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(19)

(11) EP 2 161 294 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.:

10.03.2010 Bulletin 2010/10 C08G 63/181 (2006.01) C09D 5/03 (2006.01)
C09D 167/00 (2006.01) B44C 1/17 (2006.01)
(21) Application number: 08075746.1

(22) Date of filing: 05.09.2008

(84) Designated Contracting States: (72) Inventors:

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • Beccaria, Damiano
HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT 12040 Sant’Albano Stura CN (IT)
RO SE SI SK TR • Bejko, Imir
Designated Extension States: 12040 Sant’Albano Stura CN (IT)
AL BA MK RS • Capra, Andrea
12040 Sant’Albano Stura CN (IT)
(71) Applicant: Hexion Specialty Chemicals Research • Carlevaris, Lino Natale
Belgium S.A. 12040 Sant’Albano Stura CN (IT)
1348 Ottignies Louvain-la-Neuve (BE) • Munari, Allessandro
12040 Sant’Albano Stura CN (IT)

(54) Hydroxyl polyester resins with high Tg

(57) The present invention relates to an amorphous containing at least 3 hydroxyl groups and from 0,1 to 10%
polyester containing hydroxyl groups and prepared from moles of aliphatic, cycloaliphatic, containing trimethylo-
an acid constituent comprising from 0,1% to 100% moles lethane (TME the said amorphous polyester having a
of isophthalic acid or terephthalic acid, from an alcohol glass transition (Tg) of at least 60°C, and a hydroxyl
constituent comprising from 0 to 40% moles of neo- number of 270 to 350 mgKOH/g, preferably 280 to, 310
pentylglycol, from 0 to 40% moles of at least one dihy- mgKOH/g.
droxylated compound other than neopentylglycol and
from 60 to 100% moles of polyhydroxylated compound
EP 2 161 294 A1

Printed by Jouve, 75001 PARIS (FR)

 1 EP 2 161 294 A1 2

Description [0010] It was surprisingly found the incorporation of

trimethylolethane (TME) in the polyester composition re-
[0001] The present invention relates to a thermally cur- sults in a significant increase in the Tg value of the pol-
able hydroxyl polyester resins containing trimethylo- yester resin and leading to improve the storage stability
lethane (TME) suitable for powder coating composition 5 in hot-humid conditions.
based on hydroxy functional polyester resins with a high [0011] The potential use of TME as monomer in resins
hydroxy value 280 to 340mg KOH/g and cured with a self production is known from a long time, such as listed
blocked uretdione. The powder formulations are suitable amongst other polyols in the US 6,808,821, 6,268,464,
for the preparation of a decorated substrate, by transfer 6,747,070, 6,710,137, 6,599,992, 6,635,721, US appli-
printing. 10 cation 2002/0114953 and 2005/0090636.
The transfer printing comprises the steps of: submitting US 6,635,721 patent describes TME as possible mono-
a substrate to a treatment to prepare its surface for the mer for the preparation of branched amorphous polyes-
application of a coating, applying a coating to the surface ters but no advantages coming from the use of TME are
of the substrate in one or more cycles, covering the sur- described.
face of the substrate with a sheet comprising a decoration 15 [0012] US application 2002/0114953 describes TME
which is to be transferred to said surface, and heating as typical example of polyhydric alcohol but no specific
the substrate and the sheet comprising the decoration to effect of the TME on the resin properties are described.
effect the transfer of the decoration from the sheet onto [0013] More over polyester based on isophthalic acid
the substrate. to improve the exterior durability of the cured coating has
[0002] Such a process is known from patent applica- 20 a reverse effect on the Tg of the resin and therefore in-
tion EP 0 817 728, which is directed to a process and the creases the tendency of sintering of the resins.
relevant apparatus for making decorated, extruded, pro- [0014] An amorphous polyester containing hydroxyl
filed elements. groups according to the invention, is prepared from an
[0003] EP 1 162 241 is about a powder coating com- acid constituent comprising from 0,1% to 100% moles of
position comprising a mixture of resins wherein at least 25 isophthalic acid or terephthalic acid, from 0 to 45% moles
one resin has a hydroxy number of less than 75 mg of at least one dicarboxylic acid or anhydride other than
KOH/g, at least one resin has a hydroxy number of at isophathalic or terephthalic acid and from 0 to 25% moles
least 75 mg KOH/g, and a curing agent for the resins. of polycarboxylic acid or anhydride containing at least
The curing agents used are isocyanate-functional prod- three carboxyl groups and from an alcohol constituent
ucts that are under environmental pressure due to their 30 comprising from 0 to 40% moles of neopentylglycol, from
toxicological aspects. 0 to 40% moles of at least one dihydroxylated compound
[0004] In US 3,907,974 curable decorating systems for other than neopentylglycol and from 60 to 100% moles
glass or metal containers using a heat transfer decoration of polyhydroxylated compound containing at least 3 hy-
are disclosed. droxyl groups and from 0,1 to 10% moles of aliphatic,
[0005] In WO 98/08694 a process is disclosed for dec- 35 cycloaliphatic, the said amorphous polyester having a
orating metal, plastic or the like materials. In this publi- glass transition (Tg) of at least 60°C, and a hydroxyl
cation very little information is given on the material used number of 270 to 350 mgKOH/g, preferably 280 to 310
to coat the surface of the substrate. mgKOH/g.
[0006] It was found that the resin used to coat the sub- The hydroxyl terminated polyester is formed through the
strate before the transfer printing step is of the utmost 40 esterification or condensation reaction of:
importance to the properties and appearance of the dec-
orated substrate. a dicarboxylic acid selected from the group consist-
[0007] The decorated substrate should have good me- ing of isophthalic acid (IPA), terephthalic acid (TPA)
chanical properties (e.g. scratch resistance, Tg of the 1,4-cyclohexane dicarboxylic acid (CHDA), 1,4-cy-
cured film, gloss, weathering and adhesion to the sub- 45 clohexane dimethylcarboxylic acid and mixtures
strate), the image should be transferred completely in thereof, with at least about 98% moles of the aro-
the transfer printing process, and the image’s support matic acid being isophthalic and polyol, such as tri-
(normally paper) should detach easily after transfer of methylolpropane (TMP), trimethylolethane (TME),
the image. pentaerythritol (PE), ditrimethylolpropane (DI-TMP)
[0008] The industry is also looking for resins to be used 50 and mixtures of thereof, with at least about 93%
in powder coating application with good storage stability moles is trimethylolethane (TME) and addition of di-
in hot and humid climate. Such a resin needs to have a ols selected from the group consisting of neopentyl
Tg value high enough to avoid sintering during storage. glycol, cyclohexane dimethanol, 1,6 hexane diol,
[0009] Polyester resins with hydroxyl number of 300 ethylene glycol, propylene glycol, 1,3-butylene gly-
mg KOH/g or above have a low molecular weight and 55 col, 1,4-butane diol, pentane diol, hexylene glycol,
this means a low Tg (see EP 1 162 2412 gives for exam- diethylene glycol, dipropylene glycol, triethylene gly-
ple 48-50°C); this range of temperature starts being crit- col, 2-butyl-2-ethyl diol, 1,3-propanediol, 2,2,4-tri-
ical from the storage point of view. methyl-1,3-pentane diol, hydrogenated bisphenol A,

2
 3 EP 2 161 294 A1 4

1,3-pentane diol, 3-hydroxy-2,2-diemthyl propyl 3- Example 1

hydroxy-2,2-dimethyl-propanoate, methyl propane
diol, 2-methyl, 2-ethyl, 1,3-propane diol, vinyl cy- a)Synthesis of hydroxyl functional amorphous polyes-
clohexane diol and mixtures thereof. ters:
In an alternative aspect of the invention, neopentyl 5
glycol can be replaced with a diol selected from the [0020] A mixture of 515 grams (4.95 moles) of neo-
group consisting of 2-butyl-2-ethyl-1,3 propanediol pentylglycol, 57 grams (3.17 moles) of deionized water,
(BEPD), 1,4 butane diol, 3-hydroxy-2,2-dimethyl 7865 grams (65,54 moles) of trimethylolethane, 9289
propyl-3-hydroxy-2,2-dimethyl propionate, unoxol 6 grams (55.96 moles) of isophthalic acid, 12.5 grams of
diol, 2-methyl-1,3-propane diol (MPD), hydroxy- 10 tris(2,4-ditert-butylphenyl)phosphite as antioxidant and
lpivalyl hydroxypivalate (HPHP), hydrogenated Bi- 10.7 grams of MBTO as esterification catalyst is intro-
sphenol A and mixtures thereof. duced into a 20 liters reactor provided with a stirrer, a
nitrogen inlet and a packed distillation column connected
[0015] Raw materials from renewable resources could to a water cooled condenser and an electronic thermom-
also be used as source of raw materials, like sorbitol de- 15 eter to control the reaction temperature. The mixture is
rivatives, dimer fatty acids, glycerol (derived from the pro- heated, under stirring and nitrogen sparge, to 165°C
duction of bio-diesel), lactic acid derivatives, fructose de- where water starts to distil from the reactor, then temper-
rivatives, mannitol derivatives, furfural derivatives, pyra- ature is gradually raised to 210°C and maintained until a
zol derivatives and the like. These monomers to produce clear polyester containing hydroxyl groups is obtained
the claimed resin compositions could be use alone or in 20 with these properties: ICI viscosity (at 200°C): 1800 -
combination with petrochemical based monomers. 2000 mPa.s, Acid Number: 3 - 4 mgKOH/g.
[0016] Optionally, the starting mixture for the esterifi- Set and let the temperature decrease at 200°C, maintains
cation or condensation reaction may further include from at this temperature until a polyester bearing hydroxyl
0.01 to 5% moles of a polyacid selected from the group groups is obtained with these properties: 2100 - 2300
consisting of trimellitic anhydride (TMA), citric acid, and 25 mPa.s at 200°C,
mixtures thereof. Acid Number: 2 - 3 mgKOH/g,
[0017] It will be appreciated that the incorporation of Hydroxyl value: 280 - 310 mgKOH/g.
the polyacid or the polyol may be performed during the Tg: 62 - 65 °C
first step or in the second step of preparation of the Cool the resin at 180°C and remove it from the reactor.
present resin. 30
The polyester may be prepared according to convention- Comparative example
al procedures by esterification or transesterification, op-
tionally in the presence of customary esterification cata- b)Synthesis of hydroxyl functional amorphous polyes-
lyst for example dibutyltin oxide or tetrabutyl titanate. The ters:
preparation conditions and the COOH/OH ratio may be 35
selected so as to obtain end product that have a hydroxyl [0021] A mixture of 168,4 grams (1.62 moles) of neo-
number within the targeted range of values. pentylglycol, 18.7 grams (1.04 moles) of deionized water,
8677,29 grams (64,76 moles) of trimethylolpropane,
Glass Transition measurement method 9289 grams (55.96 moles) of isophthalic acid, 12.5 grams
40 of tris(2,4-ditert-butylphenyl)phosphite as antioxidant
[0018] The following procedure was used for a Mettler and 10.7 grams of MBTO as esterification catalyst is in-
Toledo DSC 821e. 10 - 15 mg of the grinded resin is troduced into a 20 liters reactor provided with a stirrer, a
placed in an aluminium sample pan provided with a lid. nitrogen inlet and a packed distillation column connected
The lid is closed under a press and the sample pan is to a water cooled condenser and an electronic thermom-
placed in the DSC 821e. The Glass Transition Temper- 45 eter to control the reaction temperature. The mixture is
ature program is started, involving uniform heating of the heated, under stirring and nitrogen sparge, to 165°C
sample at a rate of 10°C/min from 0 °C up to 100°C. where water starts to distil from the reactor, then temper-
The program automatically generates data for the glass ature is gradually raised to 210°C and maintained until a
transition temperature, there are several calculation clear polyester containing hydroxyl groups is obtained
methods (ASTM, DIN, Midpoint STAR) to get the Tg val- 50 with these properties: ICI viscosity (at 200°C): 2500 -
ue, the ASTM is used. 2700 mPa.s, Acid Number: 3 - 4 mgKOH/g.
[0019] The examples of resins below illustrate the Cool the resin at 180°C and remove it from the reactor.
present invention and coating compositions suitable for The final specifications of the resin are:
decorated substrate, by transfer printing could be made
thereof. 55 ICI viscosity: 2700 - 2900 mPa.s at 200°C,
Acid Number: 3 - 4 mgKOH/g,
Hydroxyl value: 280 - 310 mgKOH/g.
Tg: 50 - 53 °C

3
 5 EP 2 161 294 A1 6

Claims

1. An amorphous polyester prepared from an acid con-

stituent comprising from 0,1% to 100% moles of iso-
phthalic acid or terephthalic acid, from 0 to 45% 5
moles of at least one dicarboxylic acid or anhydride
other than isophathalic or terephthalic acid and from
0,1% to 25% moles of polycarboxylic acid or anhy-
dride containing at least three carboxyl groups and
from an alcohol constituent comprising from 0,1% to 10
40% moles of neopentylglycol, from 0 to 40% moles
of at least one dihydroxylated compound other than
neopentylglycol and from 60 to 100% moles of pol-
yhydroxylated compound containing at least 3 hy-
droxyl groups and from 0,1 to 10% moles of aliphatic, 15
cycloaliphatic, containing trimethylolethane (TME),
having a glass transition (Tg) of at least 60°C, and
a hydroxyl number of 270 to 350 mgKOH/g, prefer-
ably 280 to 310 mgKOH/g.
20
2. The polyester resin prepared according to claim 1
comprising from 0,1% to 20% moles of polyhydrox-
ylated compound containing at least 93% mole on
hydroxyl groups of TME.
25
3. The polyester resin prepared according to claims 1
and 2 comprising from 0,1% to 100% moles of iso-
phthalic containing at least 98% mole of isophthalic
acid on acid groups.
30
4. The coating composition according to any one of the
preceding claims characterized in that the cured
coating has a Tg between 85 and 115°C.

5. The use of a coating according to claims 1 to 5 in 35

the preparation of a decorated substrate, by dye ink
sublimation technology.

40

45

50

55

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EP 2 161 294 A1

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 EP 2 161 294 A1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 0817728 A [0002] • US 6747070 B [0011]

• EP 1162241 A [0003] • US 6710137 B [0011]
• US 3907974 A [0004] • US 6599992 B [0011]
• WO 9808694 A [0005] • US 6635721 B [0011]
• EP 11622412 A [0009] • US 20020114953 A [0011] [0012]
• US 6808821 B [0011] • US 20050090636 A [0011]
• US 6268464 B [0011]