CA1323950C - Curable resin compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention provides a curable resin composition consisting essentially of:
(i) a resin (A) containing .alpha.,.beta.-unsaturated carbonyl group and primary and/or secondary hydroxyl group, or (ii) a mixture of a resin (B) containing .alpha.,.beta.-unsaturated carbonyl group and a resin (C) containing primary and/or secondary hydroxyl group, and (iii) at least one curing catalyst selected from the group consisting of alkali metal alkoxides, metal hydroxides, organic acid salts of metals, quaternary ammonium hydroxides, quaternary phosphonium hydroxides, tertiary sulfonium hydroxides and organic acid salts of these onium hydroxides.

Description

ii, 2 ~ ~ 3 .~
~, C ~BLE ~BSIN COM~OSI~ION5 .
.~ ~he present invention relates to novel curabl resin compositions.
Curable resin compositions heretofore widely used for coating or other purposes include those which cQmprise a r~sin containing hydroYyl grqup as ~nctional group and a Cro551iD:ki~9 ag~t ahle tQ th~rm211y react with the hy~roxyl group:, such as meIanine re~in, blocke~
isocyanate or the like. ~owever, these compo~itions have the drawback of producing by-products when heat-cured such as water, alcohol or the like which would contaminate the interior of a drying furnace and would adversely affect ~he appearance of cured coat.
: 15 Also known are curable resin composition~
comprising a resin co~taininy ~B-unsaturated carbonyl group and a polyamino compound (U.S. Patent No.
3975251). When heated, this composition is crosslinked and cured by michael addition reaction of the polyamino -~ ~ 20 compound with the ,~-unsaturated carbonyl group. Yet - this composition is likely to entail the disadvantage~
that the cured coat is sus~eptible to discoloration and is impaired in the water re~ tance due to the pol ~ no compound .r~m~ining .in the c~I~ed CQa~. ~h~ comp~sitio~ i5 urther de~ective in di~inLshing the st:ora~e stabil:i-ty , .
' ~ .
.,,, ~ .

~. ~

2 3 ~ J ~ 2 .
; because of the ~ichael additi~n Leaction gxadually : proceeding durin~ storage.
An object of the present invention is to provide ~- a novel curable resin composition which has overcome the foregoing drawbacks.
Another object of the inve~tion is to provide a novel curable resin c~mpositi~n which produces nc ~y-product during heat-curing and which, ~hen cured, gives coa~s free of discoloration and outstandi~g in water resistance.
A further object of the invention is to provide a novel curable resin composition which is excellent in storage stability.
These and other objects of the invention will ~' 15 become more apparent from the following description.
. The present invention provides a curable re~in composition consisting essentially of:
a resin (A) containing ~B-unsaturated carbonyl group , and primary and/or secondary hydroxyl group, or (ii) a mixture of a resin (B) containing ~rB-unsaturated carbonyl group and a resin (C) containing primary and/or secondary hydroxyl group, and ; ~iii) at least onE curing c~talyst selected from the group consisting of alka1i me~al alkoxides, met-al hydraxid~s, organic acid salts o~ metals, quaternary amm-onium :;
.

.

. ! , .; ~ . . ~ .
. .~ - ' ~ , - ':

: -. ' ' . ., ` . ~ ~
- . :, '`"', ~ . ` ' `

;

~ 3 2 ~ 3 _ ~yd~nYides, quaternary phosphonium hydroxLdes, tertiary sulfonium hydr~id~s and organi~ acid salts of the~e onium ` hydroxide-s.
We conducted extensive research to overcome the foreyoing drawbacks of known curable resin compositions ., . ~
and ~-ound the-following.
(1) ~ compositi~n ~c~prising (I) a specific curing catalyst a~d a resin oo~taining ~B-uns2turated carbonyl ,- group a~d p~imary and/or~secondary hydro~yl group, or (II) ~; 10 the specific curing cataly~t and a mixture o~ a resin i containing the carbonyl group and a resin containing the ~' hydroxyl group i~ curable on crosslinking at a relatively low temperature and is excellent in storage stability.
(2~ Since the heat-curing is caused mainly by addition reaction of hydroxyl group with unsaturated group, the composition is unlikely to encounter the disadvantages attributabie to the productlon of by-product or to provide a discolored coat when cured. Further the compositions afford coats outstanding in water resistance, surface smoothness and the like.
The present invention has been accomplished based on these novel findings.
I This i~vention provides a curable resin com~sltio~ c~nsisti-n~ essentiall~ o~ t~e resi~ (A) ~s -the -25 com~on~t (i) and the curing catalys-t as the component ~, , . .

::' . :. . . ~

:;
.L ~ 2 ~ 4 ~,~

(iii) and-also provide~ -a curable ~esin c~mposition consist-ing ess~ntially of ~he resin mi~ture as the : .
component ~ii) and the curi~g~ catalyst as the component - 5 In the resin (A) as the component (i) containing the ~ unsaturated c~rbonyl group an-a primary and/or secnndary hydroxyl ~roup rn the inve~t;on, th~ i~,s-u~aturated carbonyl group i~ r~present~d by the ~ormula - -c=C-I-, such ~s acryloyl, m~th~cryliDylr itaconoyl, "~ 10 U
.~ maleoyl, fumaroyl, crotonoyl, cinnamoyl, acrylamido, methacrylamido and the like. Of primary and secondary hydroxyl groups, a primary one is prefi~rred in view o curability.
Insofar a~ the resin ~A) ha~ u,i~-unsaturated carbonyl group and primasy and/or secondary hydroxyl ~, i . group, the resin i8 not limited to ~pecific type and can be any of known resins including acrylic resins, polyester resins, urethane resind, polybutadiene resins, alkyd i . 20 resins, epoxy resins, phenol resins, polyethëx resins and . ~, polyamide resins. Further ~he resin ~A) can be prepared.
by any of known processes.
rhe molecul~r-wei4ht o~ the resin (A) i5 ~i~it ~ s~cific~II-y Iimi~d. 6e~i~r~lly the resi-~ (A) IS
.
~ ~5 preferabl~ ab~-iut ~50 to- a~ut:lOOOOOr more preferabl~
. , .
;:

.

, ;, , , ~ . . , ~ , ~. ~ 2 ~ 0 .

about 50~ to about 20a00, in peak molecular weiyht as determined by gel permeation chromatography in view of curability and solubility in a solvent. From the viewpoints of curability and water resistance of coat, i~
is suitable that the resin (A) contain about 0.DI to about 20 moles, preferably about 0.1 to about 5 moles, o~
the ~B-un~tur~t~d ~arbo~yl gr.Qup, and about 0.01 o about 50 mol-~s, prefera~ly ~bout 0.1 ~o about 10 moles, of the hydroxyl group, per kilogTam of the resin.
Preferred e~a~ples of the resin (A) include urethane resin~ which have the residue of adduot of N-- methylol acrylamide or:methacrylamide with i~ocyanate, the residue being represented by the formula ,,1 j , :
. . Rl ! O
' I ~' lL
15~ CH2=C-CON~-C~2-OC-NH- . ~I) wherein Rl is hydro~en atom or methyl group and which have ~:i . primary and/or secondary hydroxyl group. These re~ins , serve to give a coat excellent in adhesion because they .; have an amide linkage and urethane linkage. The resins --- 20 also provide a ~oat which remains firmly adhered after immersion in boiling water because of high adhesion of the re~in on one hand and the amide and urethane linkages there~f be-ing le~-s prone to hydro.lysis than an es~er li~k~e or the lik~ ~n th~ other hand ` 25 The re~ln ~ont~ining th~ functional g~oup ;~;.
. .

., .

., ` .

.,: ~ . ,~

. .: . , . . .
, ~ . .
.. . .

i ~2~
: - 6 -represented by the formula 1l) and the hydrQxyl grQup can be easily prepared, for examplet by reactL~g l mule-of-N-.
methylol acrylamide or methacrylamide with 1 mole of a diisocyanate compound in ~he absence of a catalyst or in the presence of a basic catalyst at a temperature of about 20 to about 150 C for about 1 to about 10 hours; mising the resulting adduct of isocyanate-contai~ing ~-~ethylol acryl~mide or meth crylamide ~hereinaft~r re~erred-to as ~ad~uct (a) n ) with a hydro~yl-containing r~in; and reacting the isocyanate group of the adduct (al with part of hydroxyl groups in the hydroxyl-containing resin in an inactive organic solvent in the absence of a cat~ly~t or in the presence of a basic catalyst under the same . reaction conditions as above~
; 15 Preferred examples of useful diisocyanate compounds are those having two f ree isocyanate groups per . molecule, the two groups being different in reactivity .~, .: .
from each other, such as 2,4-tolylene diisocyanate, m-xylylene diisocyanate, methylcyclohexane-2,4-diisocyanate, 1,3-diisocyanate methyl cyclohexane, isophorone . diisocyanate, etc.
i E~amples of useful basic catalysts are tertiary amin~s su~h as triethylami~ dimethyl etha:nol, pyTidine, tributylami-~e a~d t~ lik~.
se~ul inac*ive ~r~anic s-olv~nt~ are tho~e in . ~ , .
, , : . . . ~, . . -: . ,, -,, ~ . : , .: . : : ~ , .. ; :

~32~3..3~

,. . .
which the adduct ~a) and the resin (C) can be dissolved or dispersed and which is free of active hydrogen at~m reactive with the isocyan~te group of the adduct (a).
Exemplary of such solvents are aromatic hydrocarbons such as xylene, toluene and the like, ketones such a~ m~thyl I ethyl ketone, acetonel met~yl isobutyl ketone, ~,~
~ cyclohe~anone and the like; ethers such as ~thyl~ne gl~col j di~ethyl ether, diethylen~ glycol dimethyl ether a~d the like; esters such as methyl cellosolve acetii~te, ethyl acetate, methyl acetate and the like; etc.

Useful hydroxyl-containing resins are not ~ limited to specific type and can be any of known ones ;, insofar as the resins have at least 2.0 hydroxyl sroups on the average per molecule. Examples of such resins are acryl polyol, polyester polyol, polyether polyol, alkyd ~; caprolactone polyol, epoxy, urethane polyol and like `~ types.
The ~ unsaturated carbonyl group of the resin (B) in the resin composition of the invention consisting essentially of the resin mixture as the component (ii) and the curing catalyst as the component (iii) is represented .j by the formula =C--C

-, O
.~ 25 Examples of the gr~up are acryloyl, methacryloyl, :

...
'~' ., ..... .
.:
.".,:, ~
.; . . .
.~.. ,~ .

~:, . :¢^.~ ~ :

ita~onoyl, maleoyl, fumaroyl, orotonoyl, cin~amoyl~
acrylamido, methacrylamido, etc. Of the hydrQ~yl groups in the resin ~C) having prLmary and/or secondary hydroxyl group, a primary one is preferred in view of curability.
~he kind of the resin (B) is not critical insofar as the resin has ~iB-unsaturated carbonyl group.
:T~e kind ~f the resin (C) i~ not specifically Iimited if ~ . .
~he resin has primary anaJor seoondary hydroxyl groupO
qhe:re~ins (s) and (C) are not limited ~o specifi~ types lo and ~an be any of known ones including acrylic resins, , ' polyester resins, urethane resins, polybutadiene resinsl i( . . i ~
alkyd resins, epoxy re~ins, phenol resins, polyether resins, polyamide res~ins and the like. The resins (B~ and ;
~. : (C) can be prepared by any of known processes.
.. ~ . . : .
- ~. 15~ The molecular weights of the resin~ (B) and (C) :
are not specifically limited. Generally the resin3 (B) ' and (C3 have a peak molecular weight of preferably about 'J 250 to about 100000, more preferably about 500 to about 20000, as determined by gel permeation chromatography, in ~, ~0 view of curability and solubility in a solvent, From the viewpoints of ourability and water resistance of coat, it is suitable that the resin ~B) contain about 0.01 to about .
20 moles, pr~ferably about 0.1 to about 5 moles, of the ,B-uns.aturated carbonyl g~up, per kilogra~ of the resi~
~ 25 an-~ th~t the re~ln (C) contain about OoOI to about 50 ., : .
, ~..

., . ~ .. , ~: ., ' ' ' ~ , ,- .

", :i 3 2 ~
: - 9 ~

moles r pre~erably about D.l to about 10 moles, of the - hydrQxyl ~roup, p~r-kilogr~m of the resin.
, Preferred e~ampl~s of the resin (B~ are urethane ; resins which have the residue ~f adduct of N-methylol S acrylamide or methacryl~mi~e with isocyanate which is represented by the formula (I)~ ~hese r~sins serve ~o give a coat particularly e~cell~nt in a~hesion and resist2nce to boili~g wa.ter~
~he resi~ havi~g he ~unction~l group of ~he formul tI) can be easily prepared, for example, by reactiny the adduct (a~ with the whole hydroxyl group , present in the resin having at least 1.0 hydroxyl group on the average per~'molecule under the same reaction , conditions as those described hereinbefore or reacting N-", lS methylol acrylamide or methacrylamide with an,isocyanate-containing resin. Exampl~is of useful isocyanate- ' , ' .,` containing resins are a' homopolymer prepared by homopolymerizing an unsaturated monomer such as isocyanate ethyl acrylate or methacrylate, ,-dimethyl m-" 20 isopropenylbenzyl isocyanate, or a reaction product of l mole of hydroxyl-containing acrylate or methacrylate with ''. 1 mole of the diisocyanate compound; a copolymer prepared by copolyme~izing the:same with other ~adically , pol~mEri~able u~satu~at~d-monQmer; ~nd a resin prepared by ,i ~ 25 reaction of hydro~yl-c~ntai~i~g resin with said .`
. .

:

, :
i .
.. .

:.~

.~ .

~ 3 2 3 ~3 ~ 1 o ` diisocyanate compound, etc.
: The mixing-ratio of the ~esi~s (B~ and (C~ inthe resin mi~ture as the component (ii) according to the invention is preferably about 99.99 to about 50% by weight, more preferably about 99.9 to about 70% by weight, of the resin (B) a~d preferably about O.Ol-to about 50% by , ~ ~eight, more preferahly ~QUt 0.1 to a~:o~t 30% by weight,: of the resi~ (C).
The curiny catalyst ~s the c~mpo~ent (ii~ in the present invention is at 1east one species selected from the group consisting of alkali metal alkoxides, metal hydroxides, organic acid~salts of metals, quaternary .. . .
~- a~monium hydroxides, quaternary phosphonium hydxoxides, ; tertiary sulfonium hydro~ides and organic acid salts of .
these onium hydroxides.
.' . Representative metals for metal hydroxides are .
:~ - alkali metals, alkalinl earth metals, cobalt, nickel, ~` copper, molybdenum, lead, iron, chromium, manganese, zinc, ~. . . .
etc.
Illustrative alkali metal alkoxides are sodium ethoxide, sodium methoxide, potassium methoxide, potassium ethoxide, etc.
Typical alkali:m~al hydr.oxides a-re sodium ~ydroxide, potassium-h~dr~xide,:`lit:hi~m hydro~ide, etc.
Representative alkalin~ ~rth m~tal ~ydrQxides are calcium .'. ' 1.
., i ' . .
' : ;
' .. ' .
~, ~ ~ .

:
.':',~ .
',''' ' . ~ ' : ' :
:`' . , ' .' " ':
,,:~ . . :

, f ~. 3 2 3 J 3 ~
.

hydroxide, magnesium hydro~ide, b~rium hydraxide, etc.
~ se~ul ouaternary ~mmQ~iUm hydroxides, quaternary phosphonium hydroxides and tertiary sulfonium hydroxides include the hydroxides ezch represented by the - ~ formulzs (II), ~ and (IY~, respect~ve]y:

1 ~) E3 ~30~ (II) ;i R~
~ 9-R3 (~OH ( III ) . R4 .

OH (IV) . R3 ~; In the formulas, Rl, R2l R3 and R4 are the same ; or different and each represent hydrogen atom or organic group having 1 to 14 carbon atoms, at least one of the Rl, R2 and R3 groups is an organic group having 1 to 14 carbon - atoms, and the Rl and R2 groups or the Rl, R2 and R3 ~`~ groups when taken together with nitrogen atom, phosphorus ~ atom or 5Ul ~ur a.om to which they are attached may form a ,lj h~terocyclic group.
:ij 2~ The type o~ organic groups represented by R
:'.~, , ' .~
.'' ~' .
:' , . . .
:,., -.
. .:

, ~ ~ 2 ~
- ~2 -.~ .
-R2, R3 and R4 and having 1 to 14 carbo~ atoms is not ; cr-Ltical insofar a~ the groups substantially do not ~in~r i:onization of ammonium hydroxides, phosphonium hydr2xides or sul~onium hydroxides. Generally usable as such organic : 5 groups are hydrocarbon groups of 1 to 14 carbon atoms which may contain hetero atom such as oxygen atom.
Ex~mpl~ of orga~ic groùps containing oxygen atom are , :.
hyaro~arhon groups substituted with hydro~yl or alk~xy group.
Examples of such hydrocarbon groups are . I
aliphatic, alicyclic or aromatic hydrocarbons such as alkyl, cycloalkylt cycloalkylalkyl, aryl and aralkyl . groups. ~he alkyl groups may be any of straight chain or J` , branched chain ones and include those of 8 or less carbon atoms. Preferable alkyl group~ are lower ones and include .: - .
methyl, ethyl, n- or i~o-propyl, n~ o-, sec- or tert-`~ butyl, pentyl, heptyl and octyl groups. Preferred examples of the cycloalkyl groups or cycloalkylalkyl . groups are those having 5 to 8 carbon atoms such as - 20 cyclopentyl, cyclohexy~, cyclohexylmethyl, cyclohexylethyl, etc. Useful aryl groups are phenyl, tolyl, xylyl and the like. Benzyl group is suitable as alalkyl group.
Preferred e~amples ~f h~drocar~on group~
2S co~taLning hetero-atom ~uch as oxygen atom are .. : , .
.~
: .

., .
., r~

.. ~.~ ' . . . .
.

:-, : , , .'`'.~ ~ ' ' ' '- ' ` ' . `
'. ~ ' , , : ~ ' :

~23~ .13 -, . .
hydro~yalkyl (particularly hydroxy-lower alkyl), specific exampl~s keing hydroxymethyl, hydroxyethyl, hydroxybutyi, hydroxypentyl, hydroxyheptyl, hydroxyoctyl, alkoxyalkyl (particularly lower alkoxy~lower alkyll such as met~axymethyl, ethoxymethyl, ethoxyethyl, n-propoxyethyl, .
iso-propoxymethyl, n-butoxymethyl, iso-butcxyethy~, tert-~ -hutoxy~thyl, etc.
.
Given below are exahlples o~ heterocyclic groups ~ormed by the Rl and R2 groups or the Rl r R2 and R3 groups when taken together with nitrogen atom, phosphorus atom or sulfur atom to which they are attached:

CH3--S~_l, CH3--S~=l, CH3--S~JO, ,, .
`:. 15 CH3 CH3 :il CH3 --P3 CH~ CH2 --P~, CH3 --N~, ." CH CH2 CH3 CH3 CH3 --N~d ~ CH3 CH~ --N O, CH3 --N
, 20 . Curing catalysts useful in the invention include ~'~! the o~ganic acid salts of hydroxides of these alkali , meta.ls, alkaline earth metals and other metals and organic aci~ salts of said onium hydroxides.

. 25 Examples of organic aci.ds use~ul for forming . ,1 .

. , .

: .

.: - .
,. ~. ' :
,"~ ' :` , .~ ~

:
~ ~ 2 ~
~ - 14 -.

organic acid sal.ts ale fQrmic acid, acetic acid, lactic acid, trimethylacetic a~id, acrylic acid, methacrylic acid, chloroacetic acid, hydroxyacetic acid, crotonic acid, monomethyl maleate, monoethyl fumaratel monomethyl itaconate, etc. Of these organic acids, those having a dissociation constant (pRa ~alue) of 1 X 10 5 or more~
particularly acetic acid, formic~cid~and acrylic acid are-preferred.
- A suitable amount of-the curi~g catalyst useful - . ~
: 10 as the component liii) is about 0.001 to about 30 parts by : weight per 100 parts of.the resin (A) as the component (i) , : or the mixture of reSinQ (B~ and (C) as the component ~ . . . .
~` (ii). A smaller amount of curing catalyst used results in ~/ , ~ , .
unsatisfactory curability, hence undesirable. On the other hand, a larger amount of curing ratalyst used is undesirable because the catalyst used tends to remain in :~ ~ the cured coat, reduci~g the water resistance. A
: . preferable amount of curing catalyst is about 0.01 to about 20 parts by weight.
When required, the curable resin composition of ...
the invention consisting essentially of the resin ~! component as the component (i) or (iil and the curing , , - catalyst ~s the component liii) may contain additives such ,~,, .

~ as a coloring pisme~t, ~tender pigment, corro~ion-'~. 25 resisting pigment~ leveling agent, anti-foamin~ agent, , .

~, :,', ~ .

:
.. . .

.. ,: :: - :

13239..0 l - 15 ~
.
. . . .
anti-sagging a~ent and,the like.
The curable ~es~n compOSitiQn of the inventi~n can be cured on crosslinking by heating at a relatively low temperature. It is suitable that the compositi~n be heated at about 60 to about 300C, preferably a~out 100 to about 170C, for about 5 to about 120 minutes, pre~erably about 10 to about 30 minutes -~ccording to the invention, the resin ~A3 having ~B-unsaturated carbonyl gro~p and primary and/or . . . .
~ 10 secondary hydroxyl group, or alternatively a mixture of : the resin IB) having ~ unsaturated carbonyl group and : ~
the resin ~C) having said hydroxyl group is combined with i : the specific cùring catalyst, thereby affording the 3 : ~. . -î : advanta~es that the addition reaction of hydroxyl group .. . . . . . . .. . . . . . .
- .15 with unsaturated ~roup is caused at a rel2tively low -temperature and that the addition reaction produces ~o by-:,. . . . . . . . .
~............... product nor entails any color change of cured coat. The .. . . . . .
compositions of the invention are also advantageou~ in being excellent in storage stability and forming a coat ~! :
. 20 excellent in water resistance, surface smoothness and the ~J! like when cured and are therefore suitable for use as ., coating compositions, particularly as paints.
'' ~hP compos;tions of the invention prepared using , ,, .' the fun~tional group of the formula (I3 ~s th~
-i~ 25 ~ unsa~urated carbonyl group can produce c~ats .. ;, . .

.

.~, :; .
: . . .
, .
. -` ~3~39~0 16 -particularly hi~h in adhesion and resistance to boiling water.
The pres~nt invention will be described below in greater detail with reference to the following Preparation Examples, Examples and Comparison Examples wherein the parts and the percentarges are all by weight.
P~eparation o~ resin_(A) havi-ng ,~-unsaturated carbonyl ~roup and ~rimary and~or secondary hydrox~l group Prepa~a.tion Example 1 Glycidyl methacrylate l 142 parts 2-Hydroxyethyl acrylate 116 part~
n-Butyl methacrylate - 742 parts .,.
: ~zobisisobutyronitrile 25 part The above mixture was added dropwise to 1000 ~,i. . .
15 parts of toluene in a 4 neched flask at 120C over a period of 3 hours. Therea~ter the mixture was aged at 120C for 5 hours.
Methacrylic acid . 86 part~
:l ~ydroquinone 0.2 part Tetraethyl ammonium bromide l.Q part , Toluene 87 parts The above mi~ture was added thereto and the resulti-ng admixture was reacted at 120~C~ ~hen an acid .~ value reached 1 or l~ss, ~he re~cti~n was terminat~d, '~ -25 giv-ing -an acrylic resin solu.tion. The thus obtaine-d resin :
, . .

, ~
.

. ~

., : . . .

13239a(3 solution had a nonvolatile ~3ntent of -50.0% and a viscosity of M (as deter~ined at 25~C by a Gardner-~oldt bubble viscometer, th~ same hereinafter). The resin was about 25000 in peak molecular weight as determined by gel S permeation chromatography and had an ~ unsaturated carbonyl group content of 0.92 mole, a primary hydro~yl g~oup conte~t of 0.92 mole and a s~condary hy~r~xyl group content of 0.92 mole, ~11 per kilogra-m of the resin solid.
Preparation E~ample 2 "Epikoat #154" ~*1~ 627 parts Acrylic acid - 252 parts ~ydroquinone 1 part Tributylamine ; 3 part~
Ethylene glycol monobutyl ether 883 parts The above mixture was charged into a 4-necked -- flask and reacted at lQ0C. When an acid value reached 0-, the reaction was terminated, giving an epoxy resin solution. The thus obtained resin solution had a nonvolatile content of 49.7~ and a viscosity of H. The - 20 - resin was about 1000 in peak molecular weight as ~
determined by gel permeation chromatography, and had an unsaturated carbonyl group content of-3.98 moles and a secondary hydroxyl group cont-ent of 3.98 mol s, p~r kilogr~am of the resin soIld, :25 Note: (~1) "Epikoat ~154":-tra~emark, product of Yuka ..
., .
'., . ~. '' , '. ........ -. . .
.'~

-"

13239 ~aO

5hell Epoxy Co., Ltd., phenQl-novolak type epoxy resin, about 500 in number-average molecular weight, about 174 in epoxy equivalent.
re~aration_Example 3 Ethylene glycol 496 parts Fumari~ acid104g parts Trimethylolpropane 240 parts The above mixture was charged into a 4-necked 1~sk and subjected to conde~sation reaction at Z0~C.
When an acid value reached 10 or less, the reaction wa~
terminated~ Thereafter 1456 parts of butyl acetate was added thereto, giving an polyester resin solutionO The thus obtained resin solution had a nonvolatile coTItent of . ~ . . ;
50.4~ and a viscosity of ~. The resin was about 5000:in i . .
1~ peak molecular weight as determined by gel permeation chromatography, and had an ~ unsaturated carbonyl group Z content of 6.18 mole~ and a primary hydroxyl group content ~, ;; of 2.34 moles, per kilogram of the resin solid~

- Pr~paration Exa~ple 4 ~~ 20 "Placcel #308" (*2) 1000 parts Isophorone diisocyanate 444 part~

Methyl ethyl ketone 1444 parts The above mixture was placed into a 4-necked ;.
Z. fla~k, and reacted at 70C. -When an NCO value reached 30, -~ 25 the reaction was terminated7 ,.Z
, ,!~

' S
~,., ' ' . ' ' '~
" . ' ' i ~': , '~J,` ' ' , ', .,', , .
''~ ' :
.~ . . .

13239~'~

2-~y*roxyethyl acrylate 232 parts ~ydroquinone i 1 pa~t Methyl ethyl ketone 233 parts The above mixture was added thereto a~d the resulting a~mixture was reacted at 80C. When an ~CO value re:ached 1 or less, the reaction W2iS
t~rmi~ated, giving a ~rethane resin solution. ~he thus obtain~d resin solution had a nonvolatil~ cont~nt o~ 50.~% and a ViscQsity of X. The resin Wa5 about 2000 in peak molecular weight as determined by ~el permeation chromatography and had an ~ uni~aturated carbonyl group content of 1.19 moles and a primary , . . .
~: hydroxyl group content of 0.89 mole, per kilogram of the , resin solid .j ~ , .
~, 15 Note: ~*2) "Placcel #308". trademark, product of Daicel . Chemical Industries~ Ltd., ~-caprolactone type , trifunctional polycaprolactone polyol~ about 1280 in weight-average molecular weight, 198 in hydroxyl value.
Pr~paration Example S
. ~ .20 Isophorone diisocyanate ~ 444 parts : 2-Hydroxyethyl acrylate 232 parts ~, Methyl ethyl ketone - 290 parts ! The abQve mixture was charged into a 4-~ecked ~ flask ~nd r~acted at:80C until a~ ~CO value reached 87, .1 25 wh~reupon an isocya-nate-contaiini~g unsaturated moniomer `~, .~

~!

,''j~ , ~ ' ~ -' .'' ' ' ~`'''~ ` ' ' .
. , : ~ . .

. ,.
:' ,~ ,~ , ' , ,~ .

13239~0 solution was o~tained.
"E~ikoat X1002" (*3) 1256 parts Diethanolamine 210 parts Methyl ethyl ketone 628 parts Aside from the above procedure, the above mixture was charged into a 4-necked flask and reacted at 80C over a p~riod af 3 hours, giving a hydroxyl-containing resin soluti,on~
`~ The monome~ solu~ion ~966 parts) and 2094 parts o~ the hydroxyl-containing resin solution were mixed and reacted at 80C for 10 hour~, giving an epoxy urethane ~ resin solution. The obtained resin solution had a .~ nonvolatile content of 70.0% and a viscosity of X. The ., resin was about 2300 in peak molecular weight as determined by gel permeation chromatography, and had an unsaturated carbonyl group content of 0.93 mole and a primary hydroxyl group content of 0.93 mole, per kilogram `1 of the resin solid.
, Note: (*3) "Epikoat #1002": trademark, product of Yuka ... .
:'!20 Shell Epoxy Co., Ltd., bisphenol A type epoxy resinl abQut 1256 in number-average molecular weight, about 630 in ` epoxy equivalent Exampl:es 1 to 17 ~he curahle res.in:composi.tions Qf thP pr~5Ent '. 25 i-~vention were prepared by ~omoseneously mixing ~he resin ., ., .~r , .:- ' :
'~: " ' '' ' , .
''.': ' ' ' :': ' ' ~,', ' : ' ` 1 3 2 3 ~ 3 - 21 solutions obtained in Preparation Examples and the curi~g , catalysts as snown below in Table 1 in the amounts listed ~, therein.

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~ote : (*4) C~mpound A is a compound repre~ented Dy C~ OE

(*5) C~mpound B is a csmpound represe~ted by L3~cs2~cl2~s2~ o~

, 10 ., Each of the compositions prepared in Examples 1 to 17 was applied to a ~lass plate to form a layer having a thickness of about 20 ~m when dried. The layer deposited on ~he glass plate was cured by baking in an oven. The coated glass plate was checked for the water - resistance and gel fraction ratio. The compositions were s also tested for the storage stability. The baking was `~!
perormed under the following conditions and the tests were conducted by the methods described below.
~0 Baking conditions The coated ~lass plate was baked at 140C for 30 ~- minutes in Examples 1 to 5 and 17, and at 100C for 10 minut~s in Ex-mple 6, aL i20C fo-r 10 minutes in Egam?les ; 7 a~d 8 and at 140C ~or I0 ~t~s in F~mDl~s 9 to 1D .
.;. 25 ~ater res:ista~ce .~, , .
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., - 25 -~ he appearance of the coated gla-~s pl~.te was checked after 7 days of immersiQn in warm wa:ter at 40C.
el fraction ratio : The layer f~rmed and cured on the glass plate was peeled and placed into a container of 300-mesh s-t~inLess steel netti~g whereupon the layer was estr~cted with a SQ2hlet's extractor ~or 6 hours using a sol~ent ~, mixture of acetone a~d methanQ1 in e~ual amounts in terms ., o~ weight. ~he geI fraction ratio was calculated according to the following equation:
:~ Gel fractio~ ratio (%)= ~weight of layer after extraction/weight of layer before extraction) X 100 Stora~e stability .; , Into a hermetically closed can 250 cc in internal volume was char~ed 200 g of each of the .`rl compositions obtained in Examples and Comparison Examples. The composition w~s checked for propertie~
after 30 days of storage at 50C. The composition ;~ :
,, involving neither significant increase of viscosity nor gelation was expressed with a mark "A".
~` Resistance to discoloration .'! . ., The layer formed and cured cn the glass plate ~;~ w~s ~isually ins~ect-ed:~or t~e deg~ee of color change.
-~ The l~res which had n~,c~lor ~h-ange was exp~.essed~as A, ,il `.; 25 and the layer which turned yellow a:s B.

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Table 2 below shows the test results.

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':: , : .. - , ~ 3239~0 - ~8 -. Re~istance to:boilin~ water Each of the comp3sitions was ~hecked f~r ~he resistance to boiling water by the following method.
The composition was applied to a steel plate treated wi-h zinc phosphate to form a layer having a 20 ~m thickness when dried. The coatPd plate was baked and then immersed in boiling wat~r ~or 1 hour or 2 hours a~d withdrawn to evaluate the ~ppearance of layer and th~
a &esion.
~i~ Appearance_of coating layer ~he coating layer was checked fox cracking, peeling and blisterlng.
(ii~ Adhesion coated plate was cut crosswise to the ~ 15 substrate to produce 100 squares having l-mm sides, . . and cellophane adhe~;ve tape was adhered and peeled .
., ~ off after uniformly pressing the tape-covered surface with an even force. ~hen the number of squares remaining adhered was counted.
Table 3 below shows the results.

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~3239~0 :
Pre~aration of resin (B) havin~ unsaturated carbonyl ., ~.
Pre~ratîon Exam~le 6 Glycidyl methacrylate 1~2 parts n~Butyl methacrylate 858 parts Azobisisobutyronitrile 25 parts T~e above mixture was added dropwise to 1000 parts of toluene in a ~-ne~ed ~lask at 120~C ~ver a 3 hours' period. The resultin~ mixture was aged at 120~C
; . .
for 5 hours. '~
Methacrylic acid 86 parts ~ydroquinone 0.2 part Tetraethyl ammonium bromide 1.0 part Toluene 87 parts The above mixture was added thereto and the .-; . :
resulting admixture was reacted at 120C. When an acid . ~ .
value reached 1 or le~s, the reaction was terminated, giving an acrylic re~in solution. The resin solution had a nonvolatile content of 50.0% and a viscosity of ~. The resin was about 25000 in peak molecular weight as determined by gel permeation chromatography and had - - - an ~ unsaturated carbonyl group content of 0.92 mole and a secondary hydroxyl ~roup content of G.92 mole, p~r kil~gram of the resLn ~olid.
~-5 Pre~ar tion Example 7 ~' ;

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13~39~

'1Epikoat ~154" * 627 parts Acrylic acid 25~ parts Hydroguinone 1 part Tributylamine 3 parts ; 5 Ethylene glycol monobutyl ether 883 parts The above mixture W2S introduced into a 4-necked flask and reacted at 100C. When an acid value reache~ 0, the reaction was terminated, giving an epa~y resi~
solution. ~he resin solution had a nonvolatile content of 49.7% and a viscosity of ~. The resin was about 1000 in peak molecular weight as determined by gel permeation chromatography and had an ~ unsaturated carbonyl group `~ ; content of 3.96 moles and a secondary hydroxyl group content of 3.96 moles, per kilogram of the resin solid.
Preparation-Example 8 Ethylene glycol 496 parts Fumaric acid 1044 parts The above mixture was placed into a 4-necked flask and subjected to condensation reaction at 200C. On ~ 20 completion of dehydration, the reaction was terminated.
- ~hereafter 1252 parts of butyl acetate was added-to the . .
reaction mixture, giving a polyester resin s~lution. The resin solution had a nonvolatile content of 50.2% and a ~ viscosity of Q. The resin was about 3500 in peak :`~ 25 molecular weight as determined-by gel permeation :,' * Trade mark : A
, . .
. . .

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13239aO - 33 -chromatography and h~d an ,B-unsaturated carbonyl group content o~ 7.19 moI2s per kilogram of the resin solid b~t no hydroxyl group.
Pre~aration Example 9 5 "Pl2ccel ~30B" * 1000 parts Isopho~one diisocyanake666 parts ; ~ethyl ethyl ketone 1666 parts ~he a~ove miYture was placed into a 4-neck~d ., .
flask and reacted at 70C~ ~he reaction was terminated 10 when an NCO value reached 38.
2-Hydroxyethyl acrylate ~48 parts j ~ydroquinone 1.5 parts : Methyl ethyl ketone 350 parts The above mixture was added thereto and the '~ ` 15 resultin~ admixture was reacted at 80C. When an NCO
, value reached 1 or less, the reaction was terminated, giving a urethane resin solution. The resin solution had ~ - a nonvolatile content of 49~8% and a viscosity of Z. The ;,;
. resin was about 2000 in peak molecular weight as :~, i 20 determined by gel permeation chromatography and had an ~ ~ .
`' ~,B-unsaturated carbonyl group content of 1.~9 moles per ..,j - kilogram of the resin solid but no hydroxyl group.
,::
- Pre~aration of resin (C~ havin~ primary and/or secondary .. hydroxyl gloup ....
~ 25 PreDaration Exam~le 10 ,, " .
,~ * Trade mark ~',' .
A
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~ ~3239aO 3~

ydroxyethyl acrylate 116 parts n-Butyl methacrylate . 884 parts . . Azobisisobutyronitrile 25 parts The above mixture was added dropwise to 1000 parts of toluene in a 4-n~cked flask at 120C over a 3 hours' period. ~he mixture was aged at 120~C for 5 hours, giving an acrylic resin solution. The resin solution had a nonvolatile content of 50.0% and a viscosity o~ O. ~he resin was about 30000 in peak molecular weight as determined by gel permeation chromatography and had a primary hydroxyl group content of 1.00 mole per kiloyram . .

i of the resin solid but no ~tB-unsaturated carbonyl group.

P eparation Exam~e 11 .
.. "Epikoat #154" 627 parts Diethanolamine 245 parts Ethylene glycol monobutyl ether 872 parts The above mixture was introduced into a 4-necked - . , flask and reacted at 100C for 1 hour, ~iving an epoxy resin solution.
, .
The resin solution had a nonvolatile content of ., .
: 49O7% and a viscosity of V. The resin was about 1000 in peak molecular weight as determined by gel permeation chromatography. The resin had a primary hydroxyl group ' content of 5.*5 moles and a secondary hydroxyl group ~-5 content of 2.73 moles, per kilogram of the resin solid hut .J

.

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13239~0 no ~,3-unsaturated carbonyl group.
Preparation Example 12 Ethylene glycol 496 parts Phthalic acid 1332 parts Trimethylolpropane 240 parts The above ml~ture was charged into a 4-necked ~lask and ~ub~ected to con~nsatio~ reaction at 200C.
When an acid v~Llue reachea 10 or less, the rea~tion was terminated. Thereto ad~ed was 1906 parts of butyl acetate, giving a polyest2r resin solution. The resin solution had a nonvolatile content of 50.5% and a viscosity of M. The resin was about S000 in peak molecular weight as determined by gel permeation chromatography. The resin contained no ~lB-unsaturated carbonyl group but had a primary hydroxyl group content of 1.78 moles per kilogram of the resin solid.
Examples 18 to 30 and Com~arison Examples 1 to 3 The curable resin compositions of the present invention and comparative curable resin compositions were prepared by homogeneously mixing the resin solutions obtained in PrPparation E~amples and the curing catalysts shown below in Tab1e 4 in the amounts listed therein.

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~323~30 Each of the com~ositiQ~s prepared L~ Examples 18 ~o 30 and Co~palison Examples 1 to 3 was applied to a glass plate to form a layer having a thickness of about ;. 20 ~m when dried. The layer deposited on the glass plate was cured by baking in an ove~. ~he cured coated plate was checked for the water resistance and gel fractio~
~i ratio. ~h~ compositio~ were also tested ~or the storag~
stability. The coated glass piates were baked at 140C
or 30 minutes in E~ample-s 18, 19 and 27 to 30 and Comparison Ex~nples 1 to 3, at 143C for 10 minutes i~
Examples 20 to 22, at 12~C for 30 minutes in Examples 23 and 24 and at 100C for 10 minutes in Examples 25 a~d 26.
,~ .
Table 5 below shows the results.

Each of the compositions was checked for the resistance to boiling water by the same method as the , foregoing one.

~able 6 below ~hows the result , ~ .

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~ ~3239 ~ 42 -.' ' Exam~les illustrative of curable resin cumpo~itions containin~ ,~-unsaturated carbo~yl group as the functional group f the ormula ( I ) E~!:ample 31 "Epikoat ~1002"* 1256 parts Diethanolamine 210 pzrts ~e~h~l ethyl keto~e 628 parts-The a~ove mixture was charged into a 4-ne~ked fl2-sX and reacted at 80C ror 3 hou~s, giving 2 hVdlO~yl-.~.
containing resin solution.
Isophorone diisocyanate444 parts N-methylol acrylamide 202 parts ~ Methyl ethyl ketone 277 parts `~ Aside f~om the above procedure, the above ... .
mixture was placed into a 4-necked flask and reacted at 80C until an NC~ value of 91 was reachedj- whereupon-~n- -,:, j ' - isocyanate-containing unsatura~ed monomer solution was :".~ . .
~ obtained.
`--, The hydroxyl-containing resin solution (2094 ~ 1 ."'!~ 20 parts) was mixed with 923 parts of the isocyanate-', containing unsaturated monomer. The mixture was sub3ected to reaction at 80~C for 10 hours, giving an epoxy urethane resin solution. The resin solution had a solids content . ., . of 70% and a viscosity of Z5. The resin was about 2200 in peak molecular weight as determined by gel permeation . ., ~ * Trade mark .~,j .

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:~ ~ 3 2~g ~0 _ ~3 _ : chromatography and had an ~t~unsatur-ated carbon~l group content of 0 . 9 5 ~ole and a primary hydroxyl group content of 0.95 mole, per kilogram of the resin solidO One part of co~alt acetate was added to 100 parts of the resin solution ~as solids), followed by mixing them, whereupon the curable resin compos-ition of the invention was obtained .
~xamDle 3Z
The curable resin comDosition of the present invention was produced by carryin~ out the same procedure as done in Example 31 with the exception of usi~g the same ~ amount of calcium acetate in place of cobalt acetate.
.. Example 33 The curable resin composition of the present invention was pxoduced by carrying out the ~ame procedure as done in Example 31 with the exception of using 0.5 part ,, . of trimethylsulfonium acetate in place of cobalt acetateO
Exam~le 34 ---- - The curable resin composition of the present invention was produced by carrying out the same procedure as done in Example 31 with the exception of usin~ 0.2 part of sodium formate in place of cobalt acetate.
Example 35 /-Dimethyl-m-isopro~enyl `~ 25 ben2yl isocyanate 210 parts :,, - , . . .

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n-~utyl acrylate 649 parts Styrene 150 parts ; Azobisisobutyronitrile 20 parts One thousand parts of toluene was charged into a 5 4-necked ~lask and heated with stirring to 120~C and the above mixture was added dropwise over a 3 hours' period.
~he re~ul~ing 2dmi~ture was aged at the same temperature for 2 houxst giving an isocyanat~co~taining acrylic resin solution havi~g a solid~ content of 50% and a viscosity of ` 10 P.
N-methylol acrylamide 101 parts Methyl ethyl ketone 101 parts .~ Hydroquinone 0.1 part .~ ~he above mixture was added dropwise to 1029 ~, 15 parts of the resin solution and the resulting admixture ' was reacted for 5 hours until an NCO value of 1 or les~
., was achieved, whereby an acryl urethane resin solution was obtained. The resin solution had a solids content of 50%
and a viscosity of Z. The resin was about 26000 in peak ~-- 20 molecular weight as determined by gel permeation -~ - -chromatography and had an 3 J ~-unsaturated carbonyl group ~-- content of 0.90 mole per kilogram of the resin solid.
. 2-~ydroxyethyl acrylat:e 232 parts n-3utyl methacrylate 768 parts hzobisisobutyr-onitrile 20 parts ' ~, , .

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~ ; 45 -:~. Aside ~rom the above procedure, 1~00 parts o-f ~ toluene was placed into a 4-necked flask and heated with :
stirring to 1~0C~ The above mixture was added dropwise over a 3 hours' period, and the resulting admixture was aged at the same temperature for 2 hou:rs, giving an :. acrylic resin solution. The resin solution had a ~olids content o~ 50% a~d a viscosity oE E. ~he resi-n was about 2400 in peak moleoular weight as determined by g~l `:;
~' permeation chromatography and had a primary hydroxyl ~roup content of 2.00 moles per kilogram of the resin solid.
:
Tetramethyl~mmonium hydroxide (OOS part) was mixed with 100 parts of a mixture of 50 parts of the acryl urethane resin solution (as solids) and 50 parts of the acrylic resin solution tais olids), whereby the curable :' 15 resin composition of the invention was obtained.
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~; . Exa~ple 36 ~ The curable resin composition of the invention `~', was prepared in the same manner as done in Example 35 with the exception of usin~ a different amount, i.e. 1.0 part, ~0 of tetramethylammonium hydroxide.
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~ The curable r~sin composition of the invention i; ~! .
was prepared in the same man~er as done in ~xample 3~ with ~i the exception of using.1.0 part of cobalt acetate in place .. 25 of tetramethiyl-ammonium-hiydro~ide.

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The curable resin compQsition of the invention was prepared in thP same manner as done in E~ample 35 with the exception of using 0.5 part of sodium formate in place of tetramethylammonium hydroxide.
Each of the compositions obtained in Examples 31 to 38 was appl1ed to a gl~ss plate to orm a layer-having a thickness of about 20 ~m when dried. ~he layer deposited on the glass plate was cured by bak:ing in a dryer. The ~oated plate was checked for the water ,. resistance and the gel fraction ratio. Also the !~ compositions were tested for the storage stability. The bakin~ was conducted by the same method as described hereinbefore, at 140C for 30 minutes in Examples 31 to 15 33, 35 and 37 and at 130C for 30 minutes in Example6 34, 36 and 38. Table 7 below shows the results.
Each of the compositions was checked for the resistance to boiling water by the same method as the foregoing one with the results shown below in Table 8.

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Claims (7)

1. A curable resin composition consisting essentially of:
(i) a resin (A) containing .alpha.,.beta.-unsaturated carbonyl group and primary and/or secondary hydroxyl group, or (ii) a mixture of a resin (B) containing .alpha.,.beta.-unsaturated carbonyl group and a resin (C) containing primary and/or secondary hydroxyl group, and (iii) at least one curing catalyst selected from the group consisting of alkali metal alkoxides, metal hydroxides, organic acid salts of metals, quaternary ammonium hydroxides, quaternary phosphonium hydroxides, tertiary sulfonium hydroxides and organic acid salts of these onium hydroxides.

2. A composition according to claim 1 wherein the resin (A) is a resin which has the residue of adduct of N-methylol acrylamide or methacrylamide with isocyanate, the residue being represented by the formula (I) wherein R1 is hydrogen atom or methyl group and which has hydroxyl group.

3. A composition according to claim 1 wherein the resin (B) is a resin which has the residue of adduct of N-methylol acrylamide or methacrylamide with isocyanate, the residue being represented by the formula (I) wherein R1 is hydrogen atom or methyl group.

4. A composition according to claim 1 wherein the resin (A) is a resin having about 0.01 to about 20 moles of the .alpha.,.beta.-unsaturated carbonyl group and about 0.01 to about 50 moles of the hydroxyl group, per kilogram of the resin.

5. A composition according to claim 1 wherein the resin (B) has about 0.01 to about 20 moles of the .alpha.,.beta.-unsaturated carbonyl group, per kilogram of the resin, and the resin (C) has about 0.01 to about 50 moles of the hydroxyl group, per kilogram of the resin.

6. A composition according to claim 1 wherein the resin mixture as the component (ii) consists of about 99.99 to about 50% by weight of the resin (B) and about 0.01 to about 50% by weight of the resin (C).

7. A composition according to claim 1 wherein the amount of the curing catalyst as the component (iii) is about 0.001 to about 30 parts by weight per 100 parts by weight of the resin (A) as the component (i) or the mixture of the resin (B) and the resin (C) as the component (ii).