CA1204547A - Curable composition based on an acid-curable resin, and process for curing this resin - Google Patents
Curable composition based on an acid-curable resin, and process for curing this resinInfo
- Publication number
- CA1204547A CA1204547A CA000396041A CA396041A CA1204547A CA 1204547 A CA1204547 A CA 1204547A CA 000396041 A CA000396041 A CA 000396041A CA 396041 A CA396041 A CA 396041A CA 1204547 A CA1204547 A CA 1204547A
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- resin
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- acid
- alkyl
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Abstract
Abstract Compounds of the formula I and II
I II
in which R, R1, R2, R3 and R4 are as defined in claim 1, are latent curing catalysts for acid-curable baking finishes. On irradiation with short-wave light, the sulfonic acid RSO3H as the actual curing catalyst is liberated therefrom.
I II
in which R, R1, R2, R3 and R4 are as defined in claim 1, are latent curing catalysts for acid-curable baking finishes. On irradiation with short-wave light, the sulfonic acid RSO3H as the actual curing catalyst is liberated therefrom.
Description
3-1~288/-~
Curable composi-tion based on an acid-curable resin9 and Err cess for c _in~_this resin _ __ The invention relates to compositions based on an acid-curable resin and containing a blocked curing cata-lyst, and to a process for curing this resin by irradia-tion with short-wave light and subsequen-t heating.
Acid-curable resins are used especially as binders for finishes, printing inks and paints, when high baking temperatures are to be avoided. The acid-curable resins can be amino resins, including etherified, esteri-fied or otherwise modified melamine resins, urea/form-aldehyde resins, phenol/formaldehyde resins as well as mixtures of such resins with alkyd resins, polyester resins or acrylic resins. Further acid-curable resins are me-thylol compounds, methylol ethers of polycarboxylic acid amides, for example deriva-tives of polyacrylic or polymethacrylic acid, urethane-alkyds as well as resins which contain carboxylic acid esters of N-methylol~amides.
Acid-polymerisable or acid-curable ethylenically unsatur-ated materials, such as N-methylol-acrylamide, vinyl carbazole, vinyl ethers9 diketene and diacetone-acrylamide can also be usedO The acid curing catalysts used are predominantly organic acids, such as sulfonic acids9 in particular p-toluenesulfonic acid, half-esters ox phthalic acid or maleic acid, or phosphoric acid and its partial esters. Since these acids effec-t slow curing even at room temperature, they are added to the resin only shor-tly before -the lat-ter is applied, and -this leads to the .
I
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known problems in main-taining defined po-t lives. To make one-componen-t sys-tems feasible, i-t has already been proposed to use blocked curing catalysts, from which -the acid is libera-ted a-t an eleva-ted tempera-ture. Ex-amples of such catalysts are amine salts of the acids, for example the pyridine sal-ts of aromatic sulfonic acids, as proposed in U.S. Patent Specification 3947L~,05L~.
These and other salts have the disadvantage that they either already effect slow curing during s-torage or -that they require very high curing temperatures or very long curing -times. Moreover 5 they cause odour problems.
Furthermore, U.S. Patent Specification 4,102,687 has proposed the use of aromatic sulfonium salts of com-plex anions, for example of BF4, PF`6, SbF6 or AsF6, as blocked curing catalys-ts, from which the actual curing catalyst is formed by irradia-tion with W light.
According to German Offenlegungsschrift 2,602,57L~, the same principle can also be realised with aromatic iodonium salts. However, it is difficult to prepare sulfonium salts or iodonium salts of this type in a pure form, and they have a low reactivity and tend to cause yellowing of the resins. There is therefore a need for compounds which can readily be prepared on an industrial scale and which, on irradiation with short-wave ligh-t, rapidly decompose -to form a highly reactive curing catalyst for acid-curable resins.
It has now been found tha-t sulfonic acid es-ters of certain cyclic hydroxamic acid deriva-tives 9 which can readily be prepared industrially, meet these requirements, since they have unlimited storage life in -the dark but, on exposure to short-wave ligh-t 9 rapidly decompose -to form sulfonic acids which make a subsequen-t acid-ca-talysed curing of the resins possible a-t a relatively low temp-erature and do not tend to cause yellowing of the resins.
The invention relates to a curable composition, comprising an acid-curable resin and, as a blocked curing catalyst, a compound of the formula I or II
5~
/ \ / 2 ~.1-0-SC
O R R"
I II
in which R is Cl-C18-alkyl, phenyl which is unsubstituted or substituted by Cl-C12-alkyl, halogen, Cl-C4-alkyl-NHCO-, phenyl-NHCO-, N02 or Cl-C4-alkoxy9 or is naphthyl which is unsubstituted or substituted by Cl-C12-alkyl or halogen, or is C5-C6-cycloalkyl, camp4horyl, CF3, CC13, CH2Cl, F or NH2 and R , R , R and R independently of one another are hydrogen, Cl-C8-alkyl, Cl C4-alkoxy, Cl-C12-alkyl-thio, phenyl-thio, N02 or halogen.
Preferably, the curing ca-talyst is a compound of the formula I or II, in which R is Cl-C18~alkyl, F9 CF3, CC13, or phenyl or naphthyl which are unsubst~tu-ted or substituted by C~-C12-alkyl, Cl or CH3CONH, or is cam-phoryl and R , R , R3 and R independently of one another are hydrogen, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkylthio.
The compounds of the formula I are derivatives of N-hydroxy-phthalimide, and the compounds of the formula II
are derivatives of N-hydroxy-naph-thalimide. They can be prepared from the corresponding N-hydroxyphthalimides or N-hydroxynaphthalimides by esterification with the corresponding sulfonic acids or -the acid chlorides or anhydrides thereof, according to the methods known for such compounds, as they are described in Annalen 616~
183 (1958) and in Journal of Organic Chemistry 20, 33 (1955) and 38, 3908 (1973).
The following are examples of individual compounds of the formula I- N-phenylsulfonyloxy-phthalimide, N-p-tolylsulfonyloxy-phthalimide, N-methylsulfonyloxy-phthal-imide, N-hexadecylsulfonyloxy-phthalimide, N -trifluoro-methylsulfonyloxy-phthalimide, N-fluorosulfonyloxy-phthalimide, N-chloromethylsulfonyloxy-ph~thalimide, N-trichlorome-thylsulfonyloxy-ph~thalimide, N-bu-tylsulfonyl-oxy-ph-thalimide, N-dodecylsul:Eonyloxy-ph-thalimide, N-naphthylsulfonyloxy-phthalimide, N-2,4,5--trichlorophenyl-sulfonyloxy-phthalimide, N-2,4,6-trime-thylphenylsulfonyl-oxy-phthalimide, N-2,~-i,6-triisopropylphenylsulfonyloxy-phthalimide, N-cyclohexylsulfonyloxy-ph-thalimide, N-4-nitrophenylsulfonyloxy-ph-thalimide, N-4-chlorophenyl-sulfonyloxy-phthalimide, N-4-acetylaminophenylsulfonyloxy-phthalimide, N-4-methoxyphenylsulfonyloxy-phthalimide, N-p-tolylsulfonyloxy-3-nitro-phthalimide, N-methylsulfonyl-oxy-3-nitro-phthalimide, N p-tolylsulfonyloxy-4-nitro-phthalimide, N-p-tolylsulfonyloxy-4-methyl-ph-thalimide, N-p--tolylsulfonyloxy-3-ethylthio-phthalimide and N-phenyl-sulfonyloxy-4-chloro-phthalimide.
The following are examples of individual compounds of the formula II: N-p-tolylsulfonyloxy-naphthalimide, N-me-thylsulfonyloxy-naph-thalimide, N-dodecylsulfonyloxy-naphthalimide~ N-butylsulfonyloxy-naphthalimide, N-tri-fluoromethylsulfonyloxy-naphthal.imide, N-fluorosulfonyl-oxy-naphthalimide, N-nonylnaph-thylsulfonyloxy-naphthal-imide, N-p-dodecylphenylsulfonyloxy-naphthalimide, N-phenylsulfonyl.oxy-naph-thalimide, N-camphor-10-sulfonyloxy-naphthalimide, N-trichlorophenylsulfonyloxy-naphthalimide 9 N-2,4,6-triisopropylsulfonyloxy naphthalimide, N-ethyl-sulfonyloxy-naph-thalimide, N-p-chlorosulfonyloxy-naphthal-imide and N-xylylsulfonyloxy-naphthalimide.
The curing catalysts according to the lnvention are added to the resins in a quantity which is sufficient for curing. The required quantity depends not only on the type of resin but also on the intended curing -tempera-ture and curing time. In general, 0.1 to 10% by weight 9 preferably 0.5 to 5% by weight, relative -to -the solvent-free resin, are used.
All those resins can be used, the curing of which can be accelerated by acid catalys-ts. These are especially surface-coa-ting resins based on acrylic resins, polyester resins, alkyd resins, melamine resins urea resins and phenolic resins, and in particular mixtures of acrylic resins, polyester resins or alkyd resins wi-th one another or wi-th a melamine resin. These also include modified surface-coating resins, for example acrylic-modified polyes-ter or alkyd resins. Examples of individual -types of resins which fall within -the scope of the term acrylic, polyes-ter and alkyd resins, are des-cribed in Wagner, Sarx '~Lackkuns-tharze (Synthe-tic Resins for Finishes)" (Munich 7 1971), pages 86 -to 123 and 229 -to 238, or in Ullmann "Encyclopadie der techn. Chemie (Encyclopaedia of Industrial Chemistry)", 4-th edition, volume 15 (1978), pages 613 -to 628. acid catalysis is of particular importance for the curing of finishes which contain etherified amino resins, for example me-thyl-a-ted or butylated melamine resins (N-methoxymethyl- or N-butoxymethyl-melamine respec-tively) or me-thylated/
bu-tylated glycol-urils o for example CH30C~l2- -clloCH
C~13C112~N~\ ~N~C~12ocH3 o and the ]iker For cer-tain purposes, resin compositions are also used which contain monomeric or oligomeric consti-tuents having unsaturated groups capable of polymerisa-tion.
Resin compositions of this -type can also be cured by the process according -to the inven-tion. In this case, free-radical polymerisation initiators or photo-initiators can also be used addi-tionally. The former initiate the polymerisa-tion of the unsa-tura-ted groups during the heat treatment, and the latter initia-te the polymerisation during the W irradia-tion. Resin compositions of this type, having ~msaturated components, can also be polymerised by elec-tron beams. However, acid-ca-talysed crosslinking mus-t always -take place in addi-tion to the polymerisa-tion of the unsatura-ted componen-ts.
The finishes can be solutions or dispersions of the surface-coa-ting resin in an organic solven-t or in wa-ter, or they can be solvent-free. Finishes wi-th a small proportion of solven-t, so-called "high solids finishes", are ox par-ticular interest. The finishes can be clear finishes, such as are used in the motor vehicle industry as topcoats of multi-coat paints. They can also contain pigments which may be inorganic or organic pigments, as well as metal pigments for metallic-effect finishes.
Moreover,the finishes can contain minor amounts of special additives conventional in surface coa-ting -tech-nology, for example flow control agents, thixo-tropic agen-ts, light-s-tabilisers or antioxidan-ts.
Examples of light-stabilisers are -those from the group comprisirg hydroxyphenyl-benzotriazoles, hydroxybenzo-phenones, cyanoacrylates, hydroxyphenyl-triazines, oxal-anilides,organic nickel compounds and polyalkylpiperidine derivatives. Since light-stabilisers of the W
absorber type can interfere with the Us irradiation according to the invention, ligh-t-stabilisers of this type can also be added to an adjacen-t coat, from which they -then gradually diffuse into that layer of the baking finish which is -to be stabilised. The adjacent coat can be a primer underneath the baking finish or a topcoat above the baking finish.
As an alternative, it is also possible to circum-vent the interfering influence of a W absorber by the use of so-called "blocked W absorbers", such as are described in German Of:Eenlegungsschrif-t 2,648,367.
Products which form a W absorber by a Fries photo rearrangemen-t, for example resorcinol monobenzoa-te, are also sui-table.
Polymethylpiperidine derivatives or combina-tions ~gs~
thereof with blocked) W -absorbers are preferred.
The following composi-tions according -to the inven-tion represen-t further special preferred embodimen-ts of the invention:
a) A composi-tion which, as -the resin, con-tains an amino resin or a mixture of an amino resin with another resin, or a resin con-taining methyl-amino groups.
b) A composition which, as the acid-curable resin, contains a phenolic resin or a phenol/formaldehyde resin, or a mix-ture of such a resin with another acid-curable resin c) A composition which, as the base resin, contains a mixture of acryla-tes and melamine resins (hybrid sys-tems) and in addition, if appropriate, free-radical polymerisation initiators or photo-initia-tors.
d) A composition which, as the acid-curable resin, contains the following mixture:
hexamethoxymethylmelamine 17.93 parts by weight butyl aceta-te 9.73 parts by weight cellulose acetobutyrate 1.83 parts by weight a silicone resin in organic solvents 2.80 parts by weight a flow control agent based on a polymer 0.29 part by weight an acrylic resin having functional hydroxyl groups 57.30 parts by weight n-butanol 10.12 parts by weight 100.00 parts by weight e) A composi-tion which, in addition to the resin and the curing catalyst1 also contains further additives con-ventional in resin technology.
f) A composition which additionally contains one or more ethylenically unsaturated compounds.
g) A composition according to f), which additionally contains a photo-initiator from the aromatic ketone series.
h) A composition which, as -the curing catalyst, contains a compound of -the formula o > 2 o in which R is-~CH3~ -C4Hg~ -C12H25' -C16H~3 or 12 25 \ /and preferably is -~4Hg or -C12H25.
i) A composition which additionally contains 0.1-5%
by weigh-t of a monohydric or polyhydric aroma-tic alcohol.
j) A composltlon according to i) which, as -the aromatic alcohol, contains hydroquinone, 2,6-di--tert.-butyl-4-me-thylphenol or bisphenol A.
k) A composition which additionally contains 0.1-2%
by weight of phenanthrenequinone.
The inven-tion also rela-tes to a process for curing acid-curable resins in the presence of curing ca-talysts of the formula I or II by irradiation wi-th short-wave light and subsequent heating.
The irradiation of -the resin wi-th short-wave ligh-t is preferably carried out wi-th W ligh-t9 a number of sui-table industrial devices being available nowadays for this purpose. These include medium-pressure, high-pressure or low-pressure mercury lamps as well as fluorescent tubes, the emission maxima of which lie at 250 to Loo nm. The required irradiation times depend on the layer thickness of the resin, on the pigmen-tation, on the ligh-t intensity of the lamps and on the dis-tance of the lampsi An unpigmented finish in the usual layer thickness requires a few seconds of exposure time in conventional W irradiation devicesO During this time, the latent catalys-t is photochemically converted to form a free sulfonic acidO
If pho-to~sensitisers are added -to the resin, the 5~7 g irradlation can also be carried ou-t wi-th daylight lamps.
Examples of known photo-sensitisers are fused aromatics, :for example perylene, aroma-tic amines (such as are described in U.S. Paten-t Specification 4,069,054) or cationic and basic dyes (for example -those described in U.S. Pa-tent Specifica-tion 4,026,705).
Since the acid-curing proceeds very slowly at room temperature, it is necessary for an industrial application of the process to follow -the irradiation wi-th a heat treatment. In contrast to other processes using curing catalysts which can be split by heat, how ever, this treatment can be carried out at rela-tively low temperatures. With a baking time of abou-t 30 minutes and the use of about 2% of catalyst, temperatures of 70 to 80C are sufficient. When 1% of ca-talyst is used, temperatures of 80 to 100C are required and, when 0.5%
of catalyst is used, temperatures of abou-t 100 to 120C
are required. Preferably, the resins catalysed in accordance with the invention are cured, after irradiation, at temperatures below 130C. By contrast, even bak-ing -temperatures of more than 130C are required in some cases for the curlng with known amine salts of sulfonic acids (without irradiation).
These relatively low baking temperatures of the process according to -the inven-tion are of considerable industrial importance in the coating and pain-ting of -temperature-sensitive substrates, for example ar-ticles of wood or cardboard, and in particular articles which con-tain components of plastics or rubbers, for example electrical appliances, vehicles of any type or machines A further advantage over other one-component resins containing a curing catalyst is that the one-component systems according -to -the invention have a vir-tually unlimited storage life at room tempera-ture, since the active catalyst is formed only during the irradiation.
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The process according to -the invention is suit-able for all -types of indus-trial coa-ting and painting, for example for painting machines, vehicles, ships or s-tructural componen-ts. I-t is of particular import-ance for mo-tor vehicle pain-ting. In this case, it can be used in a single-coa-t paint or in a mul-ti-coa-t paint. The use of the process for -the con-tinuous coating of sheet me-tal, for example s-teel sheet or aluminium sheet, by the so-called coil-coat process is also of particular in-terest. Additionally, the pro-cess is suitable for the curing of acid-curable printing inks which, because of their excellent stability in deep-drawing, are par-ticularly suitable for -the printing of shee-t metal.
When the process according -to the invention is used with compression-moulding compounds, casting resins and laminating resins, -the resins can first be irradiated in a thin layer and then be hot-formed and cured to give any desired articles. However, if these are articles of relatively small thickness, -the resins can also be shaped first and subsequently irradia-ted and heated.
In -the irradiation of the resins, the layer -thickness can be several millimetres, depending on their transparency.
A further possible application of the process is in the prepara-tion of relief forms, for example printing plates.
In -this case, the solid or liquid acid-curable resin composition which can also contain unsaturated monomers/
prepolymers as well as photo-initiators or polymerisation initiators, is first exposed through a negative :Eilm.
Subsequently, if appropria-te, a thermal after-trea-tment is carried out, the exposed areas being crosslinked.
Finally, -the printing plate is developed by washing out the uncrosslinked areas. Printing plates for letter-press printing, flexographic printing or offset printing can be prepared correspondingly.
The examples which follow explain the process in more de-tail by reference to specific compositions 5~
according -to -the inven-cion. In -the examples, -the parts and percentages are by weight. The -tempera-tures are given in degrees C.
Example 1: Curing of a finish based on an acrylic/
melamine resin.
0.5 mm thick aluminium sheets which had been coated with a whi-te-pigmented primer based on polyes-ter resin, are coated with a high-solids clear finish of -the following composition:
53.7 parts of acrylic resin (Paraloid OL 42, Rohm & Haas Co., USA) 19.3 par-ts of melamine resin (Cymel 301, Amer. Cyanamide Co. ) 1.9 parts of cellulose acetobutyrate (CAB 551, Eastman Chem. Co.) 10.6 par-ts of n-butanol 10.5 parts of butyl acetate 3.0 parts of flow control agent (Byketol Spezial, Byk-Mallinckrodt) 0.4 part of flow control agen-t (Modaflow, Monsanto Comp.) o.6 part of curing ca-talyst.
The catalyst is first dissolved in a part of the butanol. The finish has a solids content of 62.1%
(binder). The catalyst quan-tity therefore corresponds to 1% 9 relative to solvent-free binder.
The finish is applied with an electric film spreader in such a way that the dry film thickness is about 30 em. After an air-drying time of 15 minu-tes, the samples are exposed, in a PPG irradiation apparatus with 2 high-pressure mercury vapour lamps of 80 Wa-t-t each, to W irradiation, the irradiation period being varied. Subsequently, the samples are baked for 30 minu-tes a-t 100C in an oven.
To assess the degree of curing, the pendulum hard-ness of -the finish film is determined by the method according -to K8nig (DIM 53,1573, and this is done 30 minutes after baking.
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To assess -the discolora-tion (yellowing), the colour difference QE according to DIN 6,174 is de-termined.
The results are listed in Table 1.
Table 1 .
Catalyst Irradiation Pendulum Colour time hardness difference (seconds) (seconds) YE
. ...
N-Methylsulfonyl-oxy-phthalimide 2.1 102 1.9 4.2 113 3.0 12.6 120 5.2 25.2 120 6.4 N-Phenylsulfonyl-oxy-phthalimide 2.1 69 1.1 4.2 83 1.5 12.6 86 2.6 25.2 87 3.8 . I. .
N-p-Tolylsulfonyl-oxy-phthalimide 2.1 81 1.4 4.2 95 2.0 12.6 106 3.6 25.2 106 5.0 . _ . __ _ . .
Addi-tionally, the s-torage stability of the finish samples is checked by measuring the viscosity during storage at 60C for 7 days, using the ICI cone-and-plate viscometer.
In this method, the viscosi-ty is measured in poise. The difference between this viscosi-ty (I
and the viscosity of a catalyst-free finish sample is indicated in Table 2.
Table 2 _ . _ . I, Catalysts Viscosity difference A in poise after s-torage for 0 1 2 3 4 7atday600c ... . . .. _ ... . ._ _ _ _ N-Me-thylsulfonyloxy-phthalimide 0.5 1.3 2.3 2.3 3.2 2.9 N-Phenylsulfonyloxy-phthalimide 0 0.4 0.6 o.6 0.5 0.4 N-p~Tolylsulfonyloxy-phthalimide 0 002 0.7 0.7 0.4 0.5 ~,f.~5 Example 2:
The compounds listed in Table 3 below are incor-porated as catalysts in-to the high-solids clear finish described in Example 1 (amoun-t of ca-talyst: o.6 par-t).
Testing is carried ou-t as in Example 1.
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Example 3-The following base resin formula-tion is used as the raw material:
Hexamethoxy~e-thylmelamine 17.93 g (Cymel 301 I, 100%) Butyl acetate 9.73 g Cellulose ace-~obutyrate 1.83 g (CAB 551,001 from Messrs.
Eastman Chem.) Silicone resin in an organic solvent 2.80 g (flow control agent, Byketol Spezial from Messrs. Byk-Mallinckrodt) F'low contrAl agent based on a polymer 0.29 g (Modaflow~, 1% solu-tion; Monsanto) Acrylic resin having functional hydroxyl groups 57.30 g (Paraloid AT 410 , 73%; Rohm Haas) n-Butanol 10.12 g 100.00 g The compounds listed in Table 4 are incorporated in a concentration of 1% by weigh-t into this base resin.
Testing is carried out as described in Example 1. The results are shown in Table 4. The viscosity change is given here as %, relative to the initial value of -the complete resin formulation.
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En . _ 5~7 Example_4 In -the following experimen-t, -the whi-te finish formula below ls used as -the raw material.
formula for a white-pi~mented "acrylic/melami e high-solid finish"
Acryloid AT 400 (acrylic resin having (75% in MAK) functional hydroxyl groups; Rohm + Haas) 39.0 % by weight Cymel 301 ~9.75% by weight Kronos RN 57 (TiO2 from MessrsO Kronos) 26.0 % by weight n-Butanol 5.25% by weight Methyl amyl ketone (MAK) 20.0 /0 by weight lO0.0 % by weight Various blocked acid catalysts as well as co-catalysts are incorpora-ted into -this base resin.
Subsequently, -the white finishes are spread by means of a doctor blade on aluminium sheets coated with a coil-coat, in such a way tha-t (af-ter baking) a dry~film thickness of about 30 results. After a brief air-drying -time the samples are irradiated for lO minutes under Phillips TLK 40W/09 fluorescent tubes and -then baked for 30' at 120C. Af-ter s-toring for 30' 9 the pendulum hardness according to Koenig is measured.
The test results are compiled in Table 5.
3L2~4~gr7 liable 5 -Acid catalys-t Co-catalyst Pendulum hardness ~r:LO mi~u~s rradia-tion, nd baking . .. . ,,_ .,, _ Compound of -the formula ._~ o none 27 .~ '~S2(cn2~,c~l3 . _ . _ I_ Ditto 1% of hydro- >100 quinone . . .
Ditto 0.5% of phen- ~100 anthrenequinone __~ ..... --Ditto 1% of 2,6-di- 85 -tert.-bu-tyl-4-m(BthY)lphenol . _ __ .
Ditto 1% of pentaeryth- 70 rityl tetrakis-L3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate ... __ .... __ _ Ditto 1.0% of hydro- >100 quinone 0.5% of phen-an-threnequinone _ .... __ _ . , _~, --The amounts of added catalysts rela-te to solid binder.
Curable composi-tion based on an acid-curable resin9 and Err cess for c _in~_this resin _ __ The invention relates to compositions based on an acid-curable resin and containing a blocked curing cata-lyst, and to a process for curing this resin by irradia-tion with short-wave light and subsequen-t heating.
Acid-curable resins are used especially as binders for finishes, printing inks and paints, when high baking temperatures are to be avoided. The acid-curable resins can be amino resins, including etherified, esteri-fied or otherwise modified melamine resins, urea/form-aldehyde resins, phenol/formaldehyde resins as well as mixtures of such resins with alkyd resins, polyester resins or acrylic resins. Further acid-curable resins are me-thylol compounds, methylol ethers of polycarboxylic acid amides, for example deriva-tives of polyacrylic or polymethacrylic acid, urethane-alkyds as well as resins which contain carboxylic acid esters of N-methylol~amides.
Acid-polymerisable or acid-curable ethylenically unsatur-ated materials, such as N-methylol-acrylamide, vinyl carbazole, vinyl ethers9 diketene and diacetone-acrylamide can also be usedO The acid curing catalysts used are predominantly organic acids, such as sulfonic acids9 in particular p-toluenesulfonic acid, half-esters ox phthalic acid or maleic acid, or phosphoric acid and its partial esters. Since these acids effec-t slow curing even at room temperature, they are added to the resin only shor-tly before -the lat-ter is applied, and -this leads to the .
I
5~
known problems in main-taining defined po-t lives. To make one-componen-t sys-tems feasible, i-t has already been proposed to use blocked curing catalysts, from which -the acid is libera-ted a-t an eleva-ted tempera-ture. Ex-amples of such catalysts are amine salts of the acids, for example the pyridine sal-ts of aromatic sulfonic acids, as proposed in U.S. Patent Specification 3947L~,05L~.
These and other salts have the disadvantage that they either already effect slow curing during s-torage or -that they require very high curing temperatures or very long curing -times. Moreover 5 they cause odour problems.
Furthermore, U.S. Patent Specification 4,102,687 has proposed the use of aromatic sulfonium salts of com-plex anions, for example of BF4, PF`6, SbF6 or AsF6, as blocked curing catalys-ts, from which the actual curing catalyst is formed by irradia-tion with W light.
According to German Offenlegungsschrift 2,602,57L~, the same principle can also be realised with aromatic iodonium salts. However, it is difficult to prepare sulfonium salts or iodonium salts of this type in a pure form, and they have a low reactivity and tend to cause yellowing of the resins. There is therefore a need for compounds which can readily be prepared on an industrial scale and which, on irradiation with short-wave ligh-t, rapidly decompose -to form a highly reactive curing catalyst for acid-curable resins.
It has now been found tha-t sulfonic acid es-ters of certain cyclic hydroxamic acid deriva-tives 9 which can readily be prepared industrially, meet these requirements, since they have unlimited storage life in -the dark but, on exposure to short-wave ligh-t 9 rapidly decompose -to form sulfonic acids which make a subsequen-t acid-ca-talysed curing of the resins possible a-t a relatively low temp-erature and do not tend to cause yellowing of the resins.
The invention relates to a curable composition, comprising an acid-curable resin and, as a blocked curing catalyst, a compound of the formula I or II
5~
/ \ / 2 ~.1-0-SC
O R R"
I II
in which R is Cl-C18-alkyl, phenyl which is unsubstituted or substituted by Cl-C12-alkyl, halogen, Cl-C4-alkyl-NHCO-, phenyl-NHCO-, N02 or Cl-C4-alkoxy9 or is naphthyl which is unsubstituted or substituted by Cl-C12-alkyl or halogen, or is C5-C6-cycloalkyl, camp4horyl, CF3, CC13, CH2Cl, F or NH2 and R , R , R and R independently of one another are hydrogen, Cl-C8-alkyl, Cl C4-alkoxy, Cl-C12-alkyl-thio, phenyl-thio, N02 or halogen.
Preferably, the curing ca-talyst is a compound of the formula I or II, in which R is Cl-C18~alkyl, F9 CF3, CC13, or phenyl or naphthyl which are unsubst~tu-ted or substituted by C~-C12-alkyl, Cl or CH3CONH, or is cam-phoryl and R , R , R3 and R independently of one another are hydrogen, Cl-C4-alkyl, Cl-C4-alkoxy or Cl-C4-alkylthio.
The compounds of the formula I are derivatives of N-hydroxy-phthalimide, and the compounds of the formula II
are derivatives of N-hydroxy-naph-thalimide. They can be prepared from the corresponding N-hydroxyphthalimides or N-hydroxynaphthalimides by esterification with the corresponding sulfonic acids or -the acid chlorides or anhydrides thereof, according to the methods known for such compounds, as they are described in Annalen 616~
183 (1958) and in Journal of Organic Chemistry 20, 33 (1955) and 38, 3908 (1973).
The following are examples of individual compounds of the formula I- N-phenylsulfonyloxy-phthalimide, N-p-tolylsulfonyloxy-phthalimide, N-methylsulfonyloxy-phthal-imide, N-hexadecylsulfonyloxy-phthalimide, N -trifluoro-methylsulfonyloxy-phthalimide, N-fluorosulfonyloxy-phthalimide, N-chloromethylsulfonyloxy-ph~thalimide, N-trichlorome-thylsulfonyloxy-ph~thalimide, N-bu-tylsulfonyl-oxy-ph-thalimide, N-dodecylsul:Eonyloxy-ph-thalimide, N-naphthylsulfonyloxy-phthalimide, N-2,4,5--trichlorophenyl-sulfonyloxy-phthalimide, N-2,4,6-trime-thylphenylsulfonyl-oxy-phthalimide, N-2,~-i,6-triisopropylphenylsulfonyloxy-phthalimide, N-cyclohexylsulfonyloxy-ph-thalimide, N-4-nitrophenylsulfonyloxy-ph-thalimide, N-4-chlorophenyl-sulfonyloxy-phthalimide, N-4-acetylaminophenylsulfonyloxy-phthalimide, N-4-methoxyphenylsulfonyloxy-phthalimide, N-p-tolylsulfonyloxy-3-nitro-phthalimide, N-methylsulfonyl-oxy-3-nitro-phthalimide, N p-tolylsulfonyloxy-4-nitro-phthalimide, N-p-tolylsulfonyloxy-4-methyl-ph-thalimide, N-p--tolylsulfonyloxy-3-ethylthio-phthalimide and N-phenyl-sulfonyloxy-4-chloro-phthalimide.
The following are examples of individual compounds of the formula II: N-p-tolylsulfonyloxy-naphthalimide, N-me-thylsulfonyloxy-naph-thalimide, N-dodecylsulfonyloxy-naphthalimide~ N-butylsulfonyloxy-naphthalimide, N-tri-fluoromethylsulfonyloxy-naphthal.imide, N-fluorosulfonyl-oxy-naphthalimide, N-nonylnaph-thylsulfonyloxy-naphthal-imide, N-p-dodecylphenylsulfonyloxy-naphthalimide, N-phenylsulfonyl.oxy-naph-thalimide, N-camphor-10-sulfonyloxy-naphthalimide, N-trichlorophenylsulfonyloxy-naphthalimide 9 N-2,4,6-triisopropylsulfonyloxy naphthalimide, N-ethyl-sulfonyloxy-naph-thalimide, N-p-chlorosulfonyloxy-naphthal-imide and N-xylylsulfonyloxy-naphthalimide.
The curing catalysts according to the lnvention are added to the resins in a quantity which is sufficient for curing. The required quantity depends not only on the type of resin but also on the intended curing -tempera-ture and curing time. In general, 0.1 to 10% by weight 9 preferably 0.5 to 5% by weight, relative -to -the solvent-free resin, are used.
All those resins can be used, the curing of which can be accelerated by acid catalys-ts. These are especially surface-coa-ting resins based on acrylic resins, polyester resins, alkyd resins, melamine resins urea resins and phenolic resins, and in particular mixtures of acrylic resins, polyester resins or alkyd resins wi-th one another or wi-th a melamine resin. These also include modified surface-coating resins, for example acrylic-modified polyes-ter or alkyd resins. Examples of individual -types of resins which fall within -the scope of the term acrylic, polyes-ter and alkyd resins, are des-cribed in Wagner, Sarx '~Lackkuns-tharze (Synthe-tic Resins for Finishes)" (Munich 7 1971), pages 86 -to 123 and 229 -to 238, or in Ullmann "Encyclopadie der techn. Chemie (Encyclopaedia of Industrial Chemistry)", 4-th edition, volume 15 (1978), pages 613 -to 628. acid catalysis is of particular importance for the curing of finishes which contain etherified amino resins, for example me-thyl-a-ted or butylated melamine resins (N-methoxymethyl- or N-butoxymethyl-melamine respec-tively) or me-thylated/
bu-tylated glycol-urils o for example CH30C~l2- -clloCH
C~13C112~N~\ ~N~C~12ocH3 o and the ]iker For cer-tain purposes, resin compositions are also used which contain monomeric or oligomeric consti-tuents having unsaturated groups capable of polymerisa-tion.
Resin compositions of this -type can also be cured by the process according -to the inven-tion. In this case, free-radical polymerisation initiators or photo-initiators can also be used addi-tionally. The former initiate the polymerisa-tion of the unsa-tura-ted groups during the heat treatment, and the latter initia-te the polymerisation during the W irradia-tion. Resin compositions of this type, having ~msaturated components, can also be polymerised by elec-tron beams. However, acid-ca-talysed crosslinking mus-t always -take place in addi-tion to the polymerisa-tion of the unsatura-ted componen-ts.
The finishes can be solutions or dispersions of the surface-coa-ting resin in an organic solven-t or in wa-ter, or they can be solvent-free. Finishes wi-th a small proportion of solven-t, so-called "high solids finishes", are ox par-ticular interest. The finishes can be clear finishes, such as are used in the motor vehicle industry as topcoats of multi-coat paints. They can also contain pigments which may be inorganic or organic pigments, as well as metal pigments for metallic-effect finishes.
Moreover,the finishes can contain minor amounts of special additives conventional in surface coa-ting -tech-nology, for example flow control agents, thixo-tropic agen-ts, light-s-tabilisers or antioxidan-ts.
Examples of light-stabilisers are -those from the group comprisirg hydroxyphenyl-benzotriazoles, hydroxybenzo-phenones, cyanoacrylates, hydroxyphenyl-triazines, oxal-anilides,organic nickel compounds and polyalkylpiperidine derivatives. Since light-stabilisers of the W
absorber type can interfere with the Us irradiation according to the invention, ligh-t-stabilisers of this type can also be added to an adjacen-t coat, from which they -then gradually diffuse into that layer of the baking finish which is -to be stabilised. The adjacent coat can be a primer underneath the baking finish or a topcoat above the baking finish.
As an alternative, it is also possible to circum-vent the interfering influence of a W absorber by the use of so-called "blocked W absorbers", such as are described in German Of:Eenlegungsschrif-t 2,648,367.
Products which form a W absorber by a Fries photo rearrangemen-t, for example resorcinol monobenzoa-te, are also sui-table.
Polymethylpiperidine derivatives or combina-tions ~gs~
thereof with blocked) W -absorbers are preferred.
The following composi-tions according -to the inven-tion represen-t further special preferred embodimen-ts of the invention:
a) A composi-tion which, as -the resin, con-tains an amino resin or a mixture of an amino resin with another resin, or a resin con-taining methyl-amino groups.
b) A composition which, as the acid-curable resin, contains a phenolic resin or a phenol/formaldehyde resin, or a mix-ture of such a resin with another acid-curable resin c) A composition which, as the base resin, contains a mixture of acryla-tes and melamine resins (hybrid sys-tems) and in addition, if appropriate, free-radical polymerisation initiators or photo-initia-tors.
d) A composition which, as the acid-curable resin, contains the following mixture:
hexamethoxymethylmelamine 17.93 parts by weight butyl aceta-te 9.73 parts by weight cellulose acetobutyrate 1.83 parts by weight a silicone resin in organic solvents 2.80 parts by weight a flow control agent based on a polymer 0.29 part by weight an acrylic resin having functional hydroxyl groups 57.30 parts by weight n-butanol 10.12 parts by weight 100.00 parts by weight e) A composi-tion which, in addition to the resin and the curing catalyst1 also contains further additives con-ventional in resin technology.
f) A composition which additionally contains one or more ethylenically unsaturated compounds.
g) A composition according to f), which additionally contains a photo-initiator from the aromatic ketone series.
h) A composition which, as -the curing catalyst, contains a compound of -the formula o > 2 o in which R is-~CH3~ -C4Hg~ -C12H25' -C16H~3 or 12 25 \ /and preferably is -~4Hg or -C12H25.
i) A composition which additionally contains 0.1-5%
by weigh-t of a monohydric or polyhydric aroma-tic alcohol.
j) A composltlon according to i) which, as -the aromatic alcohol, contains hydroquinone, 2,6-di--tert.-butyl-4-me-thylphenol or bisphenol A.
k) A composition which additionally contains 0.1-2%
by weight of phenanthrenequinone.
The inven-tion also rela-tes to a process for curing acid-curable resins in the presence of curing ca-talysts of the formula I or II by irradiation wi-th short-wave light and subsequent heating.
The irradiation of -the resin wi-th short-wave ligh-t is preferably carried out wi-th W ligh-t9 a number of sui-table industrial devices being available nowadays for this purpose. These include medium-pressure, high-pressure or low-pressure mercury lamps as well as fluorescent tubes, the emission maxima of which lie at 250 to Loo nm. The required irradiation times depend on the layer thickness of the resin, on the pigmen-tation, on the ligh-t intensity of the lamps and on the dis-tance of the lampsi An unpigmented finish in the usual layer thickness requires a few seconds of exposure time in conventional W irradiation devicesO During this time, the latent catalys-t is photochemically converted to form a free sulfonic acidO
If pho-to~sensitisers are added -to the resin, the 5~7 g irradlation can also be carried ou-t wi-th daylight lamps.
Examples of known photo-sensitisers are fused aromatics, :for example perylene, aroma-tic amines (such as are described in U.S. Paten-t Specification 4,069,054) or cationic and basic dyes (for example -those described in U.S. Pa-tent Specifica-tion 4,026,705).
Since the acid-curing proceeds very slowly at room temperature, it is necessary for an industrial application of the process to follow -the irradiation wi-th a heat treatment. In contrast to other processes using curing catalysts which can be split by heat, how ever, this treatment can be carried out at rela-tively low temperatures. With a baking time of abou-t 30 minutes and the use of about 2% of catalyst, temperatures of 70 to 80C are sufficient. When 1% of ca-talyst is used, temperatures of 80 to 100C are required and, when 0.5%
of catalyst is used, temperatures of abou-t 100 to 120C
are required. Preferably, the resins catalysed in accordance with the invention are cured, after irradiation, at temperatures below 130C. By contrast, even bak-ing -temperatures of more than 130C are required in some cases for the curlng with known amine salts of sulfonic acids (without irradiation).
These relatively low baking temperatures of the process according to -the inven-tion are of considerable industrial importance in the coating and pain-ting of -temperature-sensitive substrates, for example ar-ticles of wood or cardboard, and in particular articles which con-tain components of plastics or rubbers, for example electrical appliances, vehicles of any type or machines A further advantage over other one-component resins containing a curing catalyst is that the one-component systems according -to -the invention have a vir-tually unlimited storage life at room tempera-ture, since the active catalyst is formed only during the irradiation.
~Z~4~
The process according to -the invention is suit-able for all -types of indus-trial coa-ting and painting, for example for painting machines, vehicles, ships or s-tructural componen-ts. I-t is of particular import-ance for mo-tor vehicle pain-ting. In this case, it can be used in a single-coa-t paint or in a mul-ti-coa-t paint. The use of the process for -the con-tinuous coating of sheet me-tal, for example s-teel sheet or aluminium sheet, by the so-called coil-coat process is also of particular in-terest. Additionally, the pro-cess is suitable for the curing of acid-curable printing inks which, because of their excellent stability in deep-drawing, are par-ticularly suitable for -the printing of shee-t metal.
When the process according -to the invention is used with compression-moulding compounds, casting resins and laminating resins, -the resins can first be irradiated in a thin layer and then be hot-formed and cured to give any desired articles. However, if these are articles of relatively small thickness, -the resins can also be shaped first and subsequently irradia-ted and heated.
In -the irradiation of the resins, the layer -thickness can be several millimetres, depending on their transparency.
A further possible application of the process is in the prepara-tion of relief forms, for example printing plates.
In -this case, the solid or liquid acid-curable resin composition which can also contain unsaturated monomers/
prepolymers as well as photo-initiators or polymerisation initiators, is first exposed through a negative :Eilm.
Subsequently, if appropria-te, a thermal after-trea-tment is carried out, the exposed areas being crosslinked.
Finally, -the printing plate is developed by washing out the uncrosslinked areas. Printing plates for letter-press printing, flexographic printing or offset printing can be prepared correspondingly.
The examples which follow explain the process in more de-tail by reference to specific compositions 5~
according -to -the inven-cion. In -the examples, -the parts and percentages are by weight. The -tempera-tures are given in degrees C.
Example 1: Curing of a finish based on an acrylic/
melamine resin.
0.5 mm thick aluminium sheets which had been coated with a whi-te-pigmented primer based on polyes-ter resin, are coated with a high-solids clear finish of -the following composition:
53.7 parts of acrylic resin (Paraloid OL 42, Rohm & Haas Co., USA) 19.3 par-ts of melamine resin (Cymel 301, Amer. Cyanamide Co. ) 1.9 parts of cellulose acetobutyrate (CAB 551, Eastman Chem. Co.) 10.6 par-ts of n-butanol 10.5 parts of butyl acetate 3.0 parts of flow control agent (Byketol Spezial, Byk-Mallinckrodt) 0.4 part of flow control agen-t (Modaflow, Monsanto Comp.) o.6 part of curing ca-talyst.
The catalyst is first dissolved in a part of the butanol. The finish has a solids content of 62.1%
(binder). The catalyst quan-tity therefore corresponds to 1% 9 relative to solvent-free binder.
The finish is applied with an electric film spreader in such a way that the dry film thickness is about 30 em. After an air-drying time of 15 minu-tes, the samples are exposed, in a PPG irradiation apparatus with 2 high-pressure mercury vapour lamps of 80 Wa-t-t each, to W irradiation, the irradiation period being varied. Subsequently, the samples are baked for 30 minu-tes a-t 100C in an oven.
To assess the degree of curing, the pendulum hard-ness of -the finish film is determined by the method according -to K8nig (DIM 53,1573, and this is done 30 minutes after baking.
4sg~
To assess -the discolora-tion (yellowing), the colour difference QE according to DIN 6,174 is de-termined.
The results are listed in Table 1.
Table 1 .
Catalyst Irradiation Pendulum Colour time hardness difference (seconds) (seconds) YE
. ...
N-Methylsulfonyl-oxy-phthalimide 2.1 102 1.9 4.2 113 3.0 12.6 120 5.2 25.2 120 6.4 N-Phenylsulfonyl-oxy-phthalimide 2.1 69 1.1 4.2 83 1.5 12.6 86 2.6 25.2 87 3.8 . I. .
N-p-Tolylsulfonyl-oxy-phthalimide 2.1 81 1.4 4.2 95 2.0 12.6 106 3.6 25.2 106 5.0 . _ . __ _ . .
Addi-tionally, the s-torage stability of the finish samples is checked by measuring the viscosity during storage at 60C for 7 days, using the ICI cone-and-plate viscometer.
In this method, the viscosi-ty is measured in poise. The difference between this viscosi-ty (I
and the viscosity of a catalyst-free finish sample is indicated in Table 2.
Table 2 _ . _ . I, Catalysts Viscosity difference A in poise after s-torage for 0 1 2 3 4 7atday600c ... . . .. _ ... . ._ _ _ _ N-Me-thylsulfonyloxy-phthalimide 0.5 1.3 2.3 2.3 3.2 2.9 N-Phenylsulfonyloxy-phthalimide 0 0.4 0.6 o.6 0.5 0.4 N-p~Tolylsulfonyloxy-phthalimide 0 002 0.7 0.7 0.4 0.5 ~,f.~5 Example 2:
The compounds listed in Table 3 below are incor-porated as catalysts in-to the high-solids clear finish described in Example 1 (amoun-t of ca-talyst: o.6 par-t).
Testing is carried ou-t as in Example 1.
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Example 3-The following base resin formula-tion is used as the raw material:
Hexamethoxy~e-thylmelamine 17.93 g (Cymel 301 I, 100%) Butyl acetate 9.73 g Cellulose ace-~obutyrate 1.83 g (CAB 551,001 from Messrs.
Eastman Chem.) Silicone resin in an organic solvent 2.80 g (flow control agent, Byketol Spezial from Messrs. Byk-Mallinckrodt) F'low contrAl agent based on a polymer 0.29 g (Modaflow~, 1% solu-tion; Monsanto) Acrylic resin having functional hydroxyl groups 57.30 g (Paraloid AT 410 , 73%; Rohm Haas) n-Butanol 10.12 g 100.00 g The compounds listed in Table 4 are incorporated in a concentration of 1% by weigh-t into this base resin.
Testing is carried out as described in Example 1. The results are shown in Table 4. The viscosity change is given here as %, relative to the initial value of -the complete resin formulation.
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it f O f r-l h O 'ED f (I I l 0~ . __ N I> f N 1 ~1 f _ . f _ r Us \I il- O f N 1--_ .. _. .
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f r-l f ,1 _ f r~l ~,~ I a) a 0~1 O I ~J I tH f f 1 l f O I X ~3 O :~
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En . _ 5~7 Example_4 In -the following experimen-t, -the whi-te finish formula below ls used as -the raw material.
formula for a white-pi~mented "acrylic/melami e high-solid finish"
Acryloid AT 400 (acrylic resin having (75% in MAK) functional hydroxyl groups; Rohm + Haas) 39.0 % by weight Cymel 301 ~9.75% by weight Kronos RN 57 (TiO2 from MessrsO Kronos) 26.0 % by weight n-Butanol 5.25% by weight Methyl amyl ketone (MAK) 20.0 /0 by weight lO0.0 % by weight Various blocked acid catalysts as well as co-catalysts are incorpora-ted into -this base resin.
Subsequently, -the white finishes are spread by means of a doctor blade on aluminium sheets coated with a coil-coat, in such a way tha-t (af-ter baking) a dry~film thickness of about 30 results. After a brief air-drying -time the samples are irradiated for lO minutes under Phillips TLK 40W/09 fluorescent tubes and -then baked for 30' at 120C. Af-ter s-toring for 30' 9 the pendulum hardness according to Koenig is measured.
The test results are compiled in Table 5.
3L2~4~gr7 liable 5 -Acid catalys-t Co-catalyst Pendulum hardness ~r:LO mi~u~s rradia-tion, nd baking . .. . ,,_ .,, _ Compound of -the formula ._~ o none 27 .~ '~S2(cn2~,c~l3 . _ . _ I_ Ditto 1% of hydro- >100 quinone . . .
Ditto 0.5% of phen- ~100 anthrenequinone __~ ..... --Ditto 1% of 2,6-di- 85 -tert.-bu-tyl-4-m(BthY)lphenol . _ __ .
Ditto 1% of pentaeryth- 70 rityl tetrakis-L3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propionate ... __ .... __ _ Ditto 1.0% of hydro- >100 quinone 0.5% of phen-an-threnequinone _ .... __ _ . , _~, --The amounts of added catalysts rela-te to solid binder.
Claims (19)
1. A curable composition, comprising an acid-curable resin and, as a blocked curing catalyst, a compound of the formula I or II
I II
in which R is C1-C18-alkyl, phenyl which is unsubstituted or substituted by C1-C12-alkyl, halogen, C1-C4-alkyl-NHCO-, phenyl-NHCO-, NO2 or C1-C4-alkoxy, or is naphthyl which is unsubstituted or substituted by C1-C12-alkyl or halogen, or is C5-C6-cycloalkyl, camphoryl, CF3, CCl3, CH2Cl, F or NH2 and R1, R2, R3 and R4 independently of one another are hydrogen, C1-C8-alkyl, C1-C4-alkoxy, C1-C12-alkylthio, phenylthio, NO2 or halogen.
I II
in which R is C1-C18-alkyl, phenyl which is unsubstituted or substituted by C1-C12-alkyl, halogen, C1-C4-alkyl-NHCO-, phenyl-NHCO-, NO2 or C1-C4-alkoxy, or is naphthyl which is unsubstituted or substituted by C1-C12-alkyl or halogen, or is C5-C6-cycloalkyl, camphoryl, CF3, CCl3, CH2Cl, F or NH2 and R1, R2, R3 and R4 independently of one another are hydrogen, C1-C8-alkyl, C1-C4-alkoxy, C1-C12-alkylthio, phenylthio, NO2 or halogen.
2. A composition according to claim 1, wherein the curing catalyst is a compound of the formula I or II, in which R is C1-C18-alkyl, F, CF3, CCl3, or phenyl or naphthyl which are unsubstituted or substituted by C1-C12-alkyl, chlorine or CH3CONH-, or is camphoryl and R1, R2, R3 and R4 independently of one another are hydrogen, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio.
3. A composition according to claim 2, which con-tains a curing catalyst of the formula I, in which R, R1 and R2 are as defined in claim 2.
4. A composition according to claim 2, which con-tains a curing catalyst of the formula II, in which R, R1, R2, R3 and R4 are as defined in claim 2.
5. A composition according to claim 1, which con-tains 0.1 to 10% by weight, relative to the solvent-free resin, of a curing catalyst of the formula I or II.
6. A composition according to claim 1, wherein the resin is an amino resin or a mixture of an amino resin with another resin, or is a resin containing methyl-amino groups.
7. A composition according to claim 1, which con-tains, as the acid-curable resin, a phenolic resin or a phenol/formaldehyde resin, or a mixture of such a resin with another acid-curable resin.
8. A composition according to claim 1, which con-tains, as the base resin, a mixture of an acrylate and a melamine resin (hybrid system) and, additionally, a free-radical polymerisation initiator and, if appropriate, a photo-initiator.
9. A composition according to claim 1, which con-tains the following mixture as the acid-curable resin:
hexamethoxymethylmelamine 17.93 parts by weight butyl acetate 9.73 parts by weight cellulose acetobutyrate 1.83 parts by weight a silicone resin in an organic solvent 2.80 parts by weight a flow control agent based on a polymer 0.29 part by weight an acrylic resin having functional hydroxyl groups 57.30 parts by weight n-butanol 10.12 parts by weight 100.00 parts by weight
hexamethoxymethylmelamine 17.93 parts by weight butyl acetate 9.73 parts by weight cellulose acetobutyrate 1.83 parts by weight a silicone resin in an organic solvent 2.80 parts by weight a flow control agent based on a polymer 0.29 part by weight an acrylic resin having functional hydroxyl groups 57.30 parts by weight n-butanol 10.12 parts by weight 100.00 parts by weight
10. A composition according to claim 1, which, in addition to the resin and the curing catalyst, also con-tains further additives conventional in resin technology.
11. A composition according to claim 1, which addi-tionally contains one or more ethylenically unsaturated compounds.
12. A composition according to claim 11, which addi-tionally contains a photo-initiator from the aromatic ketone series.
13. A composition according to claim 1, wherein the curing catalyst is a compound of the formula in which R is , -CH3, -C4H9, -C12H25, -C16H33 or C12H25 .
14. A composition according to claim 13 in which R is -C4H9 or -C12H25.
15. A composition according to claim 1, which additionally contains 0.1-5% by weight of a monohydric or polyhydric aromatic alcohol.
16. A composition according to claim 15, wherein the aromatic alcohol is hydroquinone, 2,6-di-tert.-butyl-4-methylphenol or bisphenol A.
17. A composition according to claim 1, which additionally contains 0.1-2% by weight of phenanthrenequinone.
18. A process for curing an acid-curable resin containing a curing catalyst according to claim 1, which comprises irradiating the resin with short-wave light and subsequently heating it.
19. A process according to claim 18, wherein the heating is carried out at temperatures below 130°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH97381 | 1981-02-13 | ||
| CH973/81-9 | 1981-02-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1204547A true CA1204547A (en) | 1986-05-13 |
Family
ID=4199507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000396041A Expired CA1204547A (en) | 1981-02-13 | 1982-02-11 | Curable composition based on an acid-curable resin, and process for curing this resin |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0058638B1 (en) |
| JP (1) | JPS57151651A (en) |
| BR (1) | BR8200758A (en) |
| CA (1) | CA1204547A (en) |
| DE (1) | DE3265701D1 (en) |
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| GB2120263B (en) * | 1982-05-17 | 1985-07-31 | Ciba Geigy Ag | A process for curing acid-curable abrasive compositions |
| GB8413395D0 (en) * | 1984-05-25 | 1984-07-04 | Ciba Geigy Ag | Production of images |
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|---|---|---|---|---|
| DE2107239B2 (en) * | 1971-02-16 | 1977-09-22 | Bayer Ag, 5090 Leverkusen | FAST NETWORKING BURNING SYSTEMS |
| AU521787B2 (en) * | 1975-07-12 | 1982-04-29 | E. I. Dupont De Nemours And Company | Thermosetting. electrostatically sprayable compositions containing backed acid catalyst |
-
1982
- 1982-02-08 DE DE8282810055T patent/DE3265701D1/en not_active Expired
- 1982-02-08 EP EP19820810055 patent/EP0058638B1/en not_active Expired
- 1982-02-11 CA CA000396041A patent/CA1204547A/en not_active Expired
- 1982-02-12 BR BR8200758A patent/BR8200758A/en unknown
- 1982-02-13 JP JP2192982A patent/JPS57151651A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0058638A2 (en) | 1982-08-25 |
| EP0058638B1 (en) | 1985-08-28 |
| DE3265701D1 (en) | 1985-10-03 |
| EP0058638A3 (en) | 1983-03-16 |
| JPS57151651A (en) | 1982-09-18 |
| BR8200758A (en) | 1982-12-21 |
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