise indicated, for every
kind of regional protection available): ARIPO (BW, GH,
GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,
FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,MC, MT, NL,
NO, PL, PT, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG,
CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG).
Published:
— with international search report

(54) Title: TOLUENE-FREE BALANCED SOLUTIONS OF SOLVENTS FOR CONTACT ADHESIVES

(57) Abstract: The invention relates to balanced solutions of solvents without toluene for contact adhesives based on polychloro-
prene resins, basically consisting in a mixture of mutually miscible solvents, intended to promote the solubility of the above cited
resins. Such solutions comprise in their formulation a range of organic compounds with distinct characteristics, such as aliphatic
and/or cycloaliphatic hydrocarbons, esters based on the alkyl acetates, comprising alkyl groups with 4 to 6 carbon atoms, alcohols
with straight or branched carbon chains with 2 to 6 carbon atoms and ketones with a structural composition comprised of 3 to 5
carbon atoms.
"TOLUENE-FREE BALANCED SOLUTIONS OF SOLVENTS FOR
CONTACT ADHESIVES"

Field of the invention

The present invention refers to contact adhesives, particularly
those that use in their composition a plurality of solvents of chemical
functions, and more particularly those which composition is devoid of toluene
or aromatic hydrocarbon derivatives.

Prior art
Contact adhesives are substances which purpose is to join
different parts or materials, introducing new functions and properties that
provide to the final assembly a value that is greater than the sum of its
components alone, in addition to providing a significant reduction of the time
and/or cost of assembly when compared with other production processes such
as welding of metals, weaving of fabrics or yet the mechanical joining using
rivets, screws and nails.

The extensive use of adhesives, glues and sealants in the

automotive industry, aviation, paper, electric and electronics industries,
furniture, leather and shoemaking and in civil construction entails a
continuing demand of new formulations with better stability and better
physical and mechanical properties. Such formulation is aimed at providing a
competitive end product, however less toxic than the prior art formulations,
moisture-resistant and having an excellent cost/benefit ratio, among other
properties.

Among the wide variety of existing contact adhesives there

should be pointed out those that incorporate in their formulation the polymer
polychloroprene (CR), due to the same improving the various characteristics
of the articles produced thereby. The said improvement is achieved due to the
fact that the said polymer evidences high resistance to weather exposure and
non-polar products, in addition to constituting a thermoplastic product with
weak mechanical properties prior to vulcanization, and thermo-rigid, adherent
to metals and resistant to aging, chemical agents and flame after being
vulcanized. Furthermore, it is obtained by polymerization of the monomer
chloroprene, and differently from the other elastomers, it can be vulcanized
with magnesium oxide, in addition to being resistant to chemical attack,
particularly to seawater, due to its formulation including chlorine atoms.

Furthermore, it evidences a strong tendency to crystallize and

to form crystals in the macromolecule, which occurs in the form of a more or
less strong hardening during the conservation of the rubber, of the raw
mixture, or of the vulcanized product at ambient temperature, and particularly
at low temperatures. Such tendency is stronger in rubbers whose structures
were not subject to modification, and may be weakened with the introduction
of plasticizers or resins of an adequate nature.

Crystallization is a property that is inherent to polychloroprene

rubbers, although some crystallize faster than others. As it develops, there
occurs a small reduction in volume, however without occurrence of
crystallization at locations with high temperatures, since the orientation forces
are dominated by the vigorous molecular motion.

The structure of the said polymer may be modified by means

of copolymerization of the chloroprene with sulfur and/or butadiene, aiming
to provide a family of the materials evidencing improved and increased
chemical and physical properties. To that end, the polychloroprene rubber was
split into two distinct groups, to wit: those intended for the manufacture of
adhesives and those intended for general industrial application, this latter
being characterized by being split into three families: type G family, type W
family and type T family.

Within the type G family, the most typical grades of GN

neoprene are those whose stability is limited as a raw material, while the
GNA and GT neoprenes evidence a better resistance to crystallization,
although still weak.

The neoprenes of the W family, in addition to evidencing a

better storage stability, are more resistant to crystallization, due to the
modification with mercaptan undergone thereby during production.
Furthermore, they have a more uniform distribution of molecular weight and
usually require organic accelerators in order to achieve a reasonably fast
vulcanization. The most typical grades of the W family are the neoprenes W,
WHV, WK and WRT, this latter being characterized by being more resistant
to crystallization.

Similarly to the W type family, the type T family of neoprenes,

which subdivides in to the TW and TRT neoprenes, have a gel polymer
moiety aimed at improving their behavior, are resistant to crystallization and
require organic accelerators, in addition to having low nerve and shrinkage.

Presently the contact adhesive formulations incorporate a large

amount of toluene, see for example the disclosure of document No.
PI050 1666-5, which, due to a certain amount of toxicity and rapid
evaporation, entails damage to the nervous system, entailing short-term or
long-term effects ranging from tiredness, nausea, mental confusion, weakness,
loss of memory, loss of appetite, hearing and vision, and might even cause
loss of consciousness and death.

Due to their toxic properties and the fact that they are
commercialized without restrictions, such adhesives are used as
hallucinogenic substances, a fact that causes a proliferation of chemical
substances abusers, thereby increasing the rates of criminal events and death
by intoxication. Such fact may be explained in that the applicability in
question derives from direct contact with the product.

There also exist contact adhesive formulations prepared based

on the solvent cyclohexane, see for example the disclosure of document No.
PI 9901812-8, however still implying limitations in terms of their toxic
properties, environmental issues, performance and cost-benefit ratio.

Objects of the invention

In light of what has been set forth above, the object of the
present invention consists in the provision of a composition of solvents with
various chemical functions, however devoid of the organic compound toluene
or aromatic hydrocarbon derivatives.

One other object of the invention is to provide the solubility of

the neoprene or polychloroprene polymers.

One further object of the invention consists in the provision of

a solution with less ozone formation potential at low atmospheric levels.

Yet another object of the invention consists in the provision of

a formulation comprehending not only an excellent performance but also an
excellent cost/benefit ratio.

Another object of the invention consists in the provision of a

formulation having characteristics similar to those of a formulation which
composition comprises toluene.

Brief description of the invention

The above listed objects, as well as others, are achieved by the
invention by means of the provision of balanced solvent solutions comprising
a plurality of hydrocarbons, alkyl acetates, alcohols and ketones, within the
scope of providing the solubilization of the polychloroprene resins.

According to one other characteristic of the invention, the said

solutions comprise, among a range of organic compounds, 2-butanone, 1-
methylpropanol, aliphatic and cycloaliphatic hydrocarbons and acetates.

According to one further characteristic of the invention, the

alkyl group comprises a carbon chain varying between 2 and 6 carbon atoms.

According to yet another characteristic of the invention, the

ketone group has a variance of between 3 and 5 carbon atoms.

Detailed description of the invention

The present invention is based on the fact that the total or
partial absence of the toluene or of the aromatic hydrocarbon derivative
compounds provides as a result a solution for contact adhesives which
toxicity level is substantially lesser that in formulations containing toluene.
The said solution is based on the use of mutually miscible solvents, and is
prepared by mixing a plurality of organic solvents through a range of systems
for the purpose of providing its homogenization as a product and to solubilize
the polychloroprene resins that constitute the contact adhesives.

From the physical-chemical perspective, and taking into

consideration the ample variety of possible formulations, the said solubility
will be achieved in the measure that the solutions themselves achieve an
excellent performance regarding their applicability, density, viscosity and
drying time, in order to fulfill the commercial requirements of the product
being manipulated.

Regarding the composition of the said solutions, there are

employed in the formulation thereof substances corresponding to four organic
functions, to wit: hydrocarbons, esters, alcohols and ketones.

The hydrocarbons used in the mixture comprehend, in their

entirety, both aliphatic and cycloaliphatic hydrocarbons, where the sum total
thereof comprises about 10 to 50% in mass of the total ingredients.

As for the substances that comprise the organic function of

esters, there are present therein, in a mass percentage level of 10 to 50%, the
alkyl acetates having in the alkyl group an amount of carbon which variation
ranges from 2 to 6 atoms. There is used the same percentage level for the
substances formed by oxidation of the secondary alcohols, more specifically
the ketones, however the said ketones evidence a structure comprising from 3
to 5 carbon atoms.

The alcohols employed in the formulation of the solutions

have a straight or branched carbon chain comprised of a variation of carbon
atoms in excess of 2 and of less than 6, in a concentration comprised between
5 and 30% in mass of the above cited substances.

For purposes of illustration of the substances that characterize

the solutions, there may be cited, among a wide variety thereof, the n-hexane,
n-heptane, methyl-cyclohexane, cyclohexane, acetates of ethyl, propyl,
isopropyl, butyl, isobutyl, sec-butyl, isopentyl, amyl and hexyl, ethanol,
propanol, isopropanol, n-butanol, isobutanol, sec-butanol, pentanol,
isopentanol, hexanol, propanone, methyl ethyl ketone, methyl isobutyl ketone,
methyl amyl ketone, etc.

Due to the wide variety of embodiments of the invention, we

might cite as examples for purposes of information and clarification on the
compositions, some formulations based on 2-butanone, 1-methyl propanol,
aliphatic and cycloaliphatic hydrocarbons, 1-methyl propyl acetate, 3-methyl
butyl acetate and butyl ethanoate, that provided the complete solubilization of
the polychloroprene resin, without however such formulations restricting the
scope of the invention.

FORMULATION 1
FORMULATION 2

FORMULATION 3

FORMULATION 4
 FORMULATION 5

In one other embodiment of the invention which mass

percentages encompass a wider range of levels, we may cite, as illustration,
formulations comprising about 10 to 50% aliphatic and/or cycloaliphatic
solvents, preferably based on the compounds which carbon chain has 6 to 10
atoms, about 10 to 50% ketones, preferably 2-butanone and/or propanone,
alkyl acetates with a carbon chain comprised of 4 to 6 carbon atoms,
preferably 3-methyl butyl acetate and/or 3-methyl propyl acetate and/or n-
butyl acetate in a range comprised between 10 and 40% and the alcohols
based preferably on 1-methyl propanol, in a concentration of from 5 to 30%.
 CLAIMS

1. Toluene-free balanced solutions of solvents for contact

adhesives based on polychloroprene resins comprising a plurality of miscible
solvents having various chemical functions, which may comprise
hydrocarbons, ketones, alcohols and esters, characterized in that the mixture
comprises about 10 to 50% in mass of ketones with a carbon chain comprised
of between 3 and 5 carbon atoms, about 10 to 50% in mass of aliphatic and
cycloaliphatic hydrocarbons with a carbon chain comprised of 6 to 10 carbon
atoms, about 5 to 30% in mass of alcohols with a carbon chain comprised of 2
to 6 carbon atoms and about 10 to 50% in mass of alkyl acetates with a carbon
chain comprised of 4 to 6 carbon atoms in the alkyl group.

2 . Balanced solutions of solvents, as claimed in claim 1,

characterized in that the alkyl acetates are preferably isopentyl acetate and
isomers thereof, and/or 3-methyl propyl acetate.

3 . Balanced solutions of solvents, as claimed in claim 2,

characterized in that the alkyl acetates comprise about 20 to 40% in mass of
the mixture.

4 . Balanced solutions of solvents, as claimed in claim 1,

characterized in that the said alcohols are preferably isobutanol and/or sec-
butanol and/or isopentanol.

5. Balanced solutions of solvents, as claimed in claim 4,

characterized in that the alcohols comprise about 10 to 20% in mass of the
mixture.
 6. Balanced solutions of solvents, as claimed in claim 1,
characterized in that the ketone is preferably 2-butanone.

7. Balanced solutions of solvents, as claimed in claim 6,

characterized in that the said ketone comprises about 10 to 30% in mass of
the mixture.

8. Balanced solutions of solvents, as claimed in claim 1,

characterized in that the said aliphatic and cycloaliphatic hydrocarbons
preferably have a carbon chain comprised of 6 to 8 carbon atoms.

9. Balanced solutions of solvents, as claimed in claim 8,

characterized in that the aliphatic and cycloaliphatic hydrocarbons comprise
about 20 to 40% in mass of the mixture.

10. Balanced solutions of solvents, as claimed in claims 1 to 9,

characterized by being produced by means of any substance homogenizer
system.

11. Balanced solutions of solvents, as claimed in claims 1 to 9,

characterized in that the mixture of the organic compounds provides the
solubility of the polychloroprene resins.
 A. CLASSIFICATION OF SUBJECT MATTER ,
INV. C09J1 11/00 C08K5/00

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

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C08K C09J

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 practical, search terms used)

EPO-Internal , WPI Data

C. DOCUMENTS CONSIDERED TO BE RELEVANT

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

DATABASE MPI Week 200416 1-11

Thomson Scientific, London, GB; AN
2004-159682
XP002499324
& JP 2003 226852 A (AICA KOGYO CO LTD)
15 August 2003 (2003-08-15)
abstract
paragraph [0009]

DATABASE WPI Week 200759 1-11

Thomson Scientific, London, GB; AN
2007-613833
XP002499325
& CN 1 952 031 A (CHINA PETROCHEMICAL
GROUP BALING PETROLE)
25 April 2007 (2007-04-25)
abstract

V-

Further documents are listed in the continuation of Box C. 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 document 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
"P" document published prior to the international filing date but
later than the priority date claimed
"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 docu¬
ments, 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

29 October 2008 07/11/2008

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
NL - 2280 HV Rijswijk
TeI. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Mettler, Rolf-Martin
Form PCT/ISA/210 (second sheet) (April 2005)
 C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

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

US 2004/254283 A l (MUSCH RUDIGER [DE] ET 1-11

AL MUSCH RUEDIGER [DE] ET AL)
16 December 2004 (2004-12-16)
abstract
paragraphs [0052] , [0062]

Form PCT/ISA/210 (continuation of second sheet) (April 20D5)

 Patent document Publication Patent family Publication
cited in search report date member(s) date

OP 2003226852 15-08-2003 JP 3773861 B2 10-05-2006

CN 1952031 A 25-04-2007 NONE

US 2004254283 Al 16-12-2004 CA 2527561 Al 09-12- 2004

CN 1842563 A 04-10- 2006
CN 1829767 A 06-09- 2006
DE 10324305 Al 16-12- 2004
EP 1633809 A2 15-03- 2006
WO 2004106237 Al 09-12- 2004
WO 2004106423 A2 09-12- 2004
JP 2007505196 T 08-03- 2007
KR 20060058767 A 30-05- 2006
US 2004241085 Al 02-12- 2004

Form PCT/ISA/210 (patent family annex) (April 2005)