US006268464B1

(12) United States Patent (16) Patent N68 US 6,268,464 B1

Keiniinen et al. (45) Date of Patent: Jul. 31, 2001

(54) UNSATURATED POLYESTER RESINS 0284 888 A3 10/1988 (EP) .

O 400 884 A2 12/1990 (EP) .
(75) Inventors: Kari Keinanen, Porvoo (FI); Glenn 0475 661 A3 3/1992 (EP) -
Wigington, Forth Smith, AR (US) 0722 995 A2 7/ 1996 (EP) -
OTHER PUBLICATIONS
(73) Assignee: Neste Chemicals 0y, Espoo (FI)
Tentative Rules for Certi?cation and Classi?cation of Boats,
(*) Notice: Subject to any disclaimer, the term of this D6t NOfSke Vefitas AS,_ 1366- 1997, Part 7, Chapter 1
patent is extended or adjusted under 35 “APPIOVaI Of Raw Materlals”.
U'S'C' 154(k)) by 0 days‘ Primary Examiner—Terressa M Boykin
(74) Attorney, Agent, or Firm—Birch, Stewart, Kolasch &
(21) Appl. No.: 09/515,278 Birch, LLP
(22) Filed: Feb. 29, 2000 (57) ABSTRACT
Rdated U_S_ App?cation Data The invention relates to unsaturated polyester resins With
higher molecular Weight, loW viscosity and high solubility
(63) Continuation-in-part of application No. 09/174,421, ?led on specially in reactive diluents. The invention also relates to a
00L 19, 1998, now abandoned method for the manufacture of such unsaturated polyester
(51) Int. Cl.7 ................................................... .. C08G 64/02 resins and to use thereof in Various applications Such as
(52) US. Cl. ................ .. . 528/272; 528/176; 528/271 gelcoats' The unsaturated Polyester resin Comprises 2H5
Wt % of at least one unsaturated polyester havmg a molecu
(58) Field of Search ................................... .. 5259123,8 lar Weight of 20004000, prepared from 1) 30_70 mol %,
/ preferably 40—60 mol % of at least tWo carboXylic acids or
(56) References Cited derivatives thereof and at least one of them is an unsaturated
carboXylic acid or a derivative thereof and at least one of
US. PATENT DOCUMENTS them is an aromatic carboXylic acid or a derivative thereof
and optionally of one or more carboXylic acids and deriva
gjliiglgearl et a1‘ """"""" " tives thereof, 2) 30—70 mol %, preferably 40—60 mol % of
4 038 340 7/1977 Frank et a1. ....................... .. 528/176 at least two ‘11°15 and at least one of them is 2>2>4'trimethy1'
4294:7453 10/1981 Conado et aL 525/445 1,3-pentanediol and/or 2-butyl-2-ethyl- 1,3-propane-diol the
4,921,883 5/1990 Meixner et a1. 522/107 amount of Which is 0~5—8 H101%,Pr@f@rab1y 2—6 H101 %, 3)
5,510,453 4/1996 Kressdorf et a1. 528/176 0.5—10 mol %, preferably 2—6 mol % of at least one
5,614,299 3/1997 Yamamoto et a1. .. 523/500 monoalcohol, 4) optionally a modifying chemical/chemicals
5,688,867 11/ 1997 schelbelho?ef et a1 528/176 and the total amount of monoalcohols and modifying chemi
5,874,503 2/1999 Scheibelhoffer et a1. ......... .. 528/176 Gals is 0_5_20 mol %, preferably 1_15 mol %, and 15_5() Wt
FOREIGN PATENT DOCUMENTS % of at least one reactive diluent.

0260 688 A2 3/1988 (EP) . 21 Claims, N0 Drawings

 US 6,268,464 B1
1 2
UNSATURATED POLYESTER RESINS lytic stability and loW molecular Weights (MW) of about 300
to 2500, and Which are chain-stopped or endcapped With
This application is a continuation-in-part of application monofunctional alcohols or acids. The chain-stopped resins
Ser. No. 09/174,421 ?led on Oct. 19, 1998 noW abandoned, can be modi?ed by addition of polyisocyanate and hydroxy
the entire contents of Which are hereby incorporated by acrylate to prepare resins for arti?cial marble, arti?cial onyx,
reference. ?ber glass reinforced products, laminates, sheet moulding
The invention relates to modi?ed unsaturated polyester compounds and resin transfer moulding applications.
resins With a higher molecular Weight, a loW viscosity and Alternatively, the resins can also be modi?ed by adding a
high solubility especially in reactive diluents. The invention polyisocyanate, a hydroxy acrylate and a dicyclopentadiene
also relates to a method for the manufacture of such unsat 10 based unsaturated polyester resin to produce a composition
urated polyester resins and to use thereof. suitable for loW pro?le marine applications. These unsatur
Unsaturated polyesters are polymers having structural ated polyesters are prepared by the condensation of dicar
units linked by ester groupings, and they can be manufac boxylic acids or anhydrides With polyhydric alcohols in the
tured by the condensation of carboxylic acids With polyhy presence of chain-stopping monofunctional acids or alco
dric alcohols. LoW molecular Weight unsaturated polyesters 15 hols.
are usually produced from maleic anhydride With diethylene U.S. Pat. No. 5 688 867 describes a polyester resin
glycol or, alternatively, other carboxylic acids or anhydrides comprising (A) from about 5 Wt % to about 50 Wt % of a
such as fumaric acid, and glycols such as propylene glycol reactive diluent and (B) from about 50 Wt % to about 95 Wt
are used. Typically, the obtained unsaturated polyesters are % of an unsaturated polyester resin prepared from at least
in the form of a rather viscous oil. LoW molecular Weight 20 one polycarboxylic acid anhydride or ester, at least one
unsaturated polyesters Will crosslink in the presence of a polyhydric alcohol, and at least one component selected
peroxide by copolymeriZation With reactive diluents. Unsat from a group consisting of from about 0.5 mol % up to
urated polyester resins typically contain volatile unsaturated about 8 mol % of polyhydric alcohol having at least three
organic monomers such as styrene as the reactive diluent. In hydroxyl groups, and at least one transesteri?cation catalyst,
commercially available unsaturated polyester resin 25 (ii) from about 2 mol % up to about 12 mol % of a reaction
applications, up to 50% of styrene or other vinyl monomers product of a polyol and a fatty carboxylic acid, and (iii) from
are used. During curing, some of the organic monomer is about 2 mol % up to about 12 mol % of a fatty reactant
usually lost in the atmosphere, 10—20% of the total amount selected from the group consisting of a fatty primary
of the monomer may be lost during resin spray-up and alcohol, a fatty epoxide, a fatty monocarboxylic acid and
lamination and 30—50% during gelcoat spraying and thus 30 mixtures thereof, Wherein each member of the group has up
these emissions cause occupational safety haZards and are to about 100 carbon atoms. The invention also relates to
also a problem because of environmental considerations. In mixtures of polyester resins With conventional polyester
most countries legislation introduced in recent years requires resins. This invention provides resins and methods Which
a reduction in the amount of volatile organic compounds have a loW emission of volatile organic compounds.
(VOC) Which may be released to the atmosphere. Several 35 An object of the present invention is to provide unsat
methods have been proposed for reducing VOC emissions, urated polyester resins Which have a higher molecular
for example the replacement of the reactive diluent With a Weight, a loW viscosity and Which are readily soluble in
less volatile reactive diluent. This approach has led to sloWer reactive diluents. Another object of the present invention is
curing times and/or incomplete curing at normal ambient to provide unsaturated polyester resins for applications such
temperatures. Another approach is a reduction in the amount 40 as general purpose resins and gelcoats With reduced volatile
of the reactive diluent in the composition. This approach has organic compound emissions in order to reduce the risk of
led to an increase in the viscosity of the resin beyond useable occupational safety haZards and environmental concerns.
values. If the viscosity increase is compensated for by the Additionally methods for the manufacture of such unsatur
use of a loWer molecular Weight polyester then poor ?nal ated polyester resins and unsaturated polyester systems
product properties Will result. Still another approach has 45 including products and applications, With good physical
been the use of a suppressant Which reduces the loss of properties such as good mechanical strength, Weathering
VOCs. The suppressants are often Waxes Which may lead to resistance and With good ?nal product properties are desired,
a reduction in the interlaminar adhesion of laminating lay especially for marine applications With very strict require
ers. On the other hand, requirements for the mechanical ments.
properties and for the quality of polyester resins and of their 50 Characteristic features of the unsaturated polyester
applications are constantly tightening, Which can be seen resins, of the manufacture thereof and of the use according
especially in the ?eld of marine applications. Thus, there is to the invention are stated in the claims.
a clear need for polyester resins and their applications With It has been found that the above-mentioned objects can
loW reactive diluent emissions and With superior properties be reached With the folloWing solution. In accordance With
and quality. 55 the present invention unsaturated polyester resins are pre
An unsaturated polyester resin is presented in DE 25 27 pared by condensation of at least tWo carboxylic acids or
675 Wherein the polyester resin comprises an ot,[3 derivatives thereof and at least one of them is an aromatic
ethylenically unsaturated polyester, the terminal groups of carboxylic acid or a derivative thereof, and at least one of
Which comprise a high amount of residues of monoalcohols them is an unsaturated carboxylic acid or a derivative
and a copolymeriZable monomer. High amounts of monoal 60 thereof, With at least tWo diols and at least one of them is
cohols yield rather expensive polymers With shorter molecu 2,2,4-trimethyl-1,3-pentanediol or 2-butyl-2-ethyl-1,3
lar chains and poor mechanical properties. Additionally, the propane diol, in the presence of at least one monoalcohol,
use of maleic anhydride as the sole source for a carboxylic and the obtained unsaturated polyester or mixtures of unsat
acid derivative leads to resins With inferior chemical resis urated polyesters are diluted in a reactive diluent or in
tance and mechanical properties. 65 mixtures of reactive diluents. Optionally one or more other
European patent publication EP 0 475 661 relates to carboxylic acids and one or more polyhydric alcohols may
unsaturated polyester resins Which have improved hydro also be used as Well as one or more modifying chemicals.
 US 6,268,464 B1
3 4
This speci?c combination of starting materials ie part of the vinyltoluene, esters of acrylic acid and methacrylic acid With
carboxylic acids are unsaturated carboxylic acids and part alcohols or polyols, such as methyl methacrylate, butyl
are of aromatic nature, part of the diols are speci?ed acrylate, ethyl-hexyl acrylate, hydroxpropyl methacrylate,
aliphatic branched diols, used With combination of a lauryl acrylate, stearyl methacrylate, lauryl methacrylate,
monoalcohol(s), yields the cured products the desired prop butanediol diacrylate, ethyleneglycol dimethacrylate, dieth
erties. yleneglycol dimethacrylate, triethyleneglycol
Suitably unsaturated carboxylic acids or derivatives dimethacrylate, propyleneglycol dimethacrylate, dipropyle
thereof, such as maleic acid, maleic anhydride and fumaric neglycol dimethacrylate, tripropyleneglycol dimethacrylate
acid and the like are used in an amount of at least 50 mol % and trimethylolpropane triacrylate, allyl esters, such as dial
of total amount of carboxylic acids. Preferably the aromatic 10
lyl phthalate, and vinyl esters, such as vinyl ethylhexanoate,
carboxylic acid or a derivative thereof is phthalic acid, vinyl pivalate, limonene, dipentene, vinyl ethers, indene,
allyl benZene, and the like and mixtures thereof. Preferred
phthalic anhydride, terephthalic acid, isophthalic acid, tet reactive diluents are styrene, ai-methylstyrene, vinyltoluene,
rahydrophthalic anhydride, hexahydrophthalic acid or hexa divinylbenZene, methyl methacrylate, hydroxpropyl
hydrophthalic anhydride. Suitable other carboxylic acids are methacrylate, ethyleneglycol dimethacrylate, diethylenegly
adipic acid, trimellitic acid, trimellitic anhydride, dimethyl 15 col dimethacrylate, triethyleneglycol dimethacrylate and
malonic acid, hydroxypivalic acid, 1,4 mixtures of volatile diluents With less volatile diluents such
cyclohexanedicarboxylic acid. Unsaturated carboxylic as mixtures of styrene or derivatives thereof With said
acids, aromatic and other carboxylic acids or mixtures methacrylates. The amount of the reactive diluent or mix
thereof are used in a total amount of 30—70 mol % and tures thereof varies betWeen 15 and 50 Wt %, preferably
preferably 40—60 mol %. betWeen 20 and 35 Wt %. Preferable starting materials for
2,2,4-trimethyl-1,3-pentanediol and 2-butyl-2-ethyl-1,3 the manufacture of resins especially suited for marine appli
propanediol are aliphatic branched diols, Which are used in cations comprise phthalic anhydride, isophthalic acid, tet
an amount of 0.5—8 mol %, preferably 2—6 mol %. Suitable rahydrophthalic anhydride and hexahydrophthalic anhy
other diols are such as ethylene glycol, propylene glycol, dride as aromatic carboxylic acids or derivatives thereof.
diethylene glycol, dipropylene glycol, neopentyl glycol, 25 Maleic anhydride is a suitable unsaturated carboxylic acid or
triethylene glycol, tripropylene glycol, cyclohexane a derivative thereof. 1,4-cyclohexanedicarboxylic acid and
dimethanol, hexane diol, butylene glycol, hydroxypivalyl adipic acid are suitable as other carboxylic acids or deriva
hydroxy pivalate, 2-ethyl-1,3-hexanediol, 1,3-propanediol, tives thereof. 2,2,4-trimethyl-1,3-pentanediol and 2-butyl-2
1,5-pentanediol, 2,2-diethyl-1,3-propanediol, propylene ethyl-1,3-propanediol are suitable aliphatic branched diols.
glycol, 1,2,3-propanetriol polymer With methyl oxirane, Propylene glycol, dipropylene glycol, diethylene glycol,
trimethylolpropane polymer With methyl oxirane, 2-methyl neopentyl glycol, cyclohexane dimethanol, hexanediol,
1,3-propane-diol and 2-methyl-2,4-pentanediol. The diols or hydroxypivalyl hybroxypivalate, 1,5-pentanediol, 1,3
mixtures thereof are used in a total amount of 30—70 mol % propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl- 1,3
and preferably 40—60 mol %. The amount of 40—60 mol % propanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4
is especially suited for applications requiring extremely 35 pentanediol, polypropylene glycol, 1,2,3-propanetriol
good Weather tolerance in demanding conditions such as in polymer With methyl oxirane and trimethylolpropane poly
gelcoats for marine applications. mer With methyl oxirane are suitable as other diols. As a
Monoalcohols are used as endcappers and suitable ones monoalcohol benZyl alcohol, phenyl ethanol, cyclohexanol,
are benZyl alcohol, phenylethanol, cyclohexanol, 2-cyclohexylethanol, 2-ethylhexanol, 2,2-dimethyl-1
2-ethylhexanol, 2-cyclohexyl ethanol, 2,2-dimethyl-1 propanol are suitable. Glycidyl ester of neodecanoic acid,
propanol and layryl alcohol, Which are used in an amount of epoxystyrene, benZoic acid, phenylacetic acid are suitable as
0.5—10 mol %, preferably 2—6 mol %. optional modifying chemicals.
The molar ratio of the said aliphatic branched diols to Preferable starting materials for the manufacture of res
monoalcohols is 5:1—1:5 and preferably 2:1—1:2. ins especially suited for general purpose resins and gelcoats
The optional modifying chemicals include monofunc 45 comprise phthalic anhydride, isophthalic acid, tetrahydro
tional acids, such as benZoic acid, lauric acid, 2-ethylbuturic phthalic anhydride and terephthalic acid as aromatic car
acid, 2-ethylhexanoic acid and phenylacetic acid, and gly boxylic acids or a derivative thereof. Maleic anhydride is a
cidyl ester of neodecanoic acid, epoxystyrene and dicyclo suitable unsaturated carboxylic acid or a derivative thereof.
pentadiene. Mono-alcohols and optional modifying chemi Trimellitic acid, dimethylmalonic acid and hydroxypivalic
cals or mixtures thereof are used in a total amount of 0.5—20 acid are suitable as other carboxylic acids or derivatives
mol % and preferably 4—15 mol %. thereof. 2,2,4-trimethyl-1,3-pentanediol and 2-butyl-2
Optionally, polyhydric alcohols having at least three ethyl-1,3-propanediol are used as aliphatic branched diols.
hydroxyl groups, such as trimethylol propane, trimethylol Propylene glycol, dipropylene glycol, ethylene glycol, dieth
ethane, pentane erythritol, glycerine, and the like and mix ylene glycol, triethylene glycol, tripropyleneglycol, neopen
tures thereof may be used in amounts of 0.5—20 mol % and 55 tyl glycol, hexanediol, butylene glycol, hydroxy pivalyl
preferably 1—10 mol %, the amount depending on the hybroxypivalate, 1,5-pentanediol, hexanediol, 1,3
desired properties of the application. The excess of 4—25 mol propanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4
% of total alcohols is suitable and preferably an excess of pentanediol, polypropylene glycol, 1,2,3-propanetriol poly
5—20 mol % is used. mer With methyloxirane and trimethylolpropane polymer
The reactive diluent is preferably an ethylenically With methyl oxirane are suitable as other diols. BenZyl
unsaturated, monomeric compound, Which compound alcohol, 2-ethyl-hexanol, 2,2-dimethyl-1-propanol and
includes allyl and vinyl compounds conventionally used for layryl alcohol are suitable as monoalcohols and benZoic
the preparation of unsaturated polyester based moldings, acid, 2-ethylhexanoic acid, lauric acid, phenyl acetic acid
impregnating and coating compositions. Examples of reac and dicyclopentadiene may be used as optional modifying
tive diluents include styrene, substituted styrenes, such as 65 chemicals.
methoxystyrene, divinylbenZene, 4-ethylstyrene, General purpose resins and gelcoats are suitable for
4-methylstyrene, 4-t-butylstyrene, p-chlorostyrene or applications such as ?ber glass reinforced products, arti?cial
 US 6,268,464 B1
5 6
marble, arti?cial onyx, sheet moulding compounds, resin Components or additives generally knoWn in the art may
transfer moulding applications, hand and spray lamination be employed in the process.
applications, sanitary applications, pigmented and clear The unsaturated polyesters according to the invention
gelcoats and topcoats/enamels. exhibit acid numbers from 1 to 50, based on solids or
The unsaturated polyester resin according to the inven nonvolatile content, and preferably the acid number is 3—20.
tion comprises 20—85 Wt %, preferably 30—80 Wt % of at The I.C.I viscosity of the linear unsaturated polyester is
least one unsaturated polyester having a Weight average betWeen 1—10 poise/125° C., preferably 3—8 poise/125° C.,
molecular Weight of 2000—6000, preferably 2600—6000, the Weight average molecular Weight MW of the linear
prepared from unsaturated polyester is 2000—6000, preferably 2600—6000
1) 30—70 mol %, preferably 40—60 mol % of at least tWo 10 and the number average molecular Weight Mn is 700—2500,
carboxylic acids or derivatives thereof and at least one preferably 1000—2200. Regardless of the longer chain length
of them being an unsaturated carboxylic acid or a and higher molecular Weight, the viscosity remains loW and
derivative thereof and at least one of them being an the solubility of the unsaturated polyester in reactive dilu
aromatic carboxylic acid or a derivative thereof, and ents such as styrene is good, Which signi?cantly reduces the
optionally of another carboxylic acid or a derivative 15 need for reactive diluents, doWn to 20—35 Wt %. Because of
thereof; their solubility and viscosity properties, the unsaturated
2) 30—70 mol %, preferably 40—60 mol % of at least tWo polyesters can be dissolved in smaller amounts of reactive
diols and at least one of them is selected from 2,2,4 diluents, and thus the emission of VOCs from the products
trimethyl-1,3-pentanediol and 2-butyl-2-ethyl-1,3 manufactured from the resins according to the invention are
propanediol, and the amount of 2,2,4-trimethyl-1,3 signi?cantly loWer. The loW styrene content in the resin
pentane diol and/or 2-butyl-2-ethyl-1,3-propanediol is results also in a more efficient material transfer and less loss
0.5—8 mol %, preferably 2—6 mol %. of the product in applications because the product is less
3) 0.5—10 mol %, preferably 2—6 mol % of at least one atomiZed. Mostly due to the higher molecular Weight of the
monoalcohol, unsaturated polyester, the cured unsaturated polyester resins
4) optionally a modifying chemical/chemicals and the 25 retain the mechanical properties such as Weathering
total amount of monoalcohols and modifying chemi resistance, chemical resistance and UV-resistance and thus
cals is 0.5—20 mol %, preferably 1—15 mol %; they are Well suited especially for demanding applications.
and 15—50 Wt %, preferably 20—35 Wt % of at least one The unsaturated polyesters according to the invention are
reactive diluent. compatible and readily soluble in reactive diluents, such as
Additionally an esteri?cation catalyst for decreasing of styrene and the respective resins have good curing proper
reaction time may optionally be used in the manufacture of ties. Polyester derived products With superior surface
the linear unsaturated polyesters. The catalyst may be quality, thermocycling and UV resistance and clarity are
present in an amount knoWn to a man skilled in the art. conveniently manufactured from the unsaturated polyester
Suitable esteri?cation catalyst include metal-containing resins according to the invention.
catalysts, such as metal oxides, metal hydroxides and metal 35 The unsaturated polyester resins according to the inven
acetates. The progress of the polymeriZation reaction is tion are useful for a variety of applications such as general
conventionally monitored by means of acid number. purpose resins, coating materials and reinforcing materials.
The molecular Weight MW denotes Weight average They have utility as resins With reduced reactive diluent
molecular Weight and the molecular Weight Mn denotes emissions for panels, laminates, ?ber glass reinforced
number average molecular Weight, both measured by Gel products, arti?cial marble, arti?cial onyx, sheet moulding
Permeation Chromatography (GPC) using a set of Waters compounds, resin transfer moulding applications, sanitary
Ultrastyragel (trade-mark) columns. applications and as base resins, they are also Well suited for
Suitable and preferred alternatives for the components in demanding marine applications, and products such as pig
the resins according to the invention are listed above. mented or clear gelcoats and topcoats/enamels can be manu
The unsaturated polyesters according to the invention can 45 factured Which meet the requirements described above.
be prepared in a single-stage or in a tWo-stage process. A The resins for marine applications have very tight require
solvent process Wherein an aZeotropic solvent, such as ments and Det Norske Veritas (DNV) approval and Lloyd’s
xylene is used to facilitate Water removal is also suitable. approval are required in several countries for polyester
The unsaturated polyester resins according to the invention resins used for marine purposes. DNV requirements for
are preferably manufactured in the folloWing manner. The mechanical properties of resins used in gelcoats for marine
alcohols and carboxylic acids or derivatives thereof are applications (Tentative Rules for Certi?cation and Classi?
charged to a suitable reaction vessel and the reaction is cation of Boats, Part 7 Chapter 1, Approval of RaW
carried out at a temperature of about 180—240° C., prefer Materials, December 1997) are presented in the folloWing:
ably 190—230° C. and it is continued until an acid number of Tensile strength 250 MPa.
1—50, preferably 3—20 and an I.C.I. (cone and plate) viscos 55
Tensile modulus Z3000 MPa.
ity of 1—10 poise/125° C., preferably 3—8 poise/125° C. of
the linear unsaturated polyester are reached. Finally the Bending temperature (HDT) 270° C.
linear unsaturated polyester or mixtures of linear unsaturated Water absorption E80 mg/piece/28 d.
polyesters are dissolved in a suitable reactive diluent or a Barcol hardness 235.
mixture thereof. In the case maleic anhydride and isoph The unsaturated polyester resins according to the inven
thalic acid or terephthalic acid are used, all acids except tion may be formulated together With suitable additives
maleic anhydride are charged With alcohols. The reaction is knoWn in the art to form gelcoats, resins and polyester based
then alloWed to proceed until the reaction mixture is clear, products.
and the acid number is beloW 70, more preferably beloW 30. Gelcoats are curable compositions Which contain at least
After cooling the maleic anhydride is added. The encapper, 65 one of the above unsaturated polyester resins With additives.
monohydric alcohol can be added at the ?rst or the second Suitable additives include thixotropic agents, thixotropy
stage. enhancers, suppressants, surface tension agents,
 US 6,268,464 B1
7 8
co-promoters, promoters, air release agents, ?llers, Wetting EXAMPLE 1
agents, levelling agents and pigments.
The thixotropic agents comprise silica compounds such as
General Purpose Resins 1A, 1B, 1C and 1D
fumed silica and precipitated silica and inorganic clays like
bentonite and hectorite clay. Thixotropy enhancers comprise
propylene glycol and ethylene glycol and derivatives
thereof. Promoters are usually added to unsaturated polyes Resin
ter resins to accelerate the decomposition of a peroxide 1A 1B 1C 1D
initiator into free radicals and to thereby initiate or speed up 10
the curing of the composition. The promoters are generally Starting material (mol %)
metal compounds, such as cobalt, manganese, iron, Propylene glycol 12 12 12 10
vanadium, copper, and aluminum salts of organic acids, such Neopentyl glycol 33 33 33 33
2-Butyl-2-ethyl-1,3-propanediol 4 5 4 5
as octoate or naphthenate salts. Co-promoters are Widely 1,4-Cyclohexanedicarboxylic acid 4
used in promoter systems and suitable ones are organic 15
Isophthalic acid 15 14 14 14
amines like dimethylaniline, diethylaniline, Adipic acid 3 3 3
Maleic anhydride 28 28 28 27
2-aminopyridine, N,N-dimethyl-acetoacetamide, acetoac 2-Ethylhexanoic acid 2 4
etanilide or other organic compounds like ethyl acetoacetate, 2-Phenylethyl alcohol 4
methyl acetoacetate and N,N-dimethyl-p-toluidine. Inhibi Benzyl alcohol 3 5
20 2-Ethylhexanol 5
tors are used for adjusting storage stability and gel time, and Property of linear unsaturated polyester
suitable inhibitors comprise hydroquinone,
Cook end points: I.C.I./150O C.* 1.3 1.7 1.4 0.8
toluhydroquinone, mono-tert-butylhydroquinone, hydro (poise)
quinone monomethyl ether p-benZoquinone, 2,5-di-tert Acid number 12 15 19 20
butylhydroquinone. Gelcoats may also contain ?llers such as 25 Property of linear unsaturated polyester in styrene
talc, calcium carbonate, magnesium carbonate, barium I.C.I./25O C. (poise) 3.8 3 3.5
carbonate, aluminium trihydroxide, calsium sulfate, magne Styrene % 30 35 35
MW 3200 3000 2800 3100
sium sulfate, barium sulfate, chopped glass?ber and the like. Mn 1700 1100 1600 1600
Various pigments are typically used in gelcoats and titanium 30 Mechanical properties of cured resin in styrene
dioxide is a suitable one. Air release agents, Wetting
Tensile strength (MPa) 40 65 40
additives, surfactants or levelling additives based on silicone Tensile elongation (%) 3 7 6
and ?uorocarbon, and various modi?ed polymers like acry Tensile modulus (MPa) 2600 3200 1950
late and urethane may be added to gelcoats. Suppressants for HDT (° c.) 59 57 50
Barcol 33 36 22
reducing organic emissions may be included in gelcoats and 35
such as polyethers, alcanoic acid esters of propoxylated *I.C.I viscosity Was measured at 1500 C. yielding loWer values When
phenols, propoxylated bisphenols or compared With 1250 C.
hydoxypropylphthalates, polyetherpolysiloxane
blockcopolymers, Waxes and the like are suitable. Various
40
peroxides for curing/crosslinking are used and peroxides EXAMPLE 2
like methyl ethyl ketone peroxide, cumene hydroperoxide,
t-butyl peroctoate, di-t-butyl peroxide, benZoyl peroxide and General Purpose Resins 2A, 2B, 2C and 2D
the like are suitable.
The unsaturated polyester resins according to the inven 45
tion are readily dilutable in loWer reactive monomer con
Resin
tents and the obtained products shoW loW viscosity and
excellent applicability. The mechanical properties of the 2A 2B 2C 2D
cured products comply even With the strict requirements for
50 Starting material (mol %)
marine gelcoats and products.
The unsaturated polyester resins and applications based Neopentylglycol 34 32 33 26
thereon are Well suited for hand lay up lamination, spray Propylene glycol 9 12 7 11
Dipropylene glycol 4 3
lamination, resin lamination, pultrusion, sheet moulding 2-Butyl-2-ethyl-1,3-propanediol 5 5
compounding, bulk moulding compounding and applica 55 2,2,4-Trimethyl-1,2-pentanediol 6 10
Isophthalic acid 12 11 13 14
tions Well knoWn to the man skilled in the art. The obtained Adipic acid 5 3
products achieve to reduced volatile organic compound Maleic anhydride 29 31 32 31
emissions, they have acceptable geltime, good adhesion, Benzyl alcohol 5 6 6 5
Property of linear polyester
Weathering resinstance, loW Water absorption and good ?nal
60
product properties. The UV-resistance, loW shrinkage prop Cook end points: I.C.I./150O C. 4.3 2.8 3.4 4
erties and hydrolytic stability of the products are good due (poise)
Acid number 18 9 10 16
to the loWer reactive diluent content and due to other Property of linear polyester in styrene
properties of the resins.
I.C.I./25O C. (poise) 35% styrene 2.6 2.4 2.7 3
FolloWing examples provide a better understanding of the 65 MW 2800 2600 2840 2500
present invention, hoW ever they are not be intended as Mn 1300 1200 1500 1400
limiting the scope thereof.
 US 6,268,464 B1

-continued -continued
Resin Resin

2A 2B 2c 2D 5 4A 4B 4c 4E

Mechanical properties of cured resin in 40% styrene Property of linear polyester

Tensile strength (MPa) 60 37 48 60 Cook end points: I.C.I./150O C. 3.2 2.5 2.5 1.5
Tensile elong (‘70) 5 5 4 5 (poise)
Tensile modulus (MPa) 2600 2500 2500 3000 10 Acid number 42 21 18 17
HDT (0 C.) 71 70 56 71 Property of linear polyester in styrene
Barcol 34 33 36 36
I.C.I./25O C. (poise) 35% styrene 7 4.7 4.6 3.3
MW 3100 3600 3500 3000
Mn 1700 1900 1400 1500
EXAMPLE 3 15 Mechanical properties of cured resin in 40% styrene

Tensile strength (MPa) 67 87 73 65

Gelcoats 3A, 3B, 3C and 3D Made From Resins Tensile elongation (‘70) 3 5 3 4
2A, 2B, 2C and 2D for General Purpose Tensileomodulus (MPa) 3500 4300 3800 3400
A 1. t. HDT( c.) 73 75 73 64
PP 16a 1on5 2O Barcol 39 3s 37 38
Water abs (28d)/(mg) / piece 78 73 73 73

Gelcoat EXAMPLE 5
Constituent (Wt %) 3A 3B 3C 3D 25 Gelcoats 5A, 5B, 5C, 5D and 5E Made from Resin
R _ 300] t 2A 64 2B 64 2C 64 2D 64 4A, 4B, 4C, 4D and 4E for Marine Applications
ii’sm ( 0 S yrene) and Commercial Isophthalic Based Marine Gelcoat
Air Release agent 0.2 0.2 0.2 0.2
Talc 7 7 7 7 GN 100005 (Nest 6 Oy) for R e ference Pu rp 0565
Titanium dioXide 17 17 17 17
ThiXotropic agent 1.3 1.3 1.3 1.3
Styrene 7.5 7.5 9.5 11 3O
coiiait (10%) 0.12 0.12 0.12 0.12 Reference
Inhibitor 0.13 0.13 0.13 0.13 gelcoat
—PrOperty Gelcoats GN

Styrene % _ _ 28 28 29 30 Constituent (W %) 5A 5B 5c 5D 10000s

Styrene emission ** (ppm) 145 150 185 145 35
Brook?eld viscosity/10 RPM 11940 11400 7420 8920 Resin (Styrene 4A 63 4B 63 4C 67 4D 64
ThiXotropic indeX 5/50 RPM 5.1 5.2 4.4 4.68 30%)
Accelerated Weathering test Air release agent 0.2 0.2 0.2 0.2
O Talc 7 7 7 7
Gloss 60 90 89 91 92 Titanium dioxide 15 15 15 15
QUV'A 250 h CIE L*a*b* 1-1 1 1-2 1-3 4O ThiXotropic agent 1.3 1.3 1.3 1.3
03b") 0 Styrene 13.5 14 9 12
Gloss 60 83 84 85 85 Cobalt (10%) 0.12 0.12 0.12 0.12
QIW-A 500 h CIE L*a*b* 1-4 1-3 1-7 2 Inhibitor 0.13 0.13 0.13 0.13
(1377*) Property
Gloss 60 o 81 81 84 83 —

45 Styrene % 33 33 30 28 36
** maXimum styrene concentration in eXhaust air during spraying Styrene 175 210 200 190 260
emission **
(ppm)
EXAMPLE 4 Brook?eld 8500 4160 10560 6680 7500
viscosity/10 RPM
' ' ThiXotropic 4.5 4.3 4.8 4.2 4.8
Resins 4A, 4B, 4C, and 4D and 4E for Marine 50 indeX 5/50 RPM
Applications Acceterated
Weathering test

Gloss 60 o 95 88 90 87 84
QUV-A 250 h 2 1.8 0.9 1.3 1.9
Resin 55 CIE L*a*b*
(D110
4A 4B 40 4E Gloss 60 ° s5 s4 s4 s4 s1
_ _ QUV-A 500 h 1.7 1.2 1.9 2.4 2.9
Starting material (mol %) CIE Ly?ay?by?
(D110
Neopentyl glycol 23 30 30 30 6O Gloss 60 o 84 86 83 85 81
Propylene glycol 11 10 11 12
2'Buty1'2'_ethy1'l>3'propalledlol 6 3 3 3 ** maXimum styrene concentration in eXhaust air during spraying
HydroXypivalyl hydroXypivalate 9 5 5 5
Isophthalic acid 16 14 14 13 What is Claimed is;
Adlplc acld . 2 2 2 1. An unsaturated polyester resin, Wherein said resin
Maleic anhydride 29 30 29 29 _
1_Pheny1 ethyl alcohol 3 3 3 65 comprises 20—85 Wt % of at least one unsaturated polyester
Benzyl alcohol 6 3 3 3 having a Weight average molecular Weight MW of
2000—6000, prepared from
 US 6,268,464 B1
11 12
1) 30—70 mol % of at least tWo carboXylic acids or 9. Aprocess for the manufacture of an unsaturated poly
derivatives thereof and at least one of them is an ester resin, Wherein 30—70 mol % of at least tWo carboXylic
unsaturated carboXylic acid or a derivative thereof in an acids or derivatives thereof and at least one of them is an
amount of 50 mol % from total amount of carboXylic unsaturated carboXylic acid or a derivative thereof in an
acids, and at least one of them is an aromatic carboXylic amount of 50 mol % from total amount of carboXylic acids,
acid or a derivative thereof and optionally of one or and at least one of them is an aromatic carboXylic acid or a
more other carboXylic acids or derivatives thereof; derivative thereof and optionally of one or more carboXylic
acids or derivatives thereof, and 30—70 mol % of at least tWo
2) 30—70 mol % of at least tWo diols and at least one of
diols and at least one of them is selected from 2,2,4
them is selected from 2,2,4-trimethyl-1,3-pentanediol trimethyl-1,3-pentanediol and 2-butyl-2-ethyl-1,3
and 2-butyl-2-ethyl-1,3-propanediol and the amount of propanediol and the amount of 2,2,4-trimethyl-1,3
2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl-2-ethyl pentanediol and/or 2-butyl-2-ethyl-1,3 is 0.5—8 mol %, and
1,3-propanediol is 0.5—8 mol %; 0.5—10 mol % of at least one monoalcohol, and optionally a
3) 0.5—10 mol % of at least one monoalcohol; modifying chemical/chemicals and the total amount of
4) optionally a modifying chemical/chemicals and the monoalcohol/alcohols and modifying chemical/chemicals is
15 0.5—20 mol %, are charged to a suitable reaction vessel and
total amount of monoalcohols and modifying chemi
cals is 0.5—20 mol %; the reaction is carried out at a temperature of 180—240° C.
and 15—50 Wt % of at least one reactive diluent. and is continued until the acid number of 1—50 and I.C.I.
2. The unsaturated polyester resin according to claim 1, viscosity of the linear polyester of 1—10 poise/125° C. are
Wherein said resin comprises 30—80 Wt % of at least one reached, if maleic anhydride is used With isophthalic or
unsaturated polyester having a Weight average molecular terephthalic acid, the reaction is alloWed to proceed Without
Weight of 2600—6000 as measured by Gel Permeation Chro maleic anhydride until the reaction miXture is clear and until
acid number beloW 70 is reached, then, after cooling of the
matography (GPC), prepared from reaction miXture, maleic anhydride is added, and ?nally the
1) 40—60 mol % of at least tWo carboXylic acids or linear unsaturated polyester or miXtures thereof are dis
derivatives thereof; 25 solved in an amount of 15—50 Wt % of at least one reactive
2) 40—60 mol % of at least tWo diols and the amount of diluent.
2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl-2-ethyl 10. A process for the manufacture of an unsaturated
1,3-propanediol is 2—6 mol %; polyester resin according to claim 9, Wherein 40—60 mol %
3) 2—6 mol % of at least one monoalcohol; of at least tWo carboXylic acids or derivatives thereof, and
4) optionally a modifying chemical/chemicals and the 40—60 mol % of at least tWo diols and the amount of
total amount of monoalcohols and modifying chemi 2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl-2-ethyl-1,3
cals is 1—15 mol %; propanediol is 2—6 mol %, and 2—6 mol % of at least one
and 20—35 Wt % of at least one reactive diluent. monoalcohol, and the total amount of monoalcohol/alcohols
3. The unsaturated polyester resin according to claim 1 or and modifying chemical/chemicals is 1—15 mol %, are
2, Wherein said unsaturated carboXylic acid or a derivative 35 charged to a suitable reaction vessel and the reaction is
thereof is maleic acid, maleic anhydride or fumaric acid. carried out at a temperature of 190—230° C. and it is
4. The unsaturated polyester resin according to claim 3, continued until the acid number of 3—40 and I.C.I. viscosity
Wherein said other diols are selected from ethylene glycol, of the linear polyester of 3—8 poise/125° C. are reached, if
propylene glycol, diethylene glycol, dipropylene glycol, maleic anhydride is used With isophthalic or terephthalic
neopentyl glycol, triethylene glycol, tripropylene glycol, acid the reaction is alloWed to proceed Without maleic
cycloheXane dimethanol, heXane diol, butylene glycol, anhydride until the reaction miXture is clear and until acid
hydroXypivalyl hydroXy pivalate, 2-ethyl-1,3-heXanediol, number beloW 30 is reached, then after cooling of the
1,3-propanedioll, 1,5-pentanediol, 2,2-diethyl-1,3 reaction miXture maleic anhydride is added, and ?nally the
propanediol, propylene glycol, 1,2,3-propantriol polymer linear polyester or miXtures thereof are dissolved in an
With methyl oXirane, trimethylolropane polymer With 45 amount of 20—35 Wt % of at least one reactive diluent.
methyl oXirane, 2-methyl-1,3-propanediol and 2-methyl-2, 11. Aproduct obtained by the process according to claims
4-pentanediol. 9 or 10, Wherein the Weight average molecular Weight MW
5. The unsaturated polyester resin according to claim 4, of the product is 2000—6000 and number average molecular
Wherein said monoalcohols are selected from benZyl Weight Mn of the product is 700—2500.
alcohol, phenylethanol, cycloheXanol, 2-ethylheXanol, 12. The unsaturated polyester resin according to claim 1
2-cycloheXyl ethanol, 2,2-dimethyl-l-propanol and layryl or prepared according to the process of claim 9, Wherein said
alcohol. resin comprises general purpose resins, resins for marine
6. The unsaturated polyester resin according to claim 3, applications, resins for ?ber glass reinforced products, arti
Wherein modifying chemicals are selected from benZoic ?cial marble, arti?cial onyX, sheet moulding compounds,
acid, lauric acid, 2-ethylbuturic acid, 2-ethylheXanoic acid 55 resin transfer moulding applications, resins for hand and
and phenylacetic acid, and glycidyl ester of neodecanoic spray lamination applications, resins for sanitary
acid, epoXy styrene and dicyclopentadiene. applications, pigmented and clear gelcoats and topcoats/
7. The unsaturated polyester resin according to claim 3, enamels.
Wherein said I.C.I. viscosity of the unsaturated polyester is 13. A gelcoat, comprising 20—85 Wt % of at least one
1—10 poise/125° C., the acid number is 1—50 and Mn is unsaturated polyester With a Weight average molecular
700—2500 as measured by Gel Permeation Chromatography Weight MW of 2600—6000 and 15—50 Wt % of at least one
(GPC). reactive diluent, and additives selected from the group
8. The unsaturated polyester resin according to claim 3, consisting of catalysts, inhibitors, thiXotropic agents, thiX
Wherein said I.C.I. viscosity of the unsaturated polyester is otropy enhancers, promoters, co-promoters, ?llers,
1—10 poise/125° C., the acid number is 3—20 and Mn is 65 pigments, air release agents, Wetting agents, leWelling
1000—2200 as measured by Gel Permeation Chromatogra agents, surfactants and suppressants, and that the unsatur
phy (GPC). ated polyester is prepared from
 US 6,268,464 B1
13 14
1) 30—70 Wt % of at least tWo carboXylic acids or 3) a monoalcohol/monoalcohols selected from the group
derivatives thereof and at least one of them is an consisting of benZyl alcohol, 2-ethylheXanol, 2,2
unsaturated carboXylic acid or a derivative thereof and dimethyl-l-propanol, layryl alcohol, phenyl acetic acid
at least one of them is an aromatic carboXylic acid or a and dicyclopentadiene and optionally a modifying
derivative thereof and optionally of one or more car chemical/chemicals selected from the group consisting
boXylic acids or derivatives thereof; of benZoic acid, 2-ethylheXanoic acid and lauric acid.
2) 30—70 Wt % of at least tWo diols and at least one of 17. The product according to claim 11, Wherein the Weight
them is selected from 2,2,4-trimethyl-1,3,pentanediol average molecular Weight MW is 2600—6000 and the number
and 2-butyl-2ethyl-1,3-propanediol and the amount of average molecular Weight Mn is 1000—2200.
2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl 1O 18. The gelcoat of claim 13, Wherein said unsaturated
2-ethyl-1,3-propandiol is 0.5—8 mol %. polyester With a Weight average molecular Weight MW of
3) 0.5—10 mol % of at least one monoalcohol; 2600—6000 comprises 30—80 Wt %, said reactive diluent
4) optionally a modifying chemical/chemicals and the comprises 20—35 Wt %, and additives selected from the
total amount of monoalcohols and modifying chemi group consisting of catalysts, inhibitors, thiXotropic agents,
cals is 0.5—20 mol % 15 thiXotropy enhancers, promoters, co-promoters, ?llers,
and 15—50 Wt % of at least one reactive diluent. pigments, air release agents, Wetting agents, leWelling
14. The gelcoat according to claim 13 for marine agents, surfactants and suppressants, and that the unsatur
applications, characteriZed in that the polyester is prepared ated polyester is prepared from
from 1) 40—60 mol %, of said carboXylic acids or derivatives
1) unsaturated and other carboXylic acids or derivatives thereof and at least one of them is an unsaturated
thereof, selected from the group consisting of phthalic carboXylic acid or a derivative thereof and at least one
anhydride, isophthalic acid, tetrahydrophthalic of them is an aromatic carboXylic acid or a derivative
anhydride, heXahydrophthalic anhydride, adipic acid, thereof and optionally of one or more carboXylic acids
maleic anhydride and 1,4-cycloheXanedicarboXylic or derivatives thereof;
acid; 25 2) 40—60 mol % of said diols and at least one of them is
2) other diol/diols selected from the group consisting of selected from 2,2,4-trimethyl-1,3,pentanediol and
propylene glycol, di-propylene glycol, diethylene 2-butyl-2ethyl-1,3-propanediol and the amount of said
glycol, neopentyl glycol, cycloheXane dimethanol, 2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl-2-ethyl
heXanediol, hydroXyprivalyl hy droXypivalate, 1,5 1,3-propandiol is 2—6 mol %
pentanediol, 1,3-propanediol, 2-ethyl-1,3-heXanediol, 3) 2—6 mol % of at least one monoalcohol;
2,2-diethyl-1,3-propanediol, 2-methyl-1,3 4) optionally a modifying chemical/chemicals and the
propanediol, 2-methyl-2,4-pentanediol, polypropylene total amount of monoalcohols and modifying chemi
glycol, 1,2,3-propanetriol polymer With methyl oxirane cals is 1—15 mol %;
and trimethylolpropane polymer With methyl oXirane; and 20—35 Wt % of at least one reactive diluent.
35
3) a monoalcohol/monoalcohols selected from the group 19. An unsaturated polyester resin Wherein said resin
consisting of benZyl alcohol, benZoic acid, phenyl comprises 20—85 Wt % of at least one unsaturated polyester
ethanol, cycloheXanol, 2-ethyl heXanol and optionally a having a Weight average molecular Weight MW of
modifying chemical/chemicals selected from the group 2000—6000 as measured by Gel Permeation Chromatogra
consisting of glycidyl ester of neodecanoic acid, phy (GPC), prepared from
2-cyclheXyletanol, 2,2-dimethyl-1-propanol, epoXy 1) 30—70 mol % of at least tWo carboXylic acids or
styrene and phenylacetic acid. derivatives thereof and at least one of them is an
15. The gelcoat according to claim 13 or 14, Wherein said unsaturated carboXylic acid or a derivative thereof in an
mechanical properties of the cured unsaturated polyester amount of 50 mol % from total amount of carboXylic
resin are:
45 acids, and at least one of them is an aromatic carbosylic
Tensile strength Z50 Mpa, acid or a derivative thereof and optionally of one or
Tensile modulus Z3000 Mpa, more other carboXylic acids or derivatives thereof;
Bending temperature (HDT)§70° C., 2) 30—70 mol % of at least tWo diols and at least one of
Water absorption E80 mg/piece/28, and them is selected from 2,2,4-trimethyl-1,3-pentanediol
Barcol hardness 235. and 2-butyl-2-ethyl-1,3-propanediol and the amount of
16. The gelcoat according to claim 13 for general 2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl-2-ethyl
purposes, Wherein said polyester is prepared from: 1,3-propanediol is 0.5—8 mol %;
1) unsaturated and other carboXylic acids or derivatives 3) 0.5—10 mol % of at least one monoalcohol;
thereof selected from the group consisting of phthalic 4) optionally a modifying chemical/chemicals and the
anhydride, isophthalic acid, tetrahydrophthalic 55 total amount of monoalcohols and modifying chemi
anhydride, terephtalic acid, adipic acid, maleic cals is 0.5—20 mol %;
anhydride, trimellitic acid, dimethylmalonic acid and and 15—50 Wt % of at least one reactive diluent.
hydroXypivalic acid; 20. Aproduct obtained by the process according to claims
2) other diol/diols selected from the group consisting of 9 or 10, Wherein the Weight average molecular Weight MW
propylene glycol, di-propylene glycol, ethylene glycol, of the product is 2000—6000 as measured by Gel Permeation
diethylene glycol, triethylene glycol, Chromatography (GPC)i and number average molecular
tripropyleneglycol, neopentyl glycol, heXanediol, buty Weight Mn of the product is 700—2500 as measured by Gel
lene glycol, hydro Xypivalyl hydroXypivalate, 1,5 Permeation Chromatography (GPC).
pentanediol, heXanediol, 1,3-propanediol, 2-methyl-1, 21. A i elcoat, comprising 20—85 Wt % of at least one
3-propanediol, 2-methyl-2,4-pentanediol, polyproylene 65 unsaturated polyester With a Weight average molecular
glycol, 1,2,3-propanetriol polymer With methyloXirane Weight MW of 2600—6000 as measured by Gel Permeation
and trimethylolpropane polymer With methyl oXirane; Chromatography (GPC) and 15—50 Wt % of at least one
 US 6,268,464 B1
15 16
reactive diluent, and additives selected from the group 6) 30—70 Wt % of at least tWo diols and at least one of
consisting of catalysts, inhibitors, thiXotropic agents, thiX- them is selected from 2,2,4-trimethyl-1,3,pentanediol
otropy enhancers, promoters, co-promoters, ?llers, and 2-butyl-2ethyl-1,3-propanediol and the amount of
pigments, air release agents, Wetting agents, leWelling 2,2,4-trimethyl-1,3-pentanediol and/or 2-butyl-2-ethyl
agents, surfactants and suppressants, and that the unsatur- 5 1,3-propandiol is 0.5—8 mol %
ated Polyester is Prepared from 7) 0.5—10 mol % of at least one monoalcohol;
5) 30f70_ Wt % of at least tWO carboxylic acids or 8) optionally a modifying chemical/chemicals and the
derivatives thereof and at least one of them is an total amount of monoalcohols and modifying Chemi
unsaturated carboXylic acid or a derivative thereof and Gals is ()_5_20 H101 %
at least'one of them is an aromatic carboXylic acid or a 10 and 15_50 Wt % of at least one reactive diluent
derivative thereof and optionally of one or more car
boXylic acids or derivatives thereof; * * * * *