CA2015044C - Copolymers containing hydroxyl, epoxide and anhydride groups, a process for their production and their use as binders or binder components - Google Patents

Abstract

The present invention relates to copolymers which have a weight average molecular weight of about 1,500 to 75,000, are prepared from olefinically unsaturated compounds and contain in chemically bound form i) about 0.2 to 6.0% by weight of free hydroxyl groups, ii) about 1 to 30% by weight of carboxylic anhydride groups (expressed as C4H2O3) and iii) about 0.4 to 13% by weight of epoxide groups (expressed as C2H2O).
The present invention also relates to a process for the production of these copolymers by copolymerizing a mixture of olefinically unsaturated compounds at about 60 to 120°C in the presence of compounds which initiate the polymerization reaction: Finally, the present invention also relates to the use of these copolymers as binders or binder components in one- or two-component coating or sealing compositions which may contain catalytically active organic amine compounds as an additional binder component.

Description

2~:1~044 Mo3362 LeA 26,835 COPOLYMERS CONTAINING HYDROXYL, EPOXIDE AND
ANHYDRIDE GROUPS, A PROCESS FOR THEIR PRODUCTION
AND THEIR USE AS BINDERS OR BINDER COMPONENTc BACKGROUND OF THE INVENTION
s Field of the Invention This invention relates to new copolymers which contain hydroxyl groups, epoxide groups and carboxylic anhydride groups in chemically incorporated form, to a process for the production of these copolymers and to their use as ~o binders or binder components in one- or two-component coating or sealing compositions.
Description of the Prior Art The use of mixtures of polyhydroxyl compounds and organic compounds containing at least two intramolecular carboxylic anhydride groups per molecule, especially copolymers containing succinic anhydride; as binders for paints and coating compositions is known.
FR-A-2 392 092 describes coating compositions based on hydroxyl-functional polymers and an ester anhydride 20 containing at least two anhydride groups per molecule. The ester anhydride is an oligomer of trimellitic anhydride. The disadvantage of these coating compositions is the poor solubility of the anhydride component in typical paint solvents and also its incompatibility with hydroxyl-functional polymers.
2s EP-A-48 128 describes coating compositions based on a hydroxyl component containing at least two hydroxyl groups per molecule; an anhydride component containing at least two anhydride groups per'molecuTe and, optionally, an amine component as catalyst. The catalytically active amino groups 3o may be present in the hydroxyl component. The described use of monomeric amino alcohols, such as triethanolamine, as crosslinking agents has an adverse effect on the solvent resistance of the final paints if a sufficiently long pot life is to be obtained. A sufficiently long pot life of several 35 hours can only be obtained at the expense of a low crosslink Le A 26835-US

~o~~o~~
_2_ density; paint films with poor solvent resistance are obtained.
Even in cases where relatively high molecular weight polyols are used, it is not possible to obtain a sufficiently long pot life. In addition, a further disadvantage is that the relatively high molecular weight polyols are often not compatible with copolymers containing anhydride groups.
Binder components based on carboxyl groups and epoxide groups which cure both at room temperature and at elevated temperatures are also known.
la DE-OS 2 635 177 and DE-OS 2 728 459 describe low solvent stoving enamels based on a) an acrylate resin containing carboxyl groups, b) an epoxy resin containing at least two epoxide groups per molecule and c) a solvent mixture.
EP-A-123 738 and EP-A-156 210 Vibe xt~,in oanpositirns whidi nay be i5 cured at room temperature to form coatings and adhesives and which are based on a) a component containing carboxyl and tertiary amino groups and b) a component containing epoxide groups. Component a) is obtained by reacting a copolymer containing carboxylic acid and carboxylic anhydride groups with a compound containing a tertiary amino group and a group containing active hydrogen atoms which is capable of reacting with the anhydride groups. The carboxylic acid groups produced from the anhydride groups are available together with the carboxylic acid groups directly introduced into the polymer as 2s reactive groups for the epoxide groups of component b).
However, a disadvantage of these systems is that component a) is incompatible with component bj,' resulting in unsatisfactory optical properties of the resulting paint films. Another disadvantage is it can take, as long as 4 days to obtain paint so films which do not have good resistance to solvents.
X134 691 describes compositions which may be cured at room temperature or slightly elevated temperatures and which are based on a) a component containing at least two hydroxyl groups per molecule, b) a component containing at 35 least two carboxylic anhydride groups per molecule and c) a Mo3362 20~~044 component containing at least two epoxide groups per molecule.
In this case, too, components a), b) and c) are incompatible resulting in poor optical properties in the resulting films.
An object of the present invention is to provide new binder systems wherein curing is accompanied by the crosslinking reactions which take place between carboxylic anhydride, hydroxyl or epoxide groups in the form of addition reactions and which are not attended by any of the disadvantages of the systems according to the prior art io described above.
This object has been achieved in accordance with the copolymers described in more detail hereinafter which contain free hydroxyl groups, free epoxide groups and carboxylic anhydride groups in chemically incorporated form. These 15 copolymers do not suffer from the compatibility problems of the prior art compositions and thus coatings produced therefrom are characterized in particular by extremely good optical properties.
Another advantage of the copolymers according to the 20. invention lies in the fact that they are self-crosslinking systems which can be cured by a "double-cure" mechanism.
Anhydride groups initially react with hydroxyl groups, after which the carboxyl groups resulting from this reaction can react with the epoxide groups. The number of free carboxyl 25 groups in the coating is thus reduced, so that high crosslink densities may be obtained. Stringent requirements with regard to resistance to solvents and chemicals can be satisfied.
SUMMARY OF TH~NTrnN
The present invention relates to copolymers which 3o have a weight average molecular weight of 1,500 to 75,000, are prepared from olefinically unsaturated compounds and contain in chemically bound form i) about 0.2 to 6.0% by weight of free hydroxyl groups, ii) about 1 to 30% by weight of carboxylic anhydride ss groups (expressed as C4H203) and Mo3362 ~0~ ~~~4 iii) about 0.4 to 13% by weight of epoxide groups (expressed as C2H20).
The present invention also relates to a process for the production of these copolymers by copolymerizing a mixture s of olefinically unsaturated compounds at about 60 to 120'C in the presence of compounds which initiate the polymerization reaction, characterized in that, in addition to monomers free from hydroxyl, epoxide and anhydride groups, the mixture of olefinically unsaturated compounds contains 1o a) olefinically unsaturated alcohols, b) olefinically unsaturated anhydrides and c) olefinically unsaturated epoxides in quantities sufficient to provide copolymers containing about 0.2 to 6.0% by weight hydroxyl groups, about 1 to 30% by weight is carboxylic anhydride groups (expressed as C4H203) and about 0.4 to 13% by weight epoxide groups (expressed as C2H20).
Finally, the present invention also relates to the use of these copolymers as binders or binder components in one-or two-component coating or sealing compositions which may 2o contain catalytically active organic amine compounds as an additional binder component.
DETAILED DESCRIPTION OF THE INVENTION
The copolymers according to the invention have a molecular weight (weight average); as determined by gel 2s permeation chromatography, of about 1,500 to 75,000, preferably about 2,000 to 60,000 and more preferably about 3,000 to 40,000. In addition to chemically incorporated, free hydroxyl groups in a quantity of about 0.2 to 6. Ox by weight, preferably about 0.4 to 4.OX by weight, the copolymers contain bath 3o chemically incorporated, cyclic carboxylic anhydride groups corresponding to the formula -CH- CH-i 0=C\ /C=0 Mo3362 ~o~~o~~

in a quantity of about 1 to 30% by weight, preferably about 2 to 25% by weight (expressed as C4H203) and also chemically incorporated epoxide groups corresponding to the formula -CH-CH
~0~
in a quantity of about 0.4 to 13% by weight, preferably about 0.5 to 10% by weight (expressed as C2H20). The copolymers are copolymers based on preferably monoolefinically unsaturated monomers.
Four groups of olefinically unsaturated monomers are to used as starting materials in the process according to the invention for the production of the copolymers: a) olefinically unsaturated monomers containing hydroxyl groups, b) olefini-cally unsaturated monomers containing intramolecular carboxylic anhydride groups, c) olefinically unsaturated monomers is containing epoxide groups and d) olefinically unsaturated monomers which contain no such reactive groups and which are also inert to such reactive groups.
Monomers a) are generally used in a quantity of about 1 to 50, preferably about 2 to 40 parts by weight; monomers b) ao in a quantity of about 1 to 30, preferably about 2 to 25 parts by weight; monomers c) in a quantity of about 1 to 40, preferably about 2 to 35 parts by weight; and monomers d) in a quantity of about 1 to 50, preferably about 2 to 40 parts by weight, the sum of the total parts by weight of monomers a) to 2s d) being 100. The proportions of the individual monomers in the mixture to be copolymerized are determined such that the copolymers contain the above-mentioned quantities of chemically incorporated hydroxyl, carboxylic anhydride and epoxide groups.
The content of these groups in the copolymers corresponds to 3o the content of the same groups in the monomer mixture because it may be assumed that the copolymers correspond in their Mo3362 2~~a~~~

chemical composition to the chemical composition of the monomer mixture.
The type and quantitative ratios between the monomers are selected such that for each carboxylic anhydride group, the resulting copolymers contain about 0.2 to 8, preferably about 0.4 to 4 hydroxyl groups, and about 0.2 to 8, preferably about 0.4 to 4 epoxide groups.
The fact that copolymers such as these could be produced with hydroxyl, carboxylic anhydride and epoxide groups to was not predictable because carboxylic anhydride groups are reactive with hydroxyl groups at elevated temperatures and the carboxylic acid groups formed in this reaction can undergo an addition reaction with epoxide groups at elevated temperatures.
Nevertheless; it is possible in accordance with the process of 15 the present invention to obtain these new copolymers in organic solvents by radical copolymerization.
The monomers a) are monoolefinically unsaturated alcohols which preferably have a molecular weight of 58 to about 500 and preferably contain aliphatically bound hydroxyl 2o groups. Suitable monomers a) include hydroxyalkyl esters of acrylic and methacrylic acid, such as hydroxyethyl (meth)-acrylate [(meth)acrylate meaning either methacrylate or acrylate), hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; hydroxyalkyl vinyl ethers such as hydroxyethyl 2s vinyl ether and hydroxybutyl vinyl ether; allyl alcohol;
hydroxyl derivatives of (meth)acrylamide such as N-(3-hydroxy-2,2-dimethylpropyl)-(meth)acrylamide; reaction products of glycidyl (meth)acrylate with monocarboxylic acids; reaction products of (meth)acrylic acid with monoepoxide compounds;
so reaction products of the above-mentioned OH-functional, olefinically unsaturated compounds with e-caprolactone or butyrolactone; and mixtures of these monomers.
Suitable examples of monomers b) include itaconic anhydride, malefic anhydride and mixtures of these monomers;
s5 malefic anhydride is preferred.
Mo3362 ~o~~o~~
_,_ Suitable examples of monomers c) include glycidyl acrylate, glycidyl methacrylate and mixtures of these monomers.
The monomers d) have a molecular weight of 86 to about 400 and are unsaturated monomers, preferably monoolefini-cally unsaturated monomers, free from hydroxyl groups, anhydride groups and epoxide groups and which have been used as monomers in the process according to the prior art cited above.
Suitable examples include esters of acrylic and methacrylic acid such as methyl acrylate, ethyl acryiate, n-butyl acrylate, to isobutyl acrylate, tart.-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, methyl methacrylate, n-butyl meth-acrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate;
aromatic vinyl compounds such as styrene, vinyl toluene, a-methyl styrene, a-ethyl styrene, nucleus-substituted diethyl styrenes, isopropyl styrenes, butyl styrenes and methoxy-styrenes optionally in the form of isomer mixtures; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; vinyl esters such as vinyl acetate, vinyl propionate and 2o vinyl butyrate; and mixtures of these monomers.
The process according to the invention for the production of the copolymers may be carried out by copolymeri-zation of the monomers a) to d) standard radical polymerization processes such as mass or solution polymerization.
2s The monomers are copolymerized at temperatures of about 60 to 120'C, preferably about 80 to 115'C in the presence of radical formers and, optionally, molecular weight regulators.
The process according to the invention is preferably so carried out in inert solvents. Suitable solvents include aromatic hydrocarbons such as benzene, toluene and xylene;
esters such as ethyl acetate, butyl acetate, hexyl acetate, heptyl acetate, methyl glycol acetate, ethyl glycol acetate and methoxypropyl acetate; ethers such as tetrahydrofuran, dioxane ss and diethylene glycol dimethyl ether; ketones such as acetone, Mo3362 201~0~~
_8_ methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, and methyl isoamyl ketone.
The process according to the invention may be carried out continuously or discontinuously. Generally, the monomer mixture and the initiator are introduced uniformly and continuously into a polymerization reactor and, at the same time, the corresponding quantity of polymer is continuously removed. Substantially chemically uniform copolymers can advantageously be produced in this way. Substantially chemically uniform copolymers can also be produced by running the reaction mixture into a stirred tank reactor at a constant rate without removing the polymer.
It is also possible initially to introduce a portion of the monomers, for example in solvents of the type mentioned, is and subsequently to introduce the remaining monomers and auxiliaries separately or together at the reaction temperature.
In general, the polymerization takes place under atmospheric pressure, although it may also be carried out at elevated pressures of up to about 20 bar. The initiators are ao . generally used in quantities of about 0.05 to 15% by weight, preferably in quantities of about 0.1 to 10% by weight, based on the total quantity of monomers.
Suitable radical initiators are known and include aliphatic azo compounds such as azodiisobutyronitrile, 2s azo-bis-2-methyl valeronitrile, 1,1'-azo-bis-1-cyclohexane nitrile and 2,2'-azo-bis-isobutyric acid alkyl ester;
symmetrical diacyl peroxides such as acetyl, propionyl or butyryl peroxide, benzoyl peroxides and lauryl peroxides substituted by bromine atoms, nitro, methyl or methoxy groups;
3o symmetrical peroxydicarbonates such as diethyl, diisopropyl, dicyclohexyl and benzoyl peroxydicarbonate; tert.-butyl peroxy-2-ethyl hexanoate, tert.-butyl perbenzoate and tert.-butyl phenyl peracetate; peroxycarbonates such as tert.-butyl-N-(phenylperoxy)-carbonate or tert.-butyl-N-(2-, 3-35 or 4-chlorophenylperoxy)-carbonate; hydroperoxides such as Mo3362 2~1~~4~
_g_ tert.-butyl hydroperoxide and cumene hydroperoxide; and dialkyl peroxides such as dicumyl peroxide, tert.-butyl cumyl peroxide and di-tert.-butyl peroxide.
The molecular weight of the copolymers may be regulated by the presence of regulators during their production such as tert.-dodecyl mercaptan, n-dodecyl mercaptan and diisopropyl xanthogene disulfide. The regulators may be added in quantities of up to about 10% by weight, preferably about 0.5 to 5% by weight, based on the total quantity of monomers.
to The solutions of the copolymers formed during the copolymerization reaction may then be used in accordance with the invention without further working up. However, it is also possible to free the copolymers from any residues of unreacted monomers and solvents still present by distillation and to use the copolymers obtained as distillation residue in accordance with the invention.
The copolymers according to the invention are valuable binders or binder components for one- or two-component coating or sealing compositions. Because of the reactivity of 2o cyclic carboxylic anhydride groups with hydroxyl groups in the presence of heat and the reactivity of the carboxylic acid groups formed in this reaction with epoxide groups, the copolymers are suitable as one-component, heat-crosslinkable binders: In view of the fact that the copolymers according to 2s the invention are self-crosslinking, it is not necessary to incorporate any other binder component into the coating and sealing compositions which are to be cured by heating.
The copolymers according to the invention are substantially stable in storage at room temperature, even in 3o solution in paint solvents, and may be converted into systems curing at room temperature by addition of another "binder component," e.g., a suitable catalyst. In this embodiment, the copolymers according to the invention may be considered to be "binder components for two-component coating or sealing 35 compositions."
Mo3362 2~1~~~~~
-IO-In this particular embodiment for curing the copolymers according to the invention, it is essential to increase the reactivity of the anhydride groups to the hydroxyl groups by the addition of a catalyst component so that the crosslinking reaction begins at low temperatures such as room temperature. These catalysts are preferably compounds containing tertiary amino groups. The catalysts may be compounds which are inert to anhydride groups or which, in addition to the tertiary amino group, contain a group which is to reactive with anhydride groups (e.g., a hydroxyl group or a primary or secondary amino group). In the latter case, the catalyst component is chemically incorporated into the binder component by reaction of its reactive group with anhydride or epoxide groups (in the case of primary or secondary amino i5 groups) to form semiester, semiamide or secondary and tertiary amino groups, accompanied by the formation of an additional hydroxy group (from the epoxide group).
Compounds suitable as catalysts include tertiary amines having a molecular weight of 73 to about 300 such as 2o ethyl dimethylamine, diethyl methylamine, triethylamine; ethyl diisopropylamine, tributylamine, I-methyl pyrrolidine, 1-methyl piperidine, 1,4-dimethyl piperazine, 1,4-diazabicyclo(2,2,2)-octane or 1,8-diazabicyclo(5.4.0)undec-7-ene, N,N-dimethyl ethanolamine, N,N-diethyl propanoT amine, N,N-dibutyl ethanol-25 amine, I-amino-3-(dimethylamino)-propane or I-amino-2-(diethyl-amino)-ethane. Mixtures of tertiary amine catalysts may also be used.
It is also possible to use organic compounds containing at least one tertiary amino group which have a so molecular weight above 300. These compounds include reaction products of olefinically unsaturated compounds containing (meth)acrylate groups with secondary amines such as the reaction product of I mole of trimethylol propane triacrylate and 3 moles of di-n-butylamine. In addition, reaction products 35 of polyisocyanates with N,N-dialkyl alkanolamines, such as the Mo3362 reaction product of 1 mole of a biuretized polyisocyanate based on hexamethylene diisocyanate and 3 moles of N,N-dimethyl ethanolamine, are also suitable.
Compounds containing hydroxyl groups in addition to a tertiary amino group may be prepared by the reaction of compounds containing epoxide groups with secondary amines such as the reaction product of ethyl hexyl glycidyl ether and di-n-butylamine or the reaction product of 1 mole of 1,2,7,8-diepoxyoctane with two moles of di-n-hexylamine.
to In the production of two-component systems curing at room temperature, the catalysts are generally used in quantities sufficient to provide a tertiary nitrogen content (expressed as N, atomic weight l4) in the mixture of copolymer and catalyst of about 0:001 to 1.0% by weight, preferably about 0.01 to 0.5% by weight.
The curing rate of a "two-component system" may also be accelerated by heating, e.g., at temperatures of about 60 to 80'C.
Coating and sealing compositions containing the 2o copolymers according to the invention as the binder or as the principal binder component (in addition to the catalyst as second binder component) may also contain other auxiliaries and additives such as solvents or diluents, flow control agents, antioxidants, UV absorbers or pigments.
2s The ready-to-use coating or sealing compositions are produced by mixing the individual components. When solvents or diluents are used, they may be present during the production of the copolyn~rs as previously set forth. The solvents or diluents which may be added to the coating or sealing 3o compositions include those previously set forth for use in the production of the copolymers. They are generally used in the quantities necessary to adjust the coating or sealing compositions to suitable processing viscosities. The solids content of these coating or sealing compositions is generally 35 about 20 to 80% by weight. However, it is possible to reduce Mo3362 2~1c0~~~

the solvent or diluent content even further by the use of suitable low molecular weight copolymers.
The ratio of anhydride groups to hydroxyl groups and epoxide groups in the coating and sealing compositions s corresponds to those amounts previously set forth for the copolymers. If catalysts containing groups reactive with anhydride groups or epoxide groups are used in two-component formulations, so that there is an additional consumption of such groups, this may be taken into account if desired by an to increase in the concentration of the anhydride or epoxide groups.
The coating and sealing compounds according to the invention, which are preferably dissolved in inert solvents or diluents, are generally stable in storage for several months as 15 one-component systems and have a pot life of several hours as two-component formulations. One-component systems cure by self-crosslinking at temperatures of about 140 to 200'C while two-component systems cure at temperatures as low as room temperature to form films characterized by excellent mechanical 20 and optical properties:
The copolymers according to the invention may be directly used without further additives for the production of transparent coatings. However, the paint auxiliaries and additives previously set forth are generally used. The coating 2s or sealing compositions according to the invention may be applied by known methods (such as spray coating; spread coating, dip coating, flood coating; casting and roll coating) to substrates which may optionally have been pretreated (such as metals, wood, glass, ceramics, stone, concrete, plastics, 3o textiles, leather, cardboard and paper).
In the following examples, all percentages and parts are by weight, unless otherwise indicated.
Mo3362 2~~~~44 Examnl eses I General procedure for the production of the copolymers AI to A~ containing hydroxyl, anhydride and epoxide groups Part I was introduced into a 3 liter reaction vessel equipped with a stirrer and with a heating and cooling system and heated to the reaction temperature. Part II (added over a total period of 2 hours) and part III (added over a total period of 2.5 hours) were then added at the same time, followed o by stirring for 2 hours at the reaction temperature.
The reaction temperatures and the compositions of parts I to III are set forth in Table I together with the characteristic data of the copolymers obtained.
Mo3362 20~50~4 ~N ~
~

O CO0 t Q O~ N M ~-m .-r ~ ~ t0 ~
N

Q ,"
M
y M

O 0 ~
~

4'f tOt t 0~ OO 0 1~

Q CO r.~ N
r~ r.~
,.H
r~

~
N

et CO vr 1 'f O N

Q t0 N r1 M n--1 r1 r~

O

t f ~

r'M OD O t~
~

~D M et N ri d r 0 ~ ~
rN ~ ~

1~Q l M t!"
0 r-r-e s C

~ Wit' O t0 ~

r' O N s. O
-~
~i r O

00 .. W
N N N
~ W.

w J

O

i~

b C

O

X

N

L

N

N i~ r d t b r e~!

_ 41 C1 !~ d L
i~
N

~ V
~
h b N b N
N C
i N

r ~
~ b ~
= L

. X
i~
.

rt~ a o a~ s~ E~b~

_ . ,_ .
s i.> 1~ 10 V ~1r a .~1 r r it ~

N i~ r .C r' O ~'f ~ ~
CL ~f ~1 ~
a !
~

, .f.
i C !C
t O
L
.G

. d f.. N +~
t.. N +~
L a.~
C

d t~ V .C ris a .C 41 a C1 r t0 E e0 v eo N ~
ay r r E
>, ?>
a, r ~ ~ _ ~
tt r r C1 O ~
r O O~
r O i.i~L .1-1?1 L .1.1.id L .1~
.Id ~ f~
S~ t~

a ~ +~ s .~.> s.s-~ >,+~
w w .,~
v ~
~,r-o eo s o s a.~ e~oa~ e~.
a a> ~
~ s a, ~"-eo t~ 0. m~ 2 OON'~tVN00==C3'~ d f-v Mo3362 2~~.~a~~
O u~ .., ' d w O ~ ::

Q

t0 M

u7 ~ rH

N

O tt'f O ~' d vC O ~

.-,~1i u'~u~

N

0 ~ N

~ O N

O

t0 01 ...v tp ..

Of 01 C '~

d a~ O
N

.-i01 et O ~ M 1~

P ~ Iw m0 N

p O r Q1 w M
a ~ 01 M

i~

C O

w Q t0 O

m e ~ .:;

W

m s-t~ ~. -v ci a~ L
L
X

~ E c -' .~ .
d N 07 3E .~ C
d +a ...H b m N ~

E

t~ +~ iW r O
a O

N .!~ f0 C r O L

~ ~ ' ue s r s O .
a~
' r r N tA C
G~ ~ O ~

O ~~ r V

d +~ r 6 r +~ A O

U ~ d 0 m 7.
V O

Mo3362 ~0~.5~!~4 II Production of the coating compounds according to the invention a) Films cured under stoving conditions Copolymers A1 to A~ were adjusted to a processable viscosity by the addition of an organic solvent or diluent, if necessary. The films were applied by a film applicator to test plates in a wet film thickness of 150 um. After airing for 5 minutes at room temperature, the coated test plates were cured for 30 minutes at 150'C and then cooled to room temperature.
yo Clear, colorless crosslinked films having good optical and mechanical values were obtained in this way.
Solvent resistance was tested by a rubbing test using a cotton wool plug impregnated with methyl isobutyl ketone (MIBKj. The result of the test is expressed as the number of double rubs before the film showed visible change. The tests were terminated at 200 double rubs per film.
The solvent resistance of films based on copolymers A1 to A~ after curing at 150'C are set forth in Table Ii below.
Mo3362 a a ~I ~ N
O
Q O
O
M I
N
I a Q N
N
.D
C

O

'C H

C1 0!
r N ;.
~

Gf O

r~

E

r L .G
4..

_ G) 4 E

Wd ~

OOn! P G. OD

Mo3362 ~01~~~~4 b) Film curing at room temperature Copolymers A1 to A~ were mixed with a tertiary amine at room temperature and adjusted to a processable viscosity by the addition of an organic solvent or diluent, if necessary.
The films were applied by a film applicator to test plates in a wet film thickness of 150 Nm. The films applied at room temperature were all tack-free after 60 minutes at the latest.
After drying for 24 hours at room temperature, clear, colorless crosslinked films having good optical and mechanical values to were obtained.
The paint mixtures all had a pot life of several hours.
Solvent resistance was determined as described above.
The binder compositions and the solvent resistance as 1s a measure of the degree of crosslinking are set forth in Table III below.
Mo3362 2~~.~~!~~

et st d ~ a~ s O .-~49 N

N

O O A 1~

M
d 0 o a~
o .-mn N
M ~ ~~-~ O
O O /~ uy N
d Of C1 O t N O r~ t!7 N
O
O O /~ M
d a~ cn s o ..-.an ,-, .-, O

c o n o0 ~r .~

d c -ie .a o ws c G7 L

ro d ~

~

~u +~
+~
.a a~ o d t + c o v .N +~ d .a s.4-a b d ~ ~ ~
+~

_ _ 4JC. O 'C r .J

a ~c s .o X O Z ~ m d O ef ~

H 4J V Z CC d ~
N
C

Mo3362 20.~.~0~4 Q

v~ cna~ s o .-~~ ....

N

O O n O

'd' N

t0 Q

C~ C!1Cf r O -~O .-i N

~ O ~ O

t0 N

a rn cn v~.c o ~. o .~ o N

t C n N

e C N

E d ~

- b .a ro N i +~

V d d ~ s :~ ~ o ' c ~ a ~' .., e~ ~
o 4Jd O ~ J i b i E d t r m b E Z +~.E.~00 E

H i V ~

l Z o 2 ~N C

Mo3362 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3362

Claims (13)

1. A coating or sealing composition comprising a binder and an organic solvent wherein the binder consists essentially of a copolymer which has a weight average molecular weight of about 1,500 to 75,000, is based on the addition reaction product of olefinically unsaturated compounds and contains in chemically bound form i) about 0.2 to 6.0% by weight of free hydroxyl groups, ii) about 1 to 30% by weight of carboxylic anhydride groups (expressed as C4H2O3) and iii) about 0.4 to 13% by weight of epoxide groups (expressed as C2H2O).

2. The composition of Claim 1 wherein said copolymer is based on a reaction product comprising a) an olefinically unsaturated alcohol comprising a member selected from the group consisting of hydroxyalkyl esters of acrylic acid, hydroxyalkyl esters of methacrylic acid, hydroxyl derivatives of acrylamide, hydroxyl derivatives of methacrylamide, reaction products of glycidyl acrylate with monocarboxylic acids, reaction products of glycidyl methacrylate with monocarboxylic acids, reaction products of acrylic acid with monoepoxide compounds, reaction products of methacrylic acid with monoepoxide compounds, reaction products of the preceding hydroxyl compounds with .epsilon.-caprolactone, reaction products of the preceding hydroxyl compounds with butyrolactone and mixtures thereof, b) an olefinically unsaturated carboxylic anhydride, c) an olefinically unsaturated epoxide and d) an olefinically unsaturated compound which is free from hydroxyl, carboxylic anhydride and epoxide groups.

3. The composition of Claim 2 wherein the mixture comprises about 1 to 50% by weight of component a), 1 to 30% by weight of component b), 1 to 40% by weight of component c) and 1 to 50% by weight of component d), the sum of the percentages of components a), b), c) and d) adding up to 100.

4. The composition of Claim 2 wherein component a) comprises a member selected from the group consisting of hydroxyalkyl esters of acrylic acid, hydroxyalkyl esters of methacrylic acid and mixtures thereof.

5. The composition of Claim 2 wherein component b) comprises a member selected from the group consisting of maleic anhydride, itaconic anhydride and mixtures thereof.

6. The composition of Claim 2 wherein component c) comprises a member selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and mixtures thereof.

7. A coating or sealing composition comprising a binder and an organic solvent wherein the binder consists essentially of a copolymer which has a weight average molecular weight of about 1,500 to 75,000, and contains in chemically bound form i) about 0.2 to 6.0% by weight of free hydroxyl groups, ii) about 1 to 30% by weight of carboxylic anhydride groups (expressed as C4H2O3) and iii) about 0.4 to 13% by weight of epoxide groups (expressed as C2H2O), and is based on a reaction product comprising a) an olefinically unsaturated alcohol comprising a member selected from the group consisting of hydroxyalkyl esters of acrylic acid, hydroxyalkyl esters of methacrylic acid, hydroxyl derivatives of acrylamide, hydroxyl derivatives of methacrylamide, reaction products of glycidyl acrylate with monocarboxylic acids, reaction products of glycidyl methacyrlate with monocarboxylic acids, reaction products of acrylic acid with monoepoxide compounds, reaction products of methacrylic acid with monoepoxide compounds, reaction products of the preceding hydroxyl compounds with .epsilon.-caprolactone, reaction products of the preceding hydroxyl compounds with butyrolactone and mixtures thereof, b) an olefinically unsaturated carboxylic anhydride comprising a member selected from the group consisting of malefic anhydride, itaconic anhydride and mixtures thereof, c) an olefinically unsaturated epoxide comprising a member selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and mixtures thereof and d) an olefinically unsaturated compound which is free from hydroxy, carboxylic anhydride and epoxide groups.

8. The composition of Claim 7 wherein the mixture comprises about 1 to 50% by weight of component a), 1 to 30% by weight of component b), 1 to 40% by weight of component c) and 1 to 50% by weight of component d), the sum of the percentages of components a), b), c) and d) adding up to 100.

9. The composition of Claim 7 wherein component a) comprises a member selected from the group consisting of hydroxyalkyl esters of acrylic acid, hydroxyalkyl esters of methacrylic acid and mixtures thereof.

10. The composition of Claim 9 wherein the mixture comprises about 1 to 50% by weight of component a), 1 to 30% by weight of component b), 1 to 40% by weight of component c) and 1 to 50% by weight of component d), the sum of the percentages of components a), b), c) and d) adding up to 100.

11. A two-component coating or sealing composition which may be cured at room temperature and comprises a binder and an organic solvent, wherein the binder consists essentially of a copolymer which has a weight average molecular weight of about 1,500 to 75,000, is based on the addition reaction product of olefinically unsaturated compounds and contains in chemically bound form i) about 0.2 to 6.0% by weight of free hydroxyl groups, ii) about 1 to 30% by weight of carboxylic anhydride groups (expressed as C4H2O3) and iii) about 0.4 to 13% by weight of epoxide groups (expressed as C2H2O) and an organic compound containing a tertiary amino group.

12. The composition of Claim 11 wherein said organic compound containing a tertiary amino group additionally contains at least one group which is reactive with a carboxylic anhydride group or an epoxide group comprising a member selected from the group consisting of hydroxyl groups, amino groups and mixtures thereof.

13. The composition of Claim 11 wherein said organic compound containing a tertiary amino group does not contain a group which is reactive with a carboxylic anhydride group or an epoxide group.