CA2219832A1 - Coating polyisocyanates having built-in hals stabilizer - Google Patents
Coating polyisocyanates having built-in hals stabilizer Download PDFInfo
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- CA2219832A1 CA2219832A1 CA 2219832 CA2219832A CA2219832A1 CA 2219832 A1 CA2219832 A1 CA 2219832A1 CA 2219832 CA2219832 CA 2219832 CA 2219832 A CA2219832 A CA 2219832A CA 2219832 A1 CA2219832 A1 CA 2219832A1
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- polyisocyanate
- weight
- nco
- formula
- diisocyanate
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Disclosed is a polyisocyanate having a built-in HALS
stabilizer, which is an adduct of aliphatic, (cyclo)aliphatic or cycloaliphatic diisocyanate and a compound of the formula:
stabilizer, which is an adduct of aliphatic, (cyclo)aliphatic or cycloaliphatic diisocyanate and a compound of the formula:
Description
-.
Coatinq polyisocyanates havinq built-in HALS stabilizer The present invention relates to a polyisocyanate having a built-in HALS (hindered amine light stabilizer) sta~ilizer, a process for its preparation, its use :Eor producing a two pack pol~rurethane (PUR) coating and as a reactive ingredient for a UV-stabilizing two pack polyurethane (PUR~ coating and also a molsture-curing one pack polyurethane (PUR) coating.
A two pack polyurethane coating has achie~ed importance ~or a multiplicity of very different fie:Lds of application because of its excellent technological E)roperties.
It dries at room temperature to a solvent- and chem:Lcal~
resistant coating having e~cellent optical and mechanical properties. Such a two pack polyurethane coating has to be stabilized against degradation by insolation. The stabilizers commonly used are a known UV stabilizer based on ber,Lzotriazole ~e.g. TINUVIN~ 326) and a radlcal scavenger based on a strongly sterically hindered amine (e.g. TINUVIN~ 7l'0), preferably a combination of the two (synergistic effects). A
disadvantage with the two pack polyurethane coating stabilized with such a stabilizer is the limited lifetime of t~Le stabilizer, which migrates to the surface over time, only to be destroyed there.
It is an obiect of the present invention to provide a diisocyanate adduct which makes it possible to produce a permanently stabilized two pack polyurethane coating without addition of a stabilizer.
O.Z. 5122 It has been found that many of the disadvantages associated with the prior art may be solved by using a chain-extended diisocyanate adcluct containing the following polyol or aminoalcohol (when A = H) as a diisocyanate-linking component:
~ N
X
wherein A is H or R-fH-CH2-;
OH
R is H or an alkyl, cycloalkyl or substituted ~ycloalkyl group having 1 - 20 carbon atoms;
and X is H, CH3, CH3-f- or R-fH-CH2-. When A .is H and X
O OH
is H, CH3 or CH3-CO-, the aminoalcohol may be called as TAD
monoalcohol; when A is R-CH-CH2-, X is H, CH3 or CH3-CO-, the OH
polyol may be called as l'AD diol; and when both A and X are R-CH-CH2-, the polyol ma~r be called as TAD triol, for OH
convenience.
The present invention accordingly provider, a polyisocyanate having a built-in HALS stabilizer, which is an O.Z. 5122 adduct of an aliphatic, (cyclo)aliphatic or cycloali.phatic diisocyanate with a hydroxyl compound of the followi.ng formula:
R--I --CH2~ A
~whereln A is H or R-CH-CH2-;
OH
R is H or an alkyl, cycloalkyl or substituted c!ycloalkyl havlng 1 to 20 carbon atoms; and X is H, CH3, CH3-CO- or R-CH-CH2-).
OH
The polyol of the formula (I) above may be called as TAD-OH for convenience hereinunder. The adduct has an NCO/Ha equivalent ratio of about 2. This means that the di.isocyanate and TAD-OH are reacted to form the adduct in such a~lounts that there are about 2 NCO groups per active hydrogen atc,m that takes part in the adduct :formation. The active hydrogens are those of the OH groups in R-CH(OH)-CH2- and the NH group which ls attched at the 4-position to the 2,2,6,6-tetramethylpiperidine rin~ in TAD-OH when A is H.
The present inv~ention further provides a process for preparing the polyisocyan.~te having a built-in HALS stabilizer O.Z. 5122 by reacting the diisocyanate with the TAD-OH in a molar ratio of from about 5:1 to about 20:1 and, after the react;ion has taken place, removing the unconverted diisocyanate irom the reaction product by a distillation, i-or example, a ~;hort-path distillation at 120 - 180~C/0.1 mbar.
The polyisocyanate of the invention may be~ prepared in two stages. The 1st stage involves a reaction oi the diisocyanate with the TAD-OH. In this reaction, preferably the initial charge of the diisocyanate at 80 - 120~C is admixed with the TA~-OH in the course of 2 - 3 hours under nit~ogen and in the absence of moisture with intens:Lve stirring. About 5-20 mols, preferably about l0 mol~ of the diisocyanate are added per 1 mol o~ TAD-OH. On completion of the TAD-OH addition, heating may be continued at about 100~C
until 1 NCO equivalent has reacted per equivalent oi the active hydrogen atom. After the reaction, unreacted diisocyanate is removed by means of a short-path distillation, for example, at 120 - 180~C/0.1 mbar. The monomer content of the resulting compounds according to the invention :Ls prei-erably less than 0.5%.
Suitable starting diisocyanate compounds i-or reaction with the TAD-OH are aliphatic, (cyclo)alip~latic and cycloaliphatic diisocyanates as described for examp:Le in Houben-Weyl, Methoden der Organischen Chemie, Volume 14/2, p.
61 - 70, and the paper by W. Siefken in Justus Lieb:Lgs Annalen der Chemie 562, p. 75 - 136. The (cyclo)aliphatic O.Z. 5122 diisocyanate ls understoo~ to mean a diisocyanate 1ll which one isocyanate group ls attached to an aliphatic carbon atom and the other to a cycloalkyl group, a typical example l;hereof being isophorone diisocyanate. Examples of the above mentioned dilsocyanates lnclude tetramethylene diisocyanate, hexamethylene diLsocyanate, 2-methylpentamethylene dLisocyanate, 2,2,4(2,4,4)-trlmethylhexamethylene diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 3-lsocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4'-diisocyanatodicyclo-hexylmethane, hexahydroxyxylene 1,4- and 1,3-diisoc~anate.
In the formula (I), preferably R is H, CH-~ or CH2~H3 and X is H or R-IH_CH2_, ~wLth the proviso that X is H only OH
when A is R-CH-CH2-.
OH
Examples of suitable TAD polyols or TAD mcnoalcohols are 4-(2-hydroxyethyl)amino-2,2,6,6-tetramethylpiperidine, 4-(2-hydroxypropyl)amino-2,2,6,6-tetramethylpiperidine, 4-bis(2-hydroxyethyl)amino-2,2,6",-tetramethylpiperidine, 4-bis(2-hydroxypropyl)amino-2,2,6,6~tetramethylpiperidine, 4-bis(2-hydroxybutyl)amino-2,2,6,6-tetramethylpiperidine, 4-bis(2-hydroxyethyl)amino-1,1,2,2,6,6-pentamethylpiperidine and 4-bis(2-hydroxyethyl)amino-:L-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine. In principle, the process of the lnvention can be carried out with all amlnoalcohols, diols and O.Z. 5122 triols whlch can be prepared in known manner according to the following reaction equations:
NH2 ~N CHr! CH R
a) ~ ~ ~ I CH2 CH-R ~ ~
l 2 l-(CH2--~CH-R)2 >~ ~< 2~o '>~
H H
l 2 ~ (CH2~ R)2 >~ ~< 2'o' >1~ J<
H CE2~ R
~AD) OH
wherein R is as defined above, preferably H or a lower alkyl, especially preferably H or CH3.
A particularly suitable diol is the reaction product of 1 mol of TAD and 2 mol of ethylene oxide ~e.g., 4-bis(2-hydroxyethyl)amino-2,2,~,6-tetramethylpiperidlne) ancl a particularly suitable triol is the reaction product of 1 mol O.Z. 5122 of TAD and 3 mol of ethylene oxide (i.e., 4-k)is(2-hydro~y-ethyl)amino-1-(2-hydroxyethyl)-2,2,6,6-tetramethylp:.peridine).
The TAD-OH may be prepared in a one-stage reaction from TAD and a monoepox~de at 100 - 130~C. ~-Amino--2,2,6,6-tetramethylpipe~idine (TAD) may be prepared by the process described in DE-A-28 07 172 by reductive amination c~f the triacetoneamine prepared from acetone and NH3.
The polyisocyanate compound of the invent-.on preferably has a molecular weight o~ from about 600 to about 1500. Such a product is often highly viscous liquicl or solid at room temperature. The melting point of the solicl product varies within a certain range preferably from 40 to 120~C.
Preferably, the compound of the invention may additi.onally be characterized by a sterically hindered amino group /i.e., amino group constituting the piperidine ring) content of 1 - 2 mmol/g, a basic nitrogen content of from 2 - 4 mmol~'g and a free N~O group content (calculated as N~O) of 10 - 15 %. The compound of the invention is usually readily soluble in a customary paint solvent such as toluene, xylene (including technical grade mixtures), tetrahydronaphthalene, a ketone such as methylisobutyl ketone, diisobutyl ketone ancl isophorone and an ester such as n-hexyl acetate, n-butylglycol acetate and methoxypropyl acetate. Furthermore, the compound is often highly compatible with an OH-contalning po]ymer used ~or curing.
The polyisocyanate product of the inventic,n is O.Z. 5122 useful as a curing agent for a higher functional thermoplastic compound having a Zerevitinov-active hydrogen atom. The most lmportant field of application for such a system is its use as a permanently stabilized binder for a two pack polyurethane coating composition.
The present invention accordingly also provides a transparent or pigmented two pack polyurethane coat:Lng composition which is curable at room temperature to 180~C and is based on the novel polyisocyanate, and an OH-conlaining ~0 polymer, and consists essentially o~
a) 100 parts by weight of an OH-containing polymer, b) 10 - 90 parts by weight of an NCO component comprising the coating polyisocyanate according to the invention, c) 0 - 160 parts by weight of a pigment, d) 0 - 200 parts by weight of a customary filler, e) 0 - 5 parts by weight of a catalyst, and f) 0.5 - 5 parts k~y weight o~ a flow agent.
The amounts of the OH-containing polymer ~) and the NCO component (i.e., polyisocyanate), b) are prefer~bly such that an OH/NCO ratio is 1:0.5 to 1:1.2, more prefer.~bly 1:0.8 to 1:1.1 and especially preferably 1:1.
The constituent: a) may in principle be any polymer containing more than two OH groups and having a glass transition point between about 20 and about -25OC. The polymer in ~uestion is preferably a polyester polyol, a O.Z. 5122 polyether polyol, polyesteramlde polyol, polyurethalle polyol, hydroxylated acrylate resin, etc., whose OH groups are capable of crosslinking with the diisocyanate adduct of the invention.
A polyester polyol is particularly preferred for the purpose of the invention among the numerous possible hydroxyl-bearing polymers. Such a polyesterpolyol preferably has an OH number of 25 - 300 mg of KOH/g, more prefera~ly 30 - 150 m~ of KOH/g.
The preparation of such a polyester polyol is known in prior art and described for exa.mple in DE-A-30 30 554.
A urethanization catalyst may be added to increase the gel rate of the solvent-containing two pack polyurethane coating. The catalyst used is preferably an organolin compound such as dibutyltin dilaurate (DBTL), tin(I:~) octoate, dibutyltin maleate, etc. The amount of the catalys1: if added is preferably 0.03 - 0.5 part by weight per 100 parts by weight of the OH-containing polymer. The flow agent is known in the polyurethane coating art and examples thereo:E include silicone oil and an acrylate resin. The two pack polyurethane coating of the invention are advantageously used wherever high stability to outdoor weathering is required, for example ~n the gloss retention of a pigmented coating or the cracking resistance oiE a clearcoat on a metallic basecoat.
The present invention further provides for the use of the compound of the invention for preparing a two pack polyurethane coating in combination with a known polyisocyanate suitable for coating, for example a o.Z. 5122 polyisocyanate which contain an isocyanurate group ~VESTANAT~
T 1890; DESMODUR~ N 3300), a polyisocyanate contain:Lng a biuret group (DESMODUR~N 3200), a polyisocyanate whLch contains an isocyanurate group and an allophanate group (EP O
524 500, 0 524 501, 0 535 483~ and a polyisocyanate which contains a urethane group (trimethylolpropane adducl, of isophorone diisocyanate and of he~amethylene diisocyanate).
These known polyisocyanates are preferably aliphatic or (cyclo)aliphatic and free from their corresponding ~nonomers.
In the two pack polyurethane coating composition of the invention, the NCO component generally comprises 10 - 90 % by weight, preferably 20 - 50 % by weight, of the polyisocyanate of the invention. The two pack polyurethane coatinl~ prepared using such a combination of curing agents is notable for extremely good stability under heat stress and in o~tdoor weathering.
A further large field of use for the comp~und of the invention is in a moisture-curing solvent-contalnin~ one pack polyurethane coating. It; is contained in a moisture-curing one pack polyurethane coating in an amount of 5 - 60 % by weight, preferably 20 - 40 % by weight (based on the NCO
component of the one paclc coating), and is effective in bringing about a distinct; increase in the stability to outdoor weathering. The rest of the NCO component may be any known polyisocyanate.
O.Z. 5122 Exam~les A Preparation of TAD ~lolyols Al Preparation of 4-bis(2-hYdroxyethyl)-amino-2,2,6,6-tetramethylpiperidi~e (TAD-2 EO) 780 parts by weight of 4-amino-2,2,6,6-tetramethylpiperlcllne (T~,D) were slowly admixed Wit]l 484 parts by weight of ethylene oxlde (EO) in a 2 liter steel autoclave at 100 - 120~C under nitrogen. The pressure rose to a maximum of 7 bar. After the reaction had ended, the autoclave was decompressed and its contents were subjected to a f~actional distillation.
This yielded 203 parts by weight of 4-(2-hydroxy-ethyl)amino-2,2,6,6-tetra~methylplperidine having a boiling polnt of 120 - 145~C/0.27 mbar and, as the main fraotion, 798 parts by weight of 4-bis(2-hydroxyethyl)-amino-2,2,6" 6-tetra-methylpiperidine having a boiling point of 170 - 17:3~C/0.20 mbar.
A2 Preparation of 4-bis(2-hYdroxypropyl)-amino-2 :2,6,6-tetramethylpiperidine (TAD-2 PO) TAD-2 PO was prepared similarly to TAD-2 ]30 by using propylene oxide insiead o~ e~hylene oglde. The TAD-2 P~
obtained had a melting point of 97 - 102~C and a base number of 410 mg of KOH/g.
A3 Preparation of 4-bis(2-hydroxyethyl)-amino-1-hYdroxyethyl-2~2~6~6-tetramethylpiperidine (TAD-3 EO) 780 parts by weight of TAD and 700 parts by weLght of O.Z. 5122 ethylene oxide were reacted similarly to E~ample 1. The reuslting TAD-3 EO had a base number o~ 385 mg of KOH/g.
A4 PreParation of 4-(2--hydroxypropyl)-amino-2,2,6,6-tetramethylpiperidine (TAD-1 PO) 312 parts by weight of TAD and 116 parts ~y weight of propylene oxide were heated at 40~C until PO was undetectable. The reaction product was sub~ected t~ a chain-extention reaction witho~lt further purification. Its base number was 538 mg of KOH,'g.
B PreParation of compounds of the invention General method The TAD-OH ~1 ~nol) was added a little at ~ time to the diisocyanate (10 mol'l heated to 80~C, and, on completion of the addition, heating was continued at 80~C until 1 NCO
equivalent had reacted per OH equivalent used. The course of the reaction was monitored by determining the NCO content.
After the reaction had ended, the unconverted diisocyanate was separated frorn the react:Lon product by short-path distillation at 120-180~C.
The products recited below in the table were prepared according to thLs method.
O.Z. 5122 O ~ ~ ~ ~ . .
S~
a) ~
~ N~11~1 ~ ~N ~ N
O o\~ ~ ~ . . .. o O O O O OO O
V
O
~I NLn N 1~ ~ ' t' -~ ~\ N d~ ~7 ~i ~Yl ~i (~) N
.
-~ ~ O ~ ~ dl o\~ ~ ~ ~ o ~
- H H H H H ~ H ~ _ (I) O ~ ~ ~ ~ ~ ~ ~ ~ _ ~
H H ~ E I H ~ H 1 11 ~1 ~ N N ~ ~, ~) N N N
(~ ~ ~1 ~ C~ ~) 5- ~~l ~ >~ .
C ~
., ~ O a f ~ X
u ~, r ~ ~
~ o ~ ~ ~i ~ ,~
k V O
o , v ~ ~ a O O O O O O O O .~ ~ ~ .
N N ~) t') ~) N N ~1 ~r. r o 9 9 ~
o ~ ~ ~ ~ ~ ~ ~
o ~ .~. ) r~ .L) --' (1) a) X ' N
~ ~ o ~I N ~ ~ Ln ~ ~ o~ ,~ ~-x Z m m m m m m m m ~- H L~n H
H
X ~
a E-O.Z. 5122 ' CA 022l9832 l997-lO-3l .
O ~ ~
W .. ..
~ ~ ,~
r O
~ U ~:; o\~
-' , ~ m m o o o In In U~
a C
~ 0\o o o 5~ V V
a) o\o o O
a) ~
U~ ~ ~ V V
t, ~
~ ._ -r- ~
s~ V
., ~
I
0\o O
o ~ o ~7 U~ .
~ ~ X
o ~ ~ C C
s~ o M
C ~ ~
O ~ ~, N N
o ~ ~ ~
o I ~ ~ m o a a) v JJ
u k a ~ U~
o X
a a V ~ E- ~
O.Z. 5122 D Preparation o~ two pack polyurethane coatinq compositions General method Pack A
A polyester polyol solution was admixed, ii--necessary, with a further solvent - in accordance wit:h the polyester polyol solution - and then ground with whit:e pigment (Tio2)l a ~low agent customary in polyurethane chemistry and a catalyst in a stirred ball mill.
Two pack coatina composition Pack B - the crosslinker - was added with stirring to pack A in a second step in a calculated amount. After a delay time o~ 10 to 15 minutes, the coating solution was applied to degreased, optionally pretreated steel or aluminum panels and cured between 80 and 170~C in a through-circulation laboratory drying cabinet.
o.z. 5122 ~ o O 1' ~ 00 0 o~~ o .~ o o Ln I~ m. m ~
o ~, O r-- o ~ ~ O a~ o 4-1 ~
.,_1 0 C~l ~ O - in d' d' Lfl ~~~ I-- 1~n ~ ~ cr~
S 0:
O c~ O 1' V ~ d' ~ dl ~- I
~ o~O/~ ~ A
o ~7 o~O _ o ~ ~ ~ o o .~ -~ ~ V
u ~~ oo Z) ~ o o ao ~ ~ o 4~ X o ~ ~ ~ o~~ ~ In co o I ~ u~ ~ ~r ~ a~ A
4-1 j ~ U~~
O ~ ~ _ u. I ~ c, O ~ ~ ~ ~ v o 5~ ~ ~ 40 V V
O ~, ~ Q.
Q ~ ~ ~ 5 -- v 3 o o o o 0 ~ ~ U2 0 3X - ~ , 0 o ~ C 0 ~ ~'' ~ I # # # # ~ X~
m ~ ~ ~~ ~ ~ ~ v ~ v u ~ -~ ~ u a) ~ v Q
a E~
O.Z. 5122 D 2 Piqmented two pack polyurethane coatinqs based on mixtures of novel compound.s with polyisocyanates customary in the ~olyurethane coatinqs industry Both the crosslinkers were used in the form of a 60~ strength solution:
a) VESTANAT*T 1890: NCO content: 17.2 + 0.3 %
b) VESMODUR*N 3300: NCO content: 21.8 + 0.3 ~
To prepare the two pack polyurethane coatings, the crosslinker solutions were mixed in the desired ratio and then reacted with the calculated polyester polyol quantity as per the general method of preparation.
Table 4:
Example D 2 Composition ~ by weight] NCO content Crosslinker as Crosslinker as [~ b~ weight]
per B per D2 1 10 (3~ 90 (a) 9.97 2 20 (3~ 80 (a) 9.63 3 50 (3,~ 50 (a) 8.63 4 90 (3~ 10 (a) 7.29 50 (3) 50 (b) 9.93 6 80 (3~ 20 (b) 8.15 7 50 (4) 50 (b) 9.33 8 50 (7) 50 (a) -L0.08 * Trade-mark O.Z. 5122 . CA 02219832 1997-10-31 ~~~
o ~ ô~t~ c; o a~
, ~i o î~ ~~. o 1' o r ~p ~ ~A
\D ~n In ~ ~ oa~
O 1~ ~
~ O
,1 u~ a~
4~
~r ~ o 1-1 ~ . I a~ r~
,_ ~ ~ o\~ In O~ O
C) a~ ,I C~ 4 ~'I11') t' E-i o a~ o 41 ~ O ~) ~) ~
~\C' ~ r~ Ll'l C~ Lr) ~r~ a) ~
_ ~ V
~ ~ o ~I Nl.D ~)a~ ~ . ~-u ~ l op ~ ~o~ ~o --~~ r~ E, ~ I -- ICD r~
c~ ~1 ~ _ I ~ r~ r~ ~ A ~$_1 0 V J
G ~ ~ C U2 U
~> ~ v ~) - ~r~ ~r~
r l 4~ 00 a~. _ ~ ~ ~ ~~ I ~C O ~ ~ ~ In l~ X .~
~ Q 1 U X
3 ~ Ul (L C C
a ID (D ~ ~ -, tJ7 r rc r- I QI ~ J-) l D n~ D a~ ~ ~ L l'; ~, r- r-1 r~l I r~ r3 F ~ u ~ ~11 ) O ) O ~ .L) ,-- -I -rl r~ u ~ ~ r l r~ r~r-l r-l ~ E-, ~ v H O ~ ~ :0 v ~ ~v I ~ v m v ~
.. Il 11 0 11 ~~. O
lL
E~ H
,~ V 1:3 V
E-O.Z. 5122
Coatinq polyisocyanates havinq built-in HALS stabilizer The present invention relates to a polyisocyanate having a built-in HALS (hindered amine light stabilizer) sta~ilizer, a process for its preparation, its use :Eor producing a two pack pol~rurethane (PUR) coating and as a reactive ingredient for a UV-stabilizing two pack polyurethane (PUR~ coating and also a molsture-curing one pack polyurethane (PUR) coating.
A two pack polyurethane coating has achie~ed importance ~or a multiplicity of very different fie:Lds of application because of its excellent technological E)roperties.
It dries at room temperature to a solvent- and chem:Lcal~
resistant coating having e~cellent optical and mechanical properties. Such a two pack polyurethane coating has to be stabilized against degradation by insolation. The stabilizers commonly used are a known UV stabilizer based on ber,Lzotriazole ~e.g. TINUVIN~ 326) and a radlcal scavenger based on a strongly sterically hindered amine (e.g. TINUVIN~ 7l'0), preferably a combination of the two (synergistic effects). A
disadvantage with the two pack polyurethane coating stabilized with such a stabilizer is the limited lifetime of t~Le stabilizer, which migrates to the surface over time, only to be destroyed there.
It is an obiect of the present invention to provide a diisocyanate adduct which makes it possible to produce a permanently stabilized two pack polyurethane coating without addition of a stabilizer.
O.Z. 5122 It has been found that many of the disadvantages associated with the prior art may be solved by using a chain-extended diisocyanate adcluct containing the following polyol or aminoalcohol (when A = H) as a diisocyanate-linking component:
~ N
X
wherein A is H or R-fH-CH2-;
OH
R is H or an alkyl, cycloalkyl or substituted ~ycloalkyl group having 1 - 20 carbon atoms;
and X is H, CH3, CH3-f- or R-fH-CH2-. When A .is H and X
O OH
is H, CH3 or CH3-CO-, the aminoalcohol may be called as TAD
monoalcohol; when A is R-CH-CH2-, X is H, CH3 or CH3-CO-, the OH
polyol may be called as l'AD diol; and when both A and X are R-CH-CH2-, the polyol ma~r be called as TAD triol, for OH
convenience.
The present invention accordingly provider, a polyisocyanate having a built-in HALS stabilizer, which is an O.Z. 5122 adduct of an aliphatic, (cyclo)aliphatic or cycloali.phatic diisocyanate with a hydroxyl compound of the followi.ng formula:
R--I --CH2~ A
~whereln A is H or R-CH-CH2-;
OH
R is H or an alkyl, cycloalkyl or substituted c!ycloalkyl havlng 1 to 20 carbon atoms; and X is H, CH3, CH3-CO- or R-CH-CH2-).
OH
The polyol of the formula (I) above may be called as TAD-OH for convenience hereinunder. The adduct has an NCO/Ha equivalent ratio of about 2. This means that the di.isocyanate and TAD-OH are reacted to form the adduct in such a~lounts that there are about 2 NCO groups per active hydrogen atc,m that takes part in the adduct :formation. The active hydrogens are those of the OH groups in R-CH(OH)-CH2- and the NH group which ls attched at the 4-position to the 2,2,6,6-tetramethylpiperidine rin~ in TAD-OH when A is H.
The present inv~ention further provides a process for preparing the polyisocyan.~te having a built-in HALS stabilizer O.Z. 5122 by reacting the diisocyanate with the TAD-OH in a molar ratio of from about 5:1 to about 20:1 and, after the react;ion has taken place, removing the unconverted diisocyanate irom the reaction product by a distillation, i-or example, a ~;hort-path distillation at 120 - 180~C/0.1 mbar.
The polyisocyanate of the invention may be~ prepared in two stages. The 1st stage involves a reaction oi the diisocyanate with the TAD-OH. In this reaction, preferably the initial charge of the diisocyanate at 80 - 120~C is admixed with the TA~-OH in the course of 2 - 3 hours under nit~ogen and in the absence of moisture with intens:Lve stirring. About 5-20 mols, preferably about l0 mol~ of the diisocyanate are added per 1 mol o~ TAD-OH. On completion of the TAD-OH addition, heating may be continued at about 100~C
until 1 NCO equivalent has reacted per equivalent oi the active hydrogen atom. After the reaction, unreacted diisocyanate is removed by means of a short-path distillation, for example, at 120 - 180~C/0.1 mbar. The monomer content of the resulting compounds according to the invention :Ls prei-erably less than 0.5%.
Suitable starting diisocyanate compounds i-or reaction with the TAD-OH are aliphatic, (cyclo)alip~latic and cycloaliphatic diisocyanates as described for examp:Le in Houben-Weyl, Methoden der Organischen Chemie, Volume 14/2, p.
61 - 70, and the paper by W. Siefken in Justus Lieb:Lgs Annalen der Chemie 562, p. 75 - 136. The (cyclo)aliphatic O.Z. 5122 diisocyanate ls understoo~ to mean a diisocyanate 1ll which one isocyanate group ls attached to an aliphatic carbon atom and the other to a cycloalkyl group, a typical example l;hereof being isophorone diisocyanate. Examples of the above mentioned dilsocyanates lnclude tetramethylene diisocyanate, hexamethylene diLsocyanate, 2-methylpentamethylene dLisocyanate, 2,2,4(2,4,4)-trlmethylhexamethylene diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, 3-lsocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4'-diisocyanatodicyclo-hexylmethane, hexahydroxyxylene 1,4- and 1,3-diisoc~anate.
In the formula (I), preferably R is H, CH-~ or CH2~H3 and X is H or R-IH_CH2_, ~wLth the proviso that X is H only OH
when A is R-CH-CH2-.
OH
Examples of suitable TAD polyols or TAD mcnoalcohols are 4-(2-hydroxyethyl)amino-2,2,6,6-tetramethylpiperidine, 4-(2-hydroxypropyl)amino-2,2,6,6-tetramethylpiperidine, 4-bis(2-hydroxyethyl)amino-2,2,6",-tetramethylpiperidine, 4-bis(2-hydroxypropyl)amino-2,2,6,6~tetramethylpiperidine, 4-bis(2-hydroxybutyl)amino-2,2,6,6-tetramethylpiperidine, 4-bis(2-hydroxyethyl)amino-1,1,2,2,6,6-pentamethylpiperidine and 4-bis(2-hydroxyethyl)amino-:L-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine. In principle, the process of the lnvention can be carried out with all amlnoalcohols, diols and O.Z. 5122 triols whlch can be prepared in known manner according to the following reaction equations:
NH2 ~N CHr! CH R
a) ~ ~ ~ I CH2 CH-R ~ ~
l 2 l-(CH2--~CH-R)2 >~ ~< 2~o '>~
H H
l 2 ~ (CH2~ R)2 >~ ~< 2'o' >1~ J<
H CE2~ R
~AD) OH
wherein R is as defined above, preferably H or a lower alkyl, especially preferably H or CH3.
A particularly suitable diol is the reaction product of 1 mol of TAD and 2 mol of ethylene oxide ~e.g., 4-bis(2-hydroxyethyl)amino-2,2,~,6-tetramethylpiperidlne) ancl a particularly suitable triol is the reaction product of 1 mol O.Z. 5122 of TAD and 3 mol of ethylene oxide (i.e., 4-k)is(2-hydro~y-ethyl)amino-1-(2-hydroxyethyl)-2,2,6,6-tetramethylp:.peridine).
The TAD-OH may be prepared in a one-stage reaction from TAD and a monoepox~de at 100 - 130~C. ~-Amino--2,2,6,6-tetramethylpipe~idine (TAD) may be prepared by the process described in DE-A-28 07 172 by reductive amination c~f the triacetoneamine prepared from acetone and NH3.
The polyisocyanate compound of the invent-.on preferably has a molecular weight o~ from about 600 to about 1500. Such a product is often highly viscous liquicl or solid at room temperature. The melting point of the solicl product varies within a certain range preferably from 40 to 120~C.
Preferably, the compound of the invention may additi.onally be characterized by a sterically hindered amino group /i.e., amino group constituting the piperidine ring) content of 1 - 2 mmol/g, a basic nitrogen content of from 2 - 4 mmol~'g and a free N~O group content (calculated as N~O) of 10 - 15 %. The compound of the invention is usually readily soluble in a customary paint solvent such as toluene, xylene (including technical grade mixtures), tetrahydronaphthalene, a ketone such as methylisobutyl ketone, diisobutyl ketone ancl isophorone and an ester such as n-hexyl acetate, n-butylglycol acetate and methoxypropyl acetate. Furthermore, the compound is often highly compatible with an OH-contalning po]ymer used ~or curing.
The polyisocyanate product of the inventic,n is O.Z. 5122 useful as a curing agent for a higher functional thermoplastic compound having a Zerevitinov-active hydrogen atom. The most lmportant field of application for such a system is its use as a permanently stabilized binder for a two pack polyurethane coating composition.
The present invention accordingly also provides a transparent or pigmented two pack polyurethane coat:Lng composition which is curable at room temperature to 180~C and is based on the novel polyisocyanate, and an OH-conlaining ~0 polymer, and consists essentially o~
a) 100 parts by weight of an OH-containing polymer, b) 10 - 90 parts by weight of an NCO component comprising the coating polyisocyanate according to the invention, c) 0 - 160 parts by weight of a pigment, d) 0 - 200 parts by weight of a customary filler, e) 0 - 5 parts by weight of a catalyst, and f) 0.5 - 5 parts k~y weight o~ a flow agent.
The amounts of the OH-containing polymer ~) and the NCO component (i.e., polyisocyanate), b) are prefer~bly such that an OH/NCO ratio is 1:0.5 to 1:1.2, more prefer.~bly 1:0.8 to 1:1.1 and especially preferably 1:1.
The constituent: a) may in principle be any polymer containing more than two OH groups and having a glass transition point between about 20 and about -25OC. The polymer in ~uestion is preferably a polyester polyol, a O.Z. 5122 polyether polyol, polyesteramlde polyol, polyurethalle polyol, hydroxylated acrylate resin, etc., whose OH groups are capable of crosslinking with the diisocyanate adduct of the invention.
A polyester polyol is particularly preferred for the purpose of the invention among the numerous possible hydroxyl-bearing polymers. Such a polyesterpolyol preferably has an OH number of 25 - 300 mg of KOH/g, more prefera~ly 30 - 150 m~ of KOH/g.
The preparation of such a polyester polyol is known in prior art and described for exa.mple in DE-A-30 30 554.
A urethanization catalyst may be added to increase the gel rate of the solvent-containing two pack polyurethane coating. The catalyst used is preferably an organolin compound such as dibutyltin dilaurate (DBTL), tin(I:~) octoate, dibutyltin maleate, etc. The amount of the catalys1: if added is preferably 0.03 - 0.5 part by weight per 100 parts by weight of the OH-containing polymer. The flow agent is known in the polyurethane coating art and examples thereo:E include silicone oil and an acrylate resin. The two pack polyurethane coating of the invention are advantageously used wherever high stability to outdoor weathering is required, for example ~n the gloss retention of a pigmented coating or the cracking resistance oiE a clearcoat on a metallic basecoat.
The present invention further provides for the use of the compound of the invention for preparing a two pack polyurethane coating in combination with a known polyisocyanate suitable for coating, for example a o.Z. 5122 polyisocyanate which contain an isocyanurate group ~VESTANAT~
T 1890; DESMODUR~ N 3300), a polyisocyanate contain:Lng a biuret group (DESMODUR~N 3200), a polyisocyanate whLch contains an isocyanurate group and an allophanate group (EP O
524 500, 0 524 501, 0 535 483~ and a polyisocyanate which contains a urethane group (trimethylolpropane adducl, of isophorone diisocyanate and of he~amethylene diisocyanate).
These known polyisocyanates are preferably aliphatic or (cyclo)aliphatic and free from their corresponding ~nonomers.
In the two pack polyurethane coating composition of the invention, the NCO component generally comprises 10 - 90 % by weight, preferably 20 - 50 % by weight, of the polyisocyanate of the invention. The two pack polyurethane coatinl~ prepared using such a combination of curing agents is notable for extremely good stability under heat stress and in o~tdoor weathering.
A further large field of use for the comp~und of the invention is in a moisture-curing solvent-contalnin~ one pack polyurethane coating. It; is contained in a moisture-curing one pack polyurethane coating in an amount of 5 - 60 % by weight, preferably 20 - 40 % by weight (based on the NCO
component of the one paclc coating), and is effective in bringing about a distinct; increase in the stability to outdoor weathering. The rest of the NCO component may be any known polyisocyanate.
O.Z. 5122 Exam~les A Preparation of TAD ~lolyols Al Preparation of 4-bis(2-hYdroxyethyl)-amino-2,2,6,6-tetramethylpiperidi~e (TAD-2 EO) 780 parts by weight of 4-amino-2,2,6,6-tetramethylpiperlcllne (T~,D) were slowly admixed Wit]l 484 parts by weight of ethylene oxlde (EO) in a 2 liter steel autoclave at 100 - 120~C under nitrogen. The pressure rose to a maximum of 7 bar. After the reaction had ended, the autoclave was decompressed and its contents were subjected to a f~actional distillation.
This yielded 203 parts by weight of 4-(2-hydroxy-ethyl)amino-2,2,6,6-tetra~methylplperidine having a boiling polnt of 120 - 145~C/0.27 mbar and, as the main fraotion, 798 parts by weight of 4-bis(2-hydroxyethyl)-amino-2,2,6" 6-tetra-methylpiperidine having a boiling point of 170 - 17:3~C/0.20 mbar.
A2 Preparation of 4-bis(2-hYdroxypropyl)-amino-2 :2,6,6-tetramethylpiperidine (TAD-2 PO) TAD-2 PO was prepared similarly to TAD-2 ]30 by using propylene oxide insiead o~ e~hylene oglde. The TAD-2 P~
obtained had a melting point of 97 - 102~C and a base number of 410 mg of KOH/g.
A3 Preparation of 4-bis(2-hydroxyethyl)-amino-1-hYdroxyethyl-2~2~6~6-tetramethylpiperidine (TAD-3 EO) 780 parts by weight of TAD and 700 parts by weLght of O.Z. 5122 ethylene oxide were reacted similarly to E~ample 1. The reuslting TAD-3 EO had a base number o~ 385 mg of KOH/g.
A4 PreParation of 4-(2--hydroxypropyl)-amino-2,2,6,6-tetramethylpiperidine (TAD-1 PO) 312 parts by weight of TAD and 116 parts ~y weight of propylene oxide were heated at 40~C until PO was undetectable. The reaction product was sub~ected t~ a chain-extention reaction witho~lt further purification. Its base number was 538 mg of KOH,'g.
B PreParation of compounds of the invention General method The TAD-OH ~1 ~nol) was added a little at ~ time to the diisocyanate (10 mol'l heated to 80~C, and, on completion of the addition, heating was continued at 80~C until 1 NCO
equivalent had reacted per OH equivalent used. The course of the reaction was monitored by determining the NCO content.
After the reaction had ended, the unconverted diisocyanate was separated frorn the react:Lon product by short-path distillation at 120-180~C.
The products recited below in the table were prepared according to thLs method.
O.Z. 5122 O ~ ~ ~ ~ . .
S~
a) ~
~ N~11~1 ~ ~N ~ N
O o\~ ~ ~ . . .. o O O O O OO O
V
O
~I NLn N 1~ ~ ' t' -~ ~\ N d~ ~7 ~i ~Yl ~i (~) N
.
-~ ~ O ~ ~ dl o\~ ~ ~ ~ o ~
- H H H H H ~ H ~ _ (I) O ~ ~ ~ ~ ~ ~ ~ ~ _ ~
H H ~ E I H ~ H 1 11 ~1 ~ N N ~ ~, ~) N N N
(~ ~ ~1 ~ C~ ~) 5- ~~l ~ >~ .
C ~
., ~ O a f ~ X
u ~, r ~ ~
~ o ~ ~ ~i ~ ,~
k V O
o , v ~ ~ a O O O O O O O O .~ ~ ~ .
N N ~) t') ~) N N ~1 ~r. r o 9 9 ~
o ~ ~ ~ ~ ~ ~ ~
o ~ .~. ) r~ .L) --' (1) a) X ' N
~ ~ o ~I N ~ ~ Ln ~ ~ o~ ,~ ~-x Z m m m m m m m m ~- H L~n H
H
X ~
a E-O.Z. 5122 ' CA 022l9832 l997-lO-3l .
O ~ ~
W .. ..
~ ~ ,~
r O
~ U ~:; o\~
-' , ~ m m o o o In In U~
a C
~ 0\o o o 5~ V V
a) o\o o O
a) ~
U~ ~ ~ V V
t, ~
~ ._ -r- ~
s~ V
., ~
I
0\o O
o ~ o ~7 U~ .
~ ~ X
o ~ ~ C C
s~ o M
C ~ ~
O ~ ~, N N
o ~ ~ ~
o I ~ ~ m o a a) v JJ
u k a ~ U~
o X
a a V ~ E- ~
O.Z. 5122 D Preparation o~ two pack polyurethane coatinq compositions General method Pack A
A polyester polyol solution was admixed, ii--necessary, with a further solvent - in accordance wit:h the polyester polyol solution - and then ground with whit:e pigment (Tio2)l a ~low agent customary in polyurethane chemistry and a catalyst in a stirred ball mill.
Two pack coatina composition Pack B - the crosslinker - was added with stirring to pack A in a second step in a calculated amount. After a delay time o~ 10 to 15 minutes, the coating solution was applied to degreased, optionally pretreated steel or aluminum panels and cured between 80 and 170~C in a through-circulation laboratory drying cabinet.
o.z. 5122 ~ o O 1' ~ 00 0 o~~ o .~ o o Ln I~ m. m ~
o ~, O r-- o ~ ~ O a~ o 4-1 ~
.,_1 0 C~l ~ O - in d' d' Lfl ~~~ I-- 1~n ~ ~ cr~
S 0:
O c~ O 1' V ~ d' ~ dl ~- I
~ o~O/~ ~ A
o ~7 o~O _ o ~ ~ ~ o o .~ -~ ~ V
u ~~ oo Z) ~ o o ao ~ ~ o 4~ X o ~ ~ ~ o~~ ~ In co o I ~ u~ ~ ~r ~ a~ A
4-1 j ~ U~~
O ~ ~ _ u. I ~ c, O ~ ~ ~ ~ v o 5~ ~ ~ 40 V V
O ~, ~ Q.
Q ~ ~ ~ 5 -- v 3 o o o o 0 ~ ~ U2 0 3X - ~ , 0 o ~ C 0 ~ ~'' ~ I # # # # ~ X~
m ~ ~ ~~ ~ ~ ~ v ~ v u ~ -~ ~ u a) ~ v Q
a E~
O.Z. 5122 D 2 Piqmented two pack polyurethane coatinqs based on mixtures of novel compound.s with polyisocyanates customary in the ~olyurethane coatinqs industry Both the crosslinkers were used in the form of a 60~ strength solution:
a) VESTANAT*T 1890: NCO content: 17.2 + 0.3 %
b) VESMODUR*N 3300: NCO content: 21.8 + 0.3 ~
To prepare the two pack polyurethane coatings, the crosslinker solutions were mixed in the desired ratio and then reacted with the calculated polyester polyol quantity as per the general method of preparation.
Table 4:
Example D 2 Composition ~ by weight] NCO content Crosslinker as Crosslinker as [~ b~ weight]
per B per D2 1 10 (3~ 90 (a) 9.97 2 20 (3~ 80 (a) 9.63 3 50 (3,~ 50 (a) 8.63 4 90 (3~ 10 (a) 7.29 50 (3) 50 (b) 9.93 6 80 (3~ 20 (b) 8.15 7 50 (4) 50 (b) 9.33 8 50 (7) 50 (a) -L0.08 * Trade-mark O.Z. 5122 . CA 02219832 1997-10-31 ~~~
o ~ ô~t~ c; o a~
, ~i o î~ ~~. o 1' o r ~p ~ ~A
\D ~n In ~ ~ oa~
O 1~ ~
~ O
,1 u~ a~
4~
~r ~ o 1-1 ~ . I a~ r~
,_ ~ ~ o\~ In O~ O
C) a~ ,I C~ 4 ~'I11') t' E-i o a~ o 41 ~ O ~) ~) ~
~\C' ~ r~ Ll'l C~ Lr) ~r~ a) ~
_ ~ V
~ ~ o ~I Nl.D ~)a~ ~ . ~-u ~ l op ~ ~o~ ~o --~~ r~ E, ~ I -- ICD r~
c~ ~1 ~ _ I ~ r~ r~ ~ A ~$_1 0 V J
G ~ ~ C U2 U
~> ~ v ~) - ~r~ ~r~
r l 4~ 00 a~. _ ~ ~ ~ ~~ I ~C O ~ ~ ~ In l~ X .~
~ Q 1 U X
3 ~ Ul (L C C
a ID (D ~ ~ -, tJ7 r rc r- I QI ~ J-) l D n~ D a~ ~ ~ L l'; ~, r- r-1 r~l I r~ r3 F ~ u ~ ~11 ) O ) O ~ .L) ,-- -I -rl r~ u ~ ~ r l r~ r~r-l r-l ~ E-, ~ v H O ~ ~ :0 v ~ ~v I ~ v m v ~
.. Il 11 0 11 ~~. O
lL
E~ H
,~ V 1:3 V
E-O.Z. 5122
Claims (18)
1. A polyisocyanate having a built-in hindered amine light stabilizer, which is an adduct of an aliphatic, (cyclo)aliphatic or cycloaliphatic diisocyanate with a hydroxyl compound having a 2,2,6,6-tetramethylpiperidine ring of the formula:
(wherein:
R is H or an alkyl, cycloalkyl or substituted cycloalkyl group having 1 - 20 carbon atoms) at an NCO/Ha equivalent ratio of about 2, wherein. Ha is the total of active hydrogen atoms of the hydroxyl group or groups and an NH group which is attached at the 4-position of the 2,2,6,6-tetramethylpiperidine ring and which is present in the compound of the formula (I) only when A is H.
(wherein:
R is H or an alkyl, cycloalkyl or substituted cycloalkyl group having 1 - 20 carbon atoms) at an NCO/Ha equivalent ratio of about 2, wherein. Ha is the total of active hydrogen atoms of the hydroxyl group or groups and an NH group which is attached at the 4-position of the 2,2,6,6-tetramethylpiperidine ring and which is present in the compound of the formula (I) only when A is H.
2. The polyisocyanate of claim 1, which has a molecular weight of from about 600 to about 1,500 and is highly viscous or solid at room temperature.
3. The polyisocyanate of claim 1 or 2, which has a sterically hindered amino group content of 1 - 2 mmol/g, a basic nitrogen content of 2 - 4 mmol/g and a free NCO group content (calculated as NCO) of 10 - 15%.
4. The polyisocyanate of any one of claims 1-3, wherein the diisocyanate is at least one member selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-diisocyanatodicyclohexylmethane and 2-methylpentamethylenediisocyanate.
5. The polyisocyanate of any one of claims 1-4, wherein the hydroxyl compound of the formula (I) has the formula:
wherein R is H or CH3.
wherein R is H or CH3.
6. The polyisocyanate of any one of claims 1-4, wherein the hydroxyl compound of the formula (I) has the formula:
wherein R is H or CH3.
wherein R is H or CH3.
7. The polyisocyanate of any one of claims 1-4, wherein the hydroxyl compound of the formula (I) has the formula:
wherein R is H or CH3.
wherein R is H or CH3.
8. A process for preparing the polyisocyanate as defined in any one of claims 1 to 7, which comprises:
in a first stage, reacting the diisocyanate with the hydroxyl compound of the formula (I) in a molar ratio of 5:1 to 20:1, and in a second stage, separating the diisocyanate unreacted with the hydroxyl compound from the reaction product by a distillation.
in a first stage, reacting the diisocyanate with the hydroxyl compound of the formula (I) in a molar ratio of 5:1 to 20:1, and in a second stage, separating the diisocyanate unreacted with the hydroxyl compound from the reaction product by a distillation.
9. The process of claim 8, wherein the second stage is conducted by a short path distillation at a temperature of 120-180°C at a pressure of 0.1 mbar.
10. The process of claim 8 or 9, wherein the reaction of the first stage is conducted at a temperature of 80-120°C
under nitrogen in the absence of moisture with intensive stirring.
under nitrogen in the absence of moisture with intensive stirring.
11. A transparent or pigmented two pack polyurethane coating composition, which comprises:
a) 100 parts by weight of an OH-containing polymer having more than two OH groups and a glass transition point between about 20 and about -25°C;
b) 10-90 parts by weight of an NCO component comprising the polyisocyanate as defined in any one of claims 1 to 7;
c) 0-160 parts by weight of a pigment;
d) 0-200 parts by weight of a customary filler;
e) 0-5 parts by weight of a catalyst; and f) 0.5-5 parts by weight of a flow agent, wherein the OH-containing polymer a) is contained in a first pack, the NCO component b) is contained in a second pack and the flow agent f) and the other ingredients c), d) and e) are each independently contained in either or both of the first and second packs.
a) 100 parts by weight of an OH-containing polymer having more than two OH groups and a glass transition point between about 20 and about -25°C;
b) 10-90 parts by weight of an NCO component comprising the polyisocyanate as defined in any one of claims 1 to 7;
c) 0-160 parts by weight of a pigment;
d) 0-200 parts by weight of a customary filler;
e) 0-5 parts by weight of a catalyst; and f) 0.5-5 parts by weight of a flow agent, wherein the OH-containing polymer a) is contained in a first pack, the NCO component b) is contained in a second pack and the flow agent f) and the other ingredients c), d) and e) are each independently contained in either or both of the first and second packs.
12. The coating composition of claim 11, wherein the OH-containing polymer a) and the NCO component b) are contained such that an OH/NCO ratio is from 1:0.5 to 1:1.2.
13. The coating composition of claim 11 or 12, which contains 0.03-0.5 parts by weight of the catalyst.
14. The coating composition of any one of claims 11 to 13, wherein the OH-containing polymer a) is a polyester polyol having an OH number of 25-300 mg of KOH/g.
15. The coating composition of any one of claims 11 to 14, wherein the NCO component b) is a mixture containing 90-10% by weight of the polyisocyanate as defined in any one of claims 1 to 7 and 10-90% by weight of an aliphatic polyisocyanate which contains an isocyanurate group.
16. The coating composition of any one of claims 11 to 14, wherein the NCO component b) is a mixture containing 90-10% by weight of the polyisocyanate as defined in any one of claims 1 to 7 and 10-90% by weight of a (cyclo)aliphatic polyisocyanate which contains an isocyanurate group.
17. The coating composition of any one of claims 11 to 14, wherein the NCO component b) is a mixture containing 90-10%
by weight of the polyisocyanate as defined in any one of claims 1 to 7 and 10-90% by weight of an aliphatic polyisocyanate which contains a biuret group.
by weight of the polyisocyanate as defined in any one of claims 1 to 7 and 10-90% by weight of an aliphatic polyisocyanate which contains a biuret group.
18. A moisture-curing one pack polyurethane coating composition, which comprises:
(i) an NCO component consisting of 5-60% by weight (based on the NCO component) of the polyisocyanate as defined in any one of claims 1 to 7 and the rest of at least one other polyisocyanate; and (ii) a solvent for the ingredient (i).
(i) an NCO component consisting of 5-60% by weight (based on the NCO component) of the polyisocyanate as defined in any one of claims 1 to 7 and the rest of at least one other polyisocyanate; and (ii) a solvent for the ingredient (i).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19645165.5 | 1996-11-02 | ||
| DE1996145165 DE19645165A1 (en) | 1996-11-02 | 1996-11-02 | Lacquer polyisocyanates with built-in HALS stabilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2219832A1 true CA2219832A1 (en) | 1998-05-02 |
Family
ID=7810447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2219832 Abandoned CA2219832A1 (en) | 1996-11-02 | 1997-10-31 | Coating polyisocyanates having built-in hals stabilizer |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0839844A1 (en) |
| JP (1) | JPH10139850A (en) |
| CA (1) | CA2219832A1 (en) |
| DE (1) | DE19645165A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3059704B2 (en) * | 1998-08-11 | 2000-07-04 | 大成化工株式会社 | Paint with good weather resistance |
| DE102004003024A1 (en) * | 2004-01-21 | 2005-08-11 | Basf Ag | Stabilizers based on polyisocyanates |
| DE102021000688A1 (en) | 2021-02-10 | 2022-08-11 | Giesecke+Devrient Currency Technology Gmbh | Value Document Substrate and Composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH623066A5 (en) * | 1976-05-11 | 1981-05-15 | Ciba Geigy Ag | |
| DE2642386A1 (en) * | 1976-09-21 | 1978-03-23 | Bayer Ag | PERMANENTLY STABILIZED POLYURETHANES |
| AU7424681A (en) * | 1980-09-10 | 1982-03-18 | B.F. Goodrich Company, The | Piperidine derivatives as u.v. stabilisers |
| GB8907595D0 (en) * | 1989-04-04 | 1989-05-17 | Sandoz Ltd | Improvements in or relating to organic compounds |
-
1996
- 1996-11-02 DE DE1996145165 patent/DE19645165A1/en not_active Withdrawn
-
1997
- 1997-09-09 EP EP97115601A patent/EP0839844A1/en not_active Withdrawn
- 1997-10-30 JP JP9298815A patent/JPH10139850A/en active Pending
- 1997-10-31 CA CA 2219832 patent/CA2219832A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0839844A1 (en) | 1998-05-06 |
| DE19645165A1 (en) | 1998-05-07 |
| JPH10139850A (en) | 1998-05-26 |
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