CA1065085A - Radiation curable coating - Google Patents
Radiation curable coatingInfo
- Publication number
- CA1065085A CA1065085A CA222,006A CA222006A CA1065085A CA 1065085 A CA1065085 A CA 1065085A CA 222006 A CA222006 A CA 222006A CA 1065085 A CA1065085 A CA 1065085A
- Authority
- CA
- Canada
- Prior art keywords
- coating composition
- acrylate
- acrylic acid
- coating
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
Abstract
RADIATION CURABLE COATING
ABSTRACT OF THE DISCLOSURE
A radiation curable coating composition for various substrates contains an adduct of acrylic acid and an epoxy resin (which may be modified with an anhydride, such as maleic anhydride), and a reactive acrylate monomer vehicle.
The coating composition can be pigmented and can also contain additives commonly used in coatings, such as wetting agents and flow control agents. The coating composition does not require the usual hydrocarbon vehicles that give rise to air pollution problems. Surface gloss of a UV cured film obtained from a pigmented coating composition can be increased by using a photosensitizer combination of 2-chlorothioxanihone and a phenylketone, such as benzophenone. Adhesion of a cured coating is improved by replacing the tertiary amine co-sensitizer, at least in part, with dimethylaminoethyl acrylate.
ABSTRACT OF THE DISCLOSURE
A radiation curable coating composition for various substrates contains an adduct of acrylic acid and an epoxy resin (which may be modified with an anhydride, such as maleic anhydride), and a reactive acrylate monomer vehicle.
The coating composition can be pigmented and can also contain additives commonly used in coatings, such as wetting agents and flow control agents. The coating composition does not require the usual hydrocarbon vehicles that give rise to air pollution problems. Surface gloss of a UV cured film obtained from a pigmented coating composition can be increased by using a photosensitizer combination of 2-chlorothioxanihone and a phenylketone, such as benzophenone. Adhesion of a cured coating is improved by replacing the tertiary amine co-sensitizer, at least in part, with dimethylaminoethyl acrylate.
Description
iO~S08~i BACKGROUND OF THE INVENTION
Field of the Invention This invention is directed to epoxy acrylate ester coatings for substrates, that are curable with radiation.
Description of the Prior Art British Patent No. 1,241,851 describes a process for coating an article that comprises applying a film of an ethyleni-cally unsaturated ester having hydroxyl groups and exposing it to ionizing radiation. No liquid vehicle is used.
The coating composition of this invention comprises a similar resin in a vehicle that is a reactive monomer. This vehicle, when the coating composition is exposed to radiation and set, reacts with the resin and becomes an integral part of the resultant coating.
SUMMARY OF THE INVENTION
This invention provides a coating composition that com-prises an adduct of acrylic acid and an epoxy resin, or an anhydride modified adduct, and a reactive acrylate monomer. A
photosensitizer and a tertiary amine co-sensitizer are used in the case of ultraviolet (W) light cured coatings.
It also provides a W curable pigmented coating compo-- sition that contains a photosensitizer combination of 2-chloro-thioxanthone and a phenyl ketone.
It further provides a W curable coating composition - that affords improved film adhesion, in which at least part of the tertiary amine co-sensitizer is replaced with dimethylaminoethyl acrylate.
It still further provides substrates coated with the aforedefined coating composition. - -
Field of the Invention This invention is directed to epoxy acrylate ester coatings for substrates, that are curable with radiation.
Description of the Prior Art British Patent No. 1,241,851 describes a process for coating an article that comprises applying a film of an ethyleni-cally unsaturated ester having hydroxyl groups and exposing it to ionizing radiation. No liquid vehicle is used.
The coating composition of this invention comprises a similar resin in a vehicle that is a reactive monomer. This vehicle, when the coating composition is exposed to radiation and set, reacts with the resin and becomes an integral part of the resultant coating.
SUMMARY OF THE INVENTION
This invention provides a coating composition that com-prises an adduct of acrylic acid and an epoxy resin, or an anhydride modified adduct, and a reactive acrylate monomer. A
photosensitizer and a tertiary amine co-sensitizer are used in the case of ultraviolet (W) light cured coatings.
It also provides a W curable pigmented coating compo-- sition that contains a photosensitizer combination of 2-chloro-thioxanthone and a phenyl ketone.
It further provides a W curable coating composition - that affords improved film adhesion, in which at least part of the tertiary amine co-sensitizer is replaced with dimethylaminoethyl acrylate.
It still further provides substrates coated with the aforedefined coating composition. - -
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, ;~)85 DESCRIPTION OF SPECIFIC EMBODIMENTS
Prior practice has been to coat substrates, such as metals useful for container manufacture, with a variety of coating compositions comprising heat curable resinous components and non-reactive, volatile organic solvents that are removed from the coating during the curing process. Recent restrictions on allowable atmospheric pollutants, the shortage of organic sol-vents, and the shortage of fuels useful for firing curing ovens has created a need for coating compositions which can be cured with lower energy requirements and which eliminate the need for non-reactive organic solvents.
- The coating compositions of this invention comprise a ~-W light curable coating composition that comprises 10-30 weight percent of an adduct of acrylic acid and an epoxy resin, 40-60 weight percent of a monofunctional ester of acrylic acid, 0.1-2.0 weight percent of 2-chlorothioxanthone, 0.1-2.0 weight percent of a phenyl-ketone, 0.5-6 weight percent of a tertiary amine, and a : pigment.
- The epoxy resin can be any polyglycidyl ether of poly-hydric organic compounds, especially polyhydric phenols. Parti-cularly preferred are the glycidyl ethers of bisphenols~ a class of compounds which are constituted by a pair of phenolic groups interlinked through an intervening aliphatic bridge. While any of the bisphenols may be used, the compound 2,2-bis (p-hydroxy-phenyl) propane, commonly known as bisphenol A, is more widely ~-available in commerce and is preferred. While polyglycidyl ethers can be used, diglycidyl ethers are preferred.
Depending upon whether the epoxy resin is substantially -monomeric or polymerized to some degree, the preferred epoxy 30 resins will have an epoxy equivalent weight of between about 170 -~
and about 2,000 and an epoxy value between about 0.60 and about :'
, ;~)85 DESCRIPTION OF SPECIFIC EMBODIMENTS
Prior practice has been to coat substrates, such as metals useful for container manufacture, with a variety of coating compositions comprising heat curable resinous components and non-reactive, volatile organic solvents that are removed from the coating during the curing process. Recent restrictions on allowable atmospheric pollutants, the shortage of organic sol-vents, and the shortage of fuels useful for firing curing ovens has created a need for coating compositions which can be cured with lower energy requirements and which eliminate the need for non-reactive organic solvents.
- The coating compositions of this invention comprise a ~-W light curable coating composition that comprises 10-30 weight percent of an adduct of acrylic acid and an epoxy resin, 40-60 weight percent of a monofunctional ester of acrylic acid, 0.1-2.0 weight percent of 2-chlorothioxanthone, 0.1-2.0 weight percent of a phenyl-ketone, 0.5-6 weight percent of a tertiary amine, and a : pigment.
- The epoxy resin can be any polyglycidyl ether of poly-hydric organic compounds, especially polyhydric phenols. Parti-cularly preferred are the glycidyl ethers of bisphenols~ a class of compounds which are constituted by a pair of phenolic groups interlinked through an intervening aliphatic bridge. While any of the bisphenols may be used, the compound 2,2-bis (p-hydroxy-phenyl) propane, commonly known as bisphenol A, is more widely ~-available in commerce and is preferred. While polyglycidyl ethers can be used, diglycidyl ethers are preferred.
Depending upon whether the epoxy resin is substantially -monomeric or polymerized to some degree, the preferred epoxy 30 resins will have an epoxy equivalent weight of between about 170 -~
and about 2,000 and an epoxy value between about 0.60 and about :'
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~Q65~5 0.05. The preferred epoxy resins, i.e., those made from bisphenol A, will have two epoxy groups per molecule. Accordingly, the stoichiometric amount of acrylic acid to form a diacrylate adduct would be two moles of acid for each two epoxy groups, In practice, however, it is preferred to use slightly less acid than the amount necessary to cover both epoxy groups to be certain that there is no free acrylic acid remaining in the reaction product.
Free acid would contribute to excessive volatility of deposited films, while minor amounts of free epoxy are not objectionable.
Therefore, the amount of acrylic acid reacted can be between about 1.85 moles to 2.0 moles of acid per two epoxy groups. The esterification reaction between the acrylic acid and epoxy resin is carried out at an esterification temperature, e.g. between about 90C. and about 110C. Esterification is continued until an acid number of S-lS is obtained. This reaction ordinarily takes place in 8-lS hours.
In another embodiment of this invention, the epoxy di-acrylate is further reacted with an anhydride. Maleic anhydride ` is preferred but other anhydrides are contemplated for this pur-pose, such as citraconic anhydride, succinic anhydride, ethyl-succinic anhydride, amylenesuccinic anhydride, itaconic anhydride, glutaric anhydride, ~ 4-tetrahydrophthalic anhydride, phthalic anhydride, hemimellitic anhydride, trimellitic anhydride, and - pyromellitic anhydride. The amount of anhydride used will be between about 0.1 and about 1.0 mole anhydride per mole diacrylate resin. This reaction is generally carried out at temperatures between about 80C. and about 90C. The reaction is considered complete when the alcoholic KOH and aqueous KOH acid numbers agree, i.e., about 10-40. This evidences a complete absence of anhydride functionality.
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~ 6~085 The esterification reaction and the further reaction with anhydride can occur without the aid of a catalyst. However, catalysts are preferred such as tertiary amines; quaternary ammonium hydroxides, such as benzyltrimethylammonium hydroxide;
N,N-dimethylaniline; N,N-benzylmethylamine; triethylamine; and KOH. It is also advantageous to use small amounts of hydroquinone as a polymerization inhibitor.
The epoxy diacrylate or the anhydride modified epoxy diacrylate, prepared as aforedescribed, is then dissolved in a 10 reactive monomer vehicle to prepare the coating composition. The reactive monomer vehicle contemplated herein is a monofunctional -~ ester of acrylic acid having from 4 to about 20 carbon atoms. The ;~ acrylate ester can be an alkyl or hydroxyalkyl acrylate, such as methyl acrylate, ethylacrylate, hydroxyethyl acrylate, propyl acrylate, isopropyl acrylate, hydroxypropyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, and hexadecyl acrylate. Also contemplated are the acrylic esters of the well known class of ether alcohols 20 having the formula: ROCH2CH2OH, wherein R is Cl-C6 alkyl or i phenyl, i.e. the "Cellosolves"*. Examples of such esters are methoxyethyl acrylate (Methyl "Cellosolve" acrylate), ethoxyethyl acrylate ("Cellosolve" acrylate), butoxyethyl acrylate (Butyl "Cellosolve" acrylate), isobutoxyethyl acrylate ~Isobutyl "Cello-solve" acrylate), hexoxyethyl acrylate (Hexyl "Cellosolve" acrylate), and phenoxyethyl acrylate (Phenyl "Cellosolve" acrylate). The contemplated reactive monomer vehicle can be designated by the f formula: CH2-CH2COOR', wherein R' is hydrogen, Cl-C15 alkyl, or ~-~
s -C2H4OR'' wherein R'' is Cl-C6 alkyl or phenyl. The reactive 30 monomer vehicle can contain a minor amount (up to about 20 weight * Trademark for mono- and dialkyl ethers of ethylene glycol and their derivatives.
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10~50~35 per cent) of a polyfunctional acrylate, e.g., neopentyl glycol diacrylate, but it is predominantly monofunctional.
The coating composition is cured by exposure to radia-tion. When the radiation used is electron beam radiation a ` photosensitizer is not needed, but when ultraviolet light is used, a photosensitizer is needed. Suitable sensitizers include acetophenone, benzophenone, xanthone, benzoin isobutyl ether, and 2-chlorothioxanthone. 2-Chlorothioxanthone is preferred, particularly when the formulation is pigmented. A tertiary amine ;~ 10 co-sensitizer is also used in the U.V. curable coating formula-tion and serves to speed up the cure rate. In order to realize this function, it is necessary to have free amine present.
Accordingly, the amine concentration range is from about 1.25 to about 3 times the amount required to neutralize free acidity.
The amount required for neutralization can be readily calculated from the determined acid number of the resin. The tertiary amines are normally liquid trialkylamines, trialkanolamines, or : , .
tertiary mixed alkylalkanolamines. Non-limiting examples of such amines are triethylamine, triisopropylamine, tributylamine, tri-;~20 hexylamine, tri-2-ethyl-hexylamine, tridodecylamine, methyldi-ethanolamine, dimethylethanolamine, 2-hydroxyethyldiisopropyl-amine, and triethanolamine.
The coating compositions described so far produce clear coatings and are useful as such.
Although a pigment is not necessary, it is preferred to incorporate a pigment into the coating composition of this inven-tion. The preferred pigment is titanium dioxide for white base coats, but any well known filler pigment can be used, such as zinc oxide, bentonite, silica, ochers, and chrome yellows or greens.
Depending upon whether the coating composition is pig-mented or not, the broad and preferred ranges of concentration of the components are as set forth in the following Table I.
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10~i5085 The coating composition is applied to a usual substrate metal, paper, leather, cloth, etc. using any of the usual methods of application, including wiping, spraying and rollcoat applica-tion. Suitable metallic substrates include aluminum, steel, and tin-plated steel. The rate of application will be sufficient to apply the coating at about 1-20 mg/sq. in. After application, the coating is set by exposure to radiation for between about 0.01 second and about 30 seconds. In some cases, the coating will be set by short exposure to radiation, e.g. less than one second, which is sufficient to set the film so that it will accept inks and/or a wet-ink varnish. Following the printing or varnishing .,. :
operation, these coats may be further set by baking at about 250F.
; to 450F. for between about 3 seconds and about 5 minutes.
Suitable sources of radiation are ultraviolet light or electron beam radiation. Preferably, an ultraviolet light of a wave length below 4000 Angstrom Units is used. The electron beam radiation is obtained from high energy electrons produced by high voltage electron accelerators. These are well known and include the VandeGraaff accelerator, resonant transformers, transformer rectifiers, micro-wave waveguide linear accelerator, and synchro-trons.
- The following examples demonstrate the preparation of adducts and coatings containing them, in accordance with this invention.
Using a vessel equipped with an agitator, a reflux con-denser, an inert gas inlet and a charging port, there was charged 660 grams "Epon"* 828. "Epon" 828 is a diglycidyl ether of bis-phenol A having an epoxy equivalent weight of about 185-192 and an epoxide value of 0.50-0.54. Through the gas inlet was introduced ,, : .
* "Epon" Resins is the trademark for a series of condensation products of epichlorohydrin and bisphenol-A.
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~ 0~ 5 a nitrogen flow which was maintained throughout the resin pre-paration cycle. While under agitation, 238 grams glacial acrylic acid was added and stirred until epoxy resin dissolved. Upon dissolution of the acrylic acid, 1.3 grams triethyl amine and 0.1 gram hydroquinone were added. Under continued agitation, heat was raised to 205-212F. and held at this temperature until an acid number of 5-10 was obtained (approximately 10 hours). Temper-ature was reduced to 150-160F. and 600 grams hydroxypropyl acry-late was added and the mixture was stirred until uniform. The final product was a clear solution of prepolymer in monomer at a 60/40 weight ratio.
Using a vessel equipped as in the previous example, there were charged 7200 g. "Epon" 828, 2590 g. glacial acrylic acid, 15 g. triethyl amine and 1.2 g. hydroquinone. Agitation was started along with nitrogen flow and the mixture was heated to 100C.
Temperature was maintained at 95-100C. until an acid number of 5-10 was obtained; at this point, was added 432 g. maleic anhydride and the temperature was held at 90C. until the acid number, as determined by alcoholic KOH and aqueous KOH, agreed, thereby indicating the complete absence of anhydride functionality. The normal time for this phase of the resin preparation was 1.5 hours.
At this point, was added 6835 g. hydroxypropyl acrylate. The final product was a 60/40 ratio of prepolymer/monomer having a viscosity of 850-900 cp at 80F. a w~ight/gallon of 9.5 pounds/
gallon, and an acid value of 28-35. The molar ratio of maleic anhydride to epoxy resin was 0.25.
The following Examples 3 and 4 demonstrate coatings curable by electron beam radiation.
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EXA~LE 3 In a suitable sized high speed disperser, were thorough-ly mixed 27.1 pounds of the product from Example l and 42.8 pounds titanium dioxide pigment and the mixture was stirred until a fineness of grind of 7 or better was obtained. Then were added 31.4 pounds hydroxypropyl acrylate, and 20.2 pounds of the product from Example l and the mixture was stirred until uniform. The ;
resultant finish had a pigment/binder ratio of 0.52/l and a pre-polymer~total binder ratio of 0.4/1.
Using the equipment of Example 3, were thoroughly mixed ~ 27.3 pounds of the resin solution of Example 2, and 42.9 pounds of -~ titanium dioxide pigment. Continued high speed agitation until a fineness of grind of 7 minimum was obtained. Agitation was con-tinued but at slower speed, while adding lO.0 pounds of resin solution of Example 2 and 17.5 pounds of hydroxypropyl acrylate.
This was stirred until uniform. The resultant finish had a pig-ment/binder ratio of 0.78/l and a prepolymer/total binder ratio of 0.4/l.
To a suitable sized pebble mill, were charged one pound 2-chlorothioxanthone and 2 pounds hydroxypropyl acrylate. This was ground for 24 hours, until thoroughly dispersed. The product is suited for use as a photoinitiator for pigmented finishes.
In a suitably sized high speed disperser, were thorough-ly mixed 27.1 pounds of the product from Example l, 42.8 pounds ; titanium dioxide pigment, and 1.5 pounds of the product of Example 5. This was stirred until a fineness of grind of 7 or better was obtained. Then, were added 31.4 pounds hydroxypropyl acrylate, 2.0 pounds methyldiethanolamine and 20.2 pounds of the product of .: :
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Example 1. The mixture was stirred until uniform. The resultant finish had a pigment/binder ratio of 0.52/1 and a prepolymer/
total binder ratio of 0.4/1.
' using the equipment of Example 6, were thoroughly mixed 27.3 pounds of the resin solution of Example 2, 42.9 pounds of titanium dioxide pigment, and 0.8 pounds of 2-chlorothioxanthone.
High speed agitation was continued until a fineness of grind of 7 minimum was obtained. Agitation was continued but at slower 10 speed while adding 10.0 pounds of resin solution of Example 2, 17.5 pounds of hydroxypropyl acrylate, and 1.5 pounds of methyldi-ethanolamine. This was stirred until uniform. The resultant finish had a pigment/binder ratio of 0.78/1 and a prepolymer/
`~ total binder ratio of 0.4/1.
EXAMPLES 8 through 27 . . :
In Table II are set forth data on various coatings pre-pared using the techniques and methods set forth in Examples 1 through 7. Each coating was applied to various substrates, cured by ultraviolet light (W) or electron beam (FB), and tested for -~:
20 film properties. The adhesion test is carried out by cross-- hatching a coated area with individual score lines approximately 1/16 inch apart. Then "Scotch"* tape is firmly applied to the cross-hatched area and removed with a quick snap. The amount of ~ coating remaining on the panel is observed visually and rated on ? a percentage basis. Pasteurization is carried out by immersing the coated panels in water at 155F. for 30 minutes. Then, the panels are wiped dry with an absorbent towel and the adhesion test is carried out as aforedescribed.
30 * Trademark of the 3-M Company, for a line of pressure-sensitive ~` adhesive tapes.
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11)6SV85 In Table II, the following abbreviations are used:
1004 = "Epon" 1004 Re~ction product epichlorohydrin and bisphenol A. M.W. about 1400, Epoxide value 0.10 - 0.12.
828 = "Epon" 828 Diglycidylether of bisphenol A.
M.W. about 350 - 400. Epoxide value 0.50 -0.54.
A = 2 moles acrylic acid per mole epoxy M = . 25 moles maleic anhydride per mole epoxy HPA = Hydroxypropyl Acrylate HEA = Hydroxyethyl Acrylate 2-EHA = 2-Ethylhexyl Acrylate MDEOA = Methyldiethanolamine TEOA = Triethanolamine cps = Centipoise Al = Aluminum -~
CCO = Chrome-chrome oxide treated steel -CDC5 = #5 grade of tinplate steel TiO2 = Titanium Dioxide THP = ~ 4-Tetrahydrophthalic anhydride CTX = 2-Chlorothioxanthone i Monomer = Reactive monomer vehicle UV-25 = Ultraviolet light at line speed 25 ft./min per lamp. -EB-2 = Electron beam radiation at 2 megarad dosage . ~:
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, : ~0~50~5 The results given in Table I indicate that:
a) Increasing epoxy resin molecular weight improves adhesion to metals.
b) Maleic anhydride adducts have better adhesion to metals and demonstrate better leveling than compositions contain-ing resins containing no maleic anhydride.
c) Coatings containing TiO2 have better adhesion to metals than do coatings of identical composition but without TiO2.
The coating compositions that have been described and illustrated hereinbefore can be considered the "basic" coating compositions. It has been found that certain properties of the cured film can be markedly improved by incorporating additional - chemicals into the basic coating compositions.
With the basic W curable coating compositions, the gloss of the cured film is usually lower than desired, particularly at higher cure rates. This gloss can be markedly increased by using in the coating composition a sensitizer combination of 2-chlorothioxanthone and a phenyl ketone. Benzophenone is the pre-ferred phenyl ketone, but other phenyl ketones are contemplated, 20 such as acetophenone, propiophenone, and butyrophenone. ~ -The following examples demonstrate this gloss improve-ment. In each example, using the techniques and methods of Examples 1-7, a pigmented coating composition (A) without benzo-phenone (Bzph) and (B) with benzophenone were coated on aluminum and exposed to W at various cure speeds. The resulting films were tested for 60 gloss. --An epoxy diacrylate of "Epon" 828 was modified with 0.25 mole maleic anhydride per mole epoxy. This resin (Resin A) was admixed with hydroxypropyl acrylate, TiO2 pigment, and sensitizers -~and co-sensitizers. The following tabulation sets forth amounts . .
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lOf~SOIB5 of components, pigment/binder ratio (P/B), resin/binder ratio (R/B), and pertinent test data.
Example Ti~2 CTX M~EOA Resin A
--- _ 28A 36.6 0.9 3.6 24.5 28B 36.6 0.9 3.6 24.5 Example HPA Bzph P R/B
28A 34.4 0 .58 .39 28B 32.4 2.0 .58 .39 No Bzph 2~ Bzph 10W C re Speed 25 FPMYield 90 90 Gloss 79 88 An epoxy diacrylate of "Epon" 828 (Resin B) was admixed -;
with hydroxypropyl acrylate, Tio2 pigment, and sensitizers and co-sensitizers. The following tabulation sets forth amounts of com-ponents and pertinent test data.
Exam~le TiO2Resin B HPA CTX ~-29A 42.828.6 25.6 1.0 29B 41.527.7 24.8 1.0 20Example MDEOABzph P/B R/B
29A 2.0 0 .75 .50 29B 3.0 2.0 .71 .475 W Cure Speed, FPM ~
No Bzph 2~ Bzph ~-~ 25 Yield 94 91 - Gloss 95 95 ~ ~;
Yield 91 87 Gloss 77 93 100 Yield 87 84 ; 30 Gloss 39 90 .', . ' .
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~LO~OB5 An epoxy diacrylate of "Epon" 1004 was modified with 0.25 mole m leic anhydride per mole epoxy. This resin (Resin C) was admixed with hydroxypropylacrylate, TiO2 pigment, and sensi-tizers and co-sensitizers. The following tabulation sets forth amounts of components and pertinent test data.
Example TiO2 Resin CCTX
;, 30A 33.3 20.0 1.0 30B 33.0 19.8 1.0 10Example MDEOA HPA Bzph 30A 4.0 41.7 0 ` 30B 4.0 41.2 1.0 W Cure Speed, FPM
No Bzph2% Bzph Yield 88 88 Gloss 89 89 Yield 86 85 Gloss 75 88 100 Yield 73 77 -~loss 45 62 The preceding examples illustrate that benzophenone (a phenyl ketone) combined with 2-chlorothioxanthone has essentially no effect on film yield, but increases the gloss of pigmented W
curable coatings. Each sensitizer is us~d, as described herein-before, in amounts of between about 0.1~ and about 2% by weight.
It has been found that adhesion of the cured coating to some substrates, particularly pasteurized adhesion ~Past. Adh.), is improved by using dimethylaminoethyl acrylate (DMAEA) in the coating composition. In the case of EB curable coatings, the DMAEA is added to the coating composition in amounts of between about 0.5% and about 6% by weight. In the case of W curable coatings the ~MAEA is used in amounts of between about 0.5% and about 6~ by weight to replace all or a part of the tertiary amine co-sensitizer.
, .,: `- , Resin B (Example 29) was admixed with hydroxypropyl acrylate, 2-chlorothioxanthone, and MDEOA or DMAEA. Each coating : was coated on aluminum panels and W cured. The coated panels were subjected to adhesion tests. Amounts of components and test results are set forth ln the following tabulation.
Example Resin B ''CTX HPA MDEOA DMAEA
31A 49.51.0 44.5 0 5 31B 50.01.0 47.0 2 0 ' ' _' ' 50 FPM UV'Cure '' ' Film Example YieldAdhesion P'ast.'Adh.
Resin C (Example 30) was admixed with hydroxypropyl acrylate, 2-chlorothioxanthone, and MDEOA or DMAEA. Each coating - was coated on aluminum panels and W cured. The coated panels were subjected to adhesion tests. Amounts of components and test ; 20 results are set forth in the following tabulation.
' Resin Example C HPA CTX MDEOA DMAEA -~
' 32A 29.2 68.2 0.5 ~ , 32B 29.2 68.2 0.5 0 2 ,~
, W Cure ~ '' -,',' Speed, Film Past.
s Example FPM ~ield Adh. A'dh.
, 50 87 100 70 ',' 30 32B 25 89 100 100 , 50 87 100 100 ..
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,' 106S~j5 Resin B (Example 29) was admixed with hydroxypropyl acrylate, TiO2 pigment, 1.0% 2-chlorothioxanthone, and MDEOA or DMAEA. The P/B of each coating was 0.75 and the R/B was 0.40.
Each coating was coated on metal panels and W cured. The coated panels were subjected to adhesion tests. Results are set forth in the following tabulation.
Viscosity, c~
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Example Amine222 sec 1 0228 sec 1 1033A 4% MDEOA395 29,100 33B 5% DMAEA 283 564 50 FPM Adhesion to Example Yield Al CCO
. . .
Resin B (Example 29) was admixed with hydroxypropyl acrylate, TiO2 pigment, 1.0% 2-chlorothioxanthone, and MDEOA or ~- DMAEA. The P/B of each coating was 0.75 and the R/~ was 0.6.
Each coating was coated on metal panels and UV cured. The coated panels were subjected to adhesion tests. Results are set forth ,: , in the following tabulation.
Example Amine 222 sec 1 .0228 sec 1 . . _ - 34A 4% MDEOA 80086,100 34B 5% DMAEA 59814,800 50 FPM Adhesion to Example Yield Al CCO
: 34B 89 100 100 It will be noted from the preceding examples that the use of dimethylaminoethyl acrylate gives at least equivalent W -cure. It also provides improved adhesion, both dry and wet.
The following examples are illustrative of preferred coating compositions of this invention.
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Using a reaction vessel equipped with an agitator, a reflux condenser, an inert gas inlet and a charging port, there were charged 525 g. "Epon" 1004 and 70 g. toluene. Heat, agita-tion, and slow inert gas flow were started. Temperature was raised to reflux to remove water (a pot temperature of 150-160C.).
The mixture was cooled to 80-85C. and there were added 40 g.
glacial acrylic acid, 1 g. triethyl amine and 0.1 g. hydroquinone.
Temperature was raised to 95-100C. for esterification and the reaction continued until an acid number of 8-13 was obtained.
This was cooled to 80-85C. and there was added 7 g. maleic anhydride. Temperature was held at 80-85C. for 1-1/2 to 2 hours until alcoholic KOH and aqueous KOH acid numbers agreed (10-15).
- Heat source was removed and 175 g. hydroxypropyl acrylate was added. The mixture was reheated to 80-85C. and vacuum applied for toluene removal. Removed heat and added an additional 182 g.
hydroxypropyl acrylate. The final product had a viscosity of 45-50,000 cp., a wt./gal. of 9.6 lb., an acid number of 10.5 and a `A, total solids of approximately 97%. This resin was used in the ; 20 formulations of Examples 36-38 (amounts are wt. ~ of formulation):
EXAMPLES 36-38 (Clear Finishes) Ingredient 36 37 38 Example 35 Composition 40.3 56.4 33.2 Hydroxypropyl acrylate 56.3 40.2 37.6 Phenyl "Cellosolve" acrylate - - 21.8 Methyldiethanolamine 1.9 1.9 2.9 ` Dimethylaminoethyl acrylate - - 3.5 2-Chlorothioxanthone 0.5 0.5 0.5 Fluorocarbon wetting agent - - 0.5 Silicone lubricant 1.0 1.0 Viscosity (seconds #4 Ford Cup) 50-60 175-225 30-35 Wt./gal. (lb.) 9.04 9.40 8.95 , -:
. . . -10~50l~5 Examples 36 and 37 were formulated as an abrasion resistant coating for can bottoms, which is applied by a wiping action and given a uv treatment of 1-2 seconds with no post bake required.
Example 38 was formulated as a coating for flat sheet -~and is suitable for rollcoat application and given 1 second exposure to W radiation, followed by a 10 minute oven bake at 340-400F. The Phenyl "Cellosolve" acrylate in Example 38 imparts improved corrosion resistance and flexibility.
There were charged 312 g. of an epoxy diacrylate made from "Epon" 828 and acrylic acid, 430 g. titanium dioxide, 198 g.
"Cellosolve" acrylate, 10 g. 2-chlorothioxanthone, 40 g. dimethyl-aminoethyl acrylate and 10 g. benzophenone to a suitably sized pebble mill and ground to a fineness of 7 when measured on a Hegman fineness of grind gauge. Grind time is 24-48 hours. The final product was a white finish suitable for rollcoat applica- -tion on flat sheet. The finish had a viscosity of 90-100 sec.
#4 Ford Cup and a weight per gallon of 13.1-13.3 pounds. It is normally applied at 10 mg./sq. in. and cured using a 1 sec. W
, exposure followed by a 6 minute bake at 325F. After the W
;~ exposure, the film was sufficiently set to accept inks and a wet `
ink varnish. The 6 min. at 325F. bake indicated above followed inking and varnishing operations.
It will be noted that in Examples 38 and 39, Dimethyl-aminoethyl acrylate was used. This compound has a tertiary amine functionality. Thus, as aforedescribed, it can replace the tertiary amine (used to speed up the cure rate) partially (Example 38) or entirely (Example 39). This compound also has reactive ethylenically unsaturated functionality (acrylate) and therefore acts as a reactive monomer. Its use affords a coating : , ., - .
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~ composition having improved rheology, as evidenced by better flow ; characteristics, and the cured coatlng has improved adhesion to metal substrates. The addition of benzophenone to the coating composition (Example 39) improves the gloss of the pigmented finish.
Other well known adju~ants may be added to the coating composition such as flow control agents and waxes. waxes, if used, are added as slurries or emulsions of petroleum (paraffin) wax, `~ natural waxes such as montan wax, beeswax, and carnauba wax, or 10 synthetic waxes such as polyethylene wax.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications ` and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.
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~Q65~5 0.05. The preferred epoxy resins, i.e., those made from bisphenol A, will have two epoxy groups per molecule. Accordingly, the stoichiometric amount of acrylic acid to form a diacrylate adduct would be two moles of acid for each two epoxy groups, In practice, however, it is preferred to use slightly less acid than the amount necessary to cover both epoxy groups to be certain that there is no free acrylic acid remaining in the reaction product.
Free acid would contribute to excessive volatility of deposited films, while minor amounts of free epoxy are not objectionable.
Therefore, the amount of acrylic acid reacted can be between about 1.85 moles to 2.0 moles of acid per two epoxy groups. The esterification reaction between the acrylic acid and epoxy resin is carried out at an esterification temperature, e.g. between about 90C. and about 110C. Esterification is continued until an acid number of S-lS is obtained. This reaction ordinarily takes place in 8-lS hours.
In another embodiment of this invention, the epoxy di-acrylate is further reacted with an anhydride. Maleic anhydride ` is preferred but other anhydrides are contemplated for this pur-pose, such as citraconic anhydride, succinic anhydride, ethyl-succinic anhydride, amylenesuccinic anhydride, itaconic anhydride, glutaric anhydride, ~ 4-tetrahydrophthalic anhydride, phthalic anhydride, hemimellitic anhydride, trimellitic anhydride, and - pyromellitic anhydride. The amount of anhydride used will be between about 0.1 and about 1.0 mole anhydride per mole diacrylate resin. This reaction is generally carried out at temperatures between about 80C. and about 90C. The reaction is considered complete when the alcoholic KOH and aqueous KOH acid numbers agree, i.e., about 10-40. This evidences a complete absence of anhydride functionality.
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~ 6~085 The esterification reaction and the further reaction with anhydride can occur without the aid of a catalyst. However, catalysts are preferred such as tertiary amines; quaternary ammonium hydroxides, such as benzyltrimethylammonium hydroxide;
N,N-dimethylaniline; N,N-benzylmethylamine; triethylamine; and KOH. It is also advantageous to use small amounts of hydroquinone as a polymerization inhibitor.
The epoxy diacrylate or the anhydride modified epoxy diacrylate, prepared as aforedescribed, is then dissolved in a 10 reactive monomer vehicle to prepare the coating composition. The reactive monomer vehicle contemplated herein is a monofunctional -~ ester of acrylic acid having from 4 to about 20 carbon atoms. The ;~ acrylate ester can be an alkyl or hydroxyalkyl acrylate, such as methyl acrylate, ethylacrylate, hydroxyethyl acrylate, propyl acrylate, isopropyl acrylate, hydroxypropyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, and hexadecyl acrylate. Also contemplated are the acrylic esters of the well known class of ether alcohols 20 having the formula: ROCH2CH2OH, wherein R is Cl-C6 alkyl or i phenyl, i.e. the "Cellosolves"*. Examples of such esters are methoxyethyl acrylate (Methyl "Cellosolve" acrylate), ethoxyethyl acrylate ("Cellosolve" acrylate), butoxyethyl acrylate (Butyl "Cellosolve" acrylate), isobutoxyethyl acrylate ~Isobutyl "Cello-solve" acrylate), hexoxyethyl acrylate (Hexyl "Cellosolve" acrylate), and phenoxyethyl acrylate (Phenyl "Cellosolve" acrylate). The contemplated reactive monomer vehicle can be designated by the f formula: CH2-CH2COOR', wherein R' is hydrogen, Cl-C15 alkyl, or ~-~
s -C2H4OR'' wherein R'' is Cl-C6 alkyl or phenyl. The reactive 30 monomer vehicle can contain a minor amount (up to about 20 weight * Trademark for mono- and dialkyl ethers of ethylene glycol and their derivatives.
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10~50~35 per cent) of a polyfunctional acrylate, e.g., neopentyl glycol diacrylate, but it is predominantly monofunctional.
The coating composition is cured by exposure to radia-tion. When the radiation used is electron beam radiation a ` photosensitizer is not needed, but when ultraviolet light is used, a photosensitizer is needed. Suitable sensitizers include acetophenone, benzophenone, xanthone, benzoin isobutyl ether, and 2-chlorothioxanthone. 2-Chlorothioxanthone is preferred, particularly when the formulation is pigmented. A tertiary amine ;~ 10 co-sensitizer is also used in the U.V. curable coating formula-tion and serves to speed up the cure rate. In order to realize this function, it is necessary to have free amine present.
Accordingly, the amine concentration range is from about 1.25 to about 3 times the amount required to neutralize free acidity.
The amount required for neutralization can be readily calculated from the determined acid number of the resin. The tertiary amines are normally liquid trialkylamines, trialkanolamines, or : , .
tertiary mixed alkylalkanolamines. Non-limiting examples of such amines are triethylamine, triisopropylamine, tributylamine, tri-;~20 hexylamine, tri-2-ethyl-hexylamine, tridodecylamine, methyldi-ethanolamine, dimethylethanolamine, 2-hydroxyethyldiisopropyl-amine, and triethanolamine.
The coating compositions described so far produce clear coatings and are useful as such.
Although a pigment is not necessary, it is preferred to incorporate a pigment into the coating composition of this inven-tion. The preferred pigment is titanium dioxide for white base coats, but any well known filler pigment can be used, such as zinc oxide, bentonite, silica, ochers, and chrome yellows or greens.
Depending upon whether the coating composition is pig-mented or not, the broad and preferred ranges of concentration of the components are as set forth in the following Table I.
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10~i5085 The coating composition is applied to a usual substrate metal, paper, leather, cloth, etc. using any of the usual methods of application, including wiping, spraying and rollcoat applica-tion. Suitable metallic substrates include aluminum, steel, and tin-plated steel. The rate of application will be sufficient to apply the coating at about 1-20 mg/sq. in. After application, the coating is set by exposure to radiation for between about 0.01 second and about 30 seconds. In some cases, the coating will be set by short exposure to radiation, e.g. less than one second, which is sufficient to set the film so that it will accept inks and/or a wet-ink varnish. Following the printing or varnishing .,. :
operation, these coats may be further set by baking at about 250F.
; to 450F. for between about 3 seconds and about 5 minutes.
Suitable sources of radiation are ultraviolet light or electron beam radiation. Preferably, an ultraviolet light of a wave length below 4000 Angstrom Units is used. The electron beam radiation is obtained from high energy electrons produced by high voltage electron accelerators. These are well known and include the VandeGraaff accelerator, resonant transformers, transformer rectifiers, micro-wave waveguide linear accelerator, and synchro-trons.
- The following examples demonstrate the preparation of adducts and coatings containing them, in accordance with this invention.
Using a vessel equipped with an agitator, a reflux con-denser, an inert gas inlet and a charging port, there was charged 660 grams "Epon"* 828. "Epon" 828 is a diglycidyl ether of bis-phenol A having an epoxy equivalent weight of about 185-192 and an epoxide value of 0.50-0.54. Through the gas inlet was introduced ,, : .
* "Epon" Resins is the trademark for a series of condensation products of epichlorohydrin and bisphenol-A.
- . . . :
~ 0~ 5 a nitrogen flow which was maintained throughout the resin pre-paration cycle. While under agitation, 238 grams glacial acrylic acid was added and stirred until epoxy resin dissolved. Upon dissolution of the acrylic acid, 1.3 grams triethyl amine and 0.1 gram hydroquinone were added. Under continued agitation, heat was raised to 205-212F. and held at this temperature until an acid number of 5-10 was obtained (approximately 10 hours). Temper-ature was reduced to 150-160F. and 600 grams hydroxypropyl acry-late was added and the mixture was stirred until uniform. The final product was a clear solution of prepolymer in monomer at a 60/40 weight ratio.
Using a vessel equipped as in the previous example, there were charged 7200 g. "Epon" 828, 2590 g. glacial acrylic acid, 15 g. triethyl amine and 1.2 g. hydroquinone. Agitation was started along with nitrogen flow and the mixture was heated to 100C.
Temperature was maintained at 95-100C. until an acid number of 5-10 was obtained; at this point, was added 432 g. maleic anhydride and the temperature was held at 90C. until the acid number, as determined by alcoholic KOH and aqueous KOH, agreed, thereby indicating the complete absence of anhydride functionality. The normal time for this phase of the resin preparation was 1.5 hours.
At this point, was added 6835 g. hydroxypropyl acrylate. The final product was a 60/40 ratio of prepolymer/monomer having a viscosity of 850-900 cp at 80F. a w~ight/gallon of 9.5 pounds/
gallon, and an acid value of 28-35. The molar ratio of maleic anhydride to epoxy resin was 0.25.
The following Examples 3 and 4 demonstrate coatings curable by electron beam radiation.
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EXA~LE 3 In a suitable sized high speed disperser, were thorough-ly mixed 27.1 pounds of the product from Example l and 42.8 pounds titanium dioxide pigment and the mixture was stirred until a fineness of grind of 7 or better was obtained. Then were added 31.4 pounds hydroxypropyl acrylate, and 20.2 pounds of the product from Example l and the mixture was stirred until uniform. The ;
resultant finish had a pigment/binder ratio of 0.52/l and a pre-polymer~total binder ratio of 0.4/1.
Using the equipment of Example 3, were thoroughly mixed ~ 27.3 pounds of the resin solution of Example 2, and 42.9 pounds of -~ titanium dioxide pigment. Continued high speed agitation until a fineness of grind of 7 minimum was obtained. Agitation was con-tinued but at slower speed, while adding lO.0 pounds of resin solution of Example 2 and 17.5 pounds of hydroxypropyl acrylate.
This was stirred until uniform. The resultant finish had a pig-ment/binder ratio of 0.78/l and a prepolymer/total binder ratio of 0.4/l.
To a suitable sized pebble mill, were charged one pound 2-chlorothioxanthone and 2 pounds hydroxypropyl acrylate. This was ground for 24 hours, until thoroughly dispersed. The product is suited for use as a photoinitiator for pigmented finishes.
In a suitably sized high speed disperser, were thorough-ly mixed 27.1 pounds of the product from Example l, 42.8 pounds ; titanium dioxide pigment, and 1.5 pounds of the product of Example 5. This was stirred until a fineness of grind of 7 or better was obtained. Then, were added 31.4 pounds hydroxypropyl acrylate, 2.0 pounds methyldiethanolamine and 20.2 pounds of the product of .: :
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Example 1. The mixture was stirred until uniform. The resultant finish had a pigment/binder ratio of 0.52/1 and a prepolymer/
total binder ratio of 0.4/1.
' using the equipment of Example 6, were thoroughly mixed 27.3 pounds of the resin solution of Example 2, 42.9 pounds of titanium dioxide pigment, and 0.8 pounds of 2-chlorothioxanthone.
High speed agitation was continued until a fineness of grind of 7 minimum was obtained. Agitation was continued but at slower 10 speed while adding 10.0 pounds of resin solution of Example 2, 17.5 pounds of hydroxypropyl acrylate, and 1.5 pounds of methyldi-ethanolamine. This was stirred until uniform. The resultant finish had a pigment/binder ratio of 0.78/1 and a prepolymer/
`~ total binder ratio of 0.4/1.
EXAMPLES 8 through 27 . . :
In Table II are set forth data on various coatings pre-pared using the techniques and methods set forth in Examples 1 through 7. Each coating was applied to various substrates, cured by ultraviolet light (W) or electron beam (FB), and tested for -~:
20 film properties. The adhesion test is carried out by cross-- hatching a coated area with individual score lines approximately 1/16 inch apart. Then "Scotch"* tape is firmly applied to the cross-hatched area and removed with a quick snap. The amount of ~ coating remaining on the panel is observed visually and rated on ? a percentage basis. Pasteurization is carried out by immersing the coated panels in water at 155F. for 30 minutes. Then, the panels are wiped dry with an absorbent towel and the adhesion test is carried out as aforedescribed.
30 * Trademark of the 3-M Company, for a line of pressure-sensitive ~` adhesive tapes.
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11)6SV85 In Table II, the following abbreviations are used:
1004 = "Epon" 1004 Re~ction product epichlorohydrin and bisphenol A. M.W. about 1400, Epoxide value 0.10 - 0.12.
828 = "Epon" 828 Diglycidylether of bisphenol A.
M.W. about 350 - 400. Epoxide value 0.50 -0.54.
A = 2 moles acrylic acid per mole epoxy M = . 25 moles maleic anhydride per mole epoxy HPA = Hydroxypropyl Acrylate HEA = Hydroxyethyl Acrylate 2-EHA = 2-Ethylhexyl Acrylate MDEOA = Methyldiethanolamine TEOA = Triethanolamine cps = Centipoise Al = Aluminum -~
CCO = Chrome-chrome oxide treated steel -CDC5 = #5 grade of tinplate steel TiO2 = Titanium Dioxide THP = ~ 4-Tetrahydrophthalic anhydride CTX = 2-Chlorothioxanthone i Monomer = Reactive monomer vehicle UV-25 = Ultraviolet light at line speed 25 ft./min per lamp. -EB-2 = Electron beam radiation at 2 megarad dosage . ~:
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, : ~0~50~5 The results given in Table I indicate that:
a) Increasing epoxy resin molecular weight improves adhesion to metals.
b) Maleic anhydride adducts have better adhesion to metals and demonstrate better leveling than compositions contain-ing resins containing no maleic anhydride.
c) Coatings containing TiO2 have better adhesion to metals than do coatings of identical composition but without TiO2.
The coating compositions that have been described and illustrated hereinbefore can be considered the "basic" coating compositions. It has been found that certain properties of the cured film can be markedly improved by incorporating additional - chemicals into the basic coating compositions.
With the basic W curable coating compositions, the gloss of the cured film is usually lower than desired, particularly at higher cure rates. This gloss can be markedly increased by using in the coating composition a sensitizer combination of 2-chlorothioxanthone and a phenyl ketone. Benzophenone is the pre-ferred phenyl ketone, but other phenyl ketones are contemplated, 20 such as acetophenone, propiophenone, and butyrophenone. ~ -The following examples demonstrate this gloss improve-ment. In each example, using the techniques and methods of Examples 1-7, a pigmented coating composition (A) without benzo-phenone (Bzph) and (B) with benzophenone were coated on aluminum and exposed to W at various cure speeds. The resulting films were tested for 60 gloss. --An epoxy diacrylate of "Epon" 828 was modified with 0.25 mole maleic anhydride per mole epoxy. This resin (Resin A) was admixed with hydroxypropyl acrylate, TiO2 pigment, and sensitizers -~and co-sensitizers. The following tabulation sets forth amounts . .
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lOf~SOIB5 of components, pigment/binder ratio (P/B), resin/binder ratio (R/B), and pertinent test data.
Example Ti~2 CTX M~EOA Resin A
--- _ 28A 36.6 0.9 3.6 24.5 28B 36.6 0.9 3.6 24.5 Example HPA Bzph P R/B
28A 34.4 0 .58 .39 28B 32.4 2.0 .58 .39 No Bzph 2~ Bzph 10W C re Speed 25 FPMYield 90 90 Gloss 79 88 An epoxy diacrylate of "Epon" 828 (Resin B) was admixed -;
with hydroxypropyl acrylate, Tio2 pigment, and sensitizers and co-sensitizers. The following tabulation sets forth amounts of com-ponents and pertinent test data.
Exam~le TiO2Resin B HPA CTX ~-29A 42.828.6 25.6 1.0 29B 41.527.7 24.8 1.0 20Example MDEOABzph P/B R/B
29A 2.0 0 .75 .50 29B 3.0 2.0 .71 .475 W Cure Speed, FPM ~
No Bzph 2~ Bzph ~-~ 25 Yield 94 91 - Gloss 95 95 ~ ~;
Yield 91 87 Gloss 77 93 100 Yield 87 84 ; 30 Gloss 39 90 .', . ' .
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~LO~OB5 An epoxy diacrylate of "Epon" 1004 was modified with 0.25 mole m leic anhydride per mole epoxy. This resin (Resin C) was admixed with hydroxypropylacrylate, TiO2 pigment, and sensi-tizers and co-sensitizers. The following tabulation sets forth amounts of components and pertinent test data.
Example TiO2 Resin CCTX
;, 30A 33.3 20.0 1.0 30B 33.0 19.8 1.0 10Example MDEOA HPA Bzph 30A 4.0 41.7 0 ` 30B 4.0 41.2 1.0 W Cure Speed, FPM
No Bzph2% Bzph Yield 88 88 Gloss 89 89 Yield 86 85 Gloss 75 88 100 Yield 73 77 -~loss 45 62 The preceding examples illustrate that benzophenone (a phenyl ketone) combined with 2-chlorothioxanthone has essentially no effect on film yield, but increases the gloss of pigmented W
curable coatings. Each sensitizer is us~d, as described herein-before, in amounts of between about 0.1~ and about 2% by weight.
It has been found that adhesion of the cured coating to some substrates, particularly pasteurized adhesion ~Past. Adh.), is improved by using dimethylaminoethyl acrylate (DMAEA) in the coating composition. In the case of EB curable coatings, the DMAEA is added to the coating composition in amounts of between about 0.5% and about 6% by weight. In the case of W curable coatings the ~MAEA is used in amounts of between about 0.5% and about 6~ by weight to replace all or a part of the tertiary amine co-sensitizer.
, .,: `- , Resin B (Example 29) was admixed with hydroxypropyl acrylate, 2-chlorothioxanthone, and MDEOA or DMAEA. Each coating : was coated on aluminum panels and W cured. The coated panels were subjected to adhesion tests. Amounts of components and test results are set forth ln the following tabulation.
Example Resin B ''CTX HPA MDEOA DMAEA
31A 49.51.0 44.5 0 5 31B 50.01.0 47.0 2 0 ' ' _' ' 50 FPM UV'Cure '' ' Film Example YieldAdhesion P'ast.'Adh.
Resin C (Example 30) was admixed with hydroxypropyl acrylate, 2-chlorothioxanthone, and MDEOA or DMAEA. Each coating - was coated on aluminum panels and W cured. The coated panels were subjected to adhesion tests. Amounts of components and test ; 20 results are set forth in the following tabulation.
' Resin Example C HPA CTX MDEOA DMAEA -~
' 32A 29.2 68.2 0.5 ~ , 32B 29.2 68.2 0.5 0 2 ,~
, W Cure ~ '' -,',' Speed, Film Past.
s Example FPM ~ield Adh. A'dh.
, 50 87 100 70 ',' 30 32B 25 89 100 100 , 50 87 100 100 ..
., .~, .
: ' ' _.. .... . ..
~ -18-,, .
,' 106S~j5 Resin B (Example 29) was admixed with hydroxypropyl acrylate, TiO2 pigment, 1.0% 2-chlorothioxanthone, and MDEOA or DMAEA. The P/B of each coating was 0.75 and the R/B was 0.40.
Each coating was coated on metal panels and W cured. The coated panels were subjected to adhesion tests. Results are set forth in the following tabulation.
Viscosity, c~
, , _ ~
Example Amine222 sec 1 0228 sec 1 1033A 4% MDEOA395 29,100 33B 5% DMAEA 283 564 50 FPM Adhesion to Example Yield Al CCO
. . .
Resin B (Example 29) was admixed with hydroxypropyl acrylate, TiO2 pigment, 1.0% 2-chlorothioxanthone, and MDEOA or ~- DMAEA. The P/B of each coating was 0.75 and the R/~ was 0.6.
Each coating was coated on metal panels and UV cured. The coated panels were subjected to adhesion tests. Results are set forth ,: , in the following tabulation.
Example Amine 222 sec 1 .0228 sec 1 . . _ - 34A 4% MDEOA 80086,100 34B 5% DMAEA 59814,800 50 FPM Adhesion to Example Yield Al CCO
: 34B 89 100 100 It will be noted from the preceding examples that the use of dimethylaminoethyl acrylate gives at least equivalent W -cure. It also provides improved adhesion, both dry and wet.
The following examples are illustrative of preferred coating compositions of this invention.
.,.
:
-`- 10~;508~
Using a reaction vessel equipped with an agitator, a reflux condenser, an inert gas inlet and a charging port, there were charged 525 g. "Epon" 1004 and 70 g. toluene. Heat, agita-tion, and slow inert gas flow were started. Temperature was raised to reflux to remove water (a pot temperature of 150-160C.).
The mixture was cooled to 80-85C. and there were added 40 g.
glacial acrylic acid, 1 g. triethyl amine and 0.1 g. hydroquinone.
Temperature was raised to 95-100C. for esterification and the reaction continued until an acid number of 8-13 was obtained.
This was cooled to 80-85C. and there was added 7 g. maleic anhydride. Temperature was held at 80-85C. for 1-1/2 to 2 hours until alcoholic KOH and aqueous KOH acid numbers agreed (10-15).
- Heat source was removed and 175 g. hydroxypropyl acrylate was added. The mixture was reheated to 80-85C. and vacuum applied for toluene removal. Removed heat and added an additional 182 g.
hydroxypropyl acrylate. The final product had a viscosity of 45-50,000 cp., a wt./gal. of 9.6 lb., an acid number of 10.5 and a `A, total solids of approximately 97%. This resin was used in the ; 20 formulations of Examples 36-38 (amounts are wt. ~ of formulation):
EXAMPLES 36-38 (Clear Finishes) Ingredient 36 37 38 Example 35 Composition 40.3 56.4 33.2 Hydroxypropyl acrylate 56.3 40.2 37.6 Phenyl "Cellosolve" acrylate - - 21.8 Methyldiethanolamine 1.9 1.9 2.9 ` Dimethylaminoethyl acrylate - - 3.5 2-Chlorothioxanthone 0.5 0.5 0.5 Fluorocarbon wetting agent - - 0.5 Silicone lubricant 1.0 1.0 Viscosity (seconds #4 Ford Cup) 50-60 175-225 30-35 Wt./gal. (lb.) 9.04 9.40 8.95 , -:
. . . -10~50l~5 Examples 36 and 37 were formulated as an abrasion resistant coating for can bottoms, which is applied by a wiping action and given a uv treatment of 1-2 seconds with no post bake required.
Example 38 was formulated as a coating for flat sheet -~and is suitable for rollcoat application and given 1 second exposure to W radiation, followed by a 10 minute oven bake at 340-400F. The Phenyl "Cellosolve" acrylate in Example 38 imparts improved corrosion resistance and flexibility.
There were charged 312 g. of an epoxy diacrylate made from "Epon" 828 and acrylic acid, 430 g. titanium dioxide, 198 g.
"Cellosolve" acrylate, 10 g. 2-chlorothioxanthone, 40 g. dimethyl-aminoethyl acrylate and 10 g. benzophenone to a suitably sized pebble mill and ground to a fineness of 7 when measured on a Hegman fineness of grind gauge. Grind time is 24-48 hours. The final product was a white finish suitable for rollcoat applica- -tion on flat sheet. The finish had a viscosity of 90-100 sec.
#4 Ford Cup and a weight per gallon of 13.1-13.3 pounds. It is normally applied at 10 mg./sq. in. and cured using a 1 sec. W
, exposure followed by a 6 minute bake at 325F. After the W
;~ exposure, the film was sufficiently set to accept inks and a wet `
ink varnish. The 6 min. at 325F. bake indicated above followed inking and varnishing operations.
It will be noted that in Examples 38 and 39, Dimethyl-aminoethyl acrylate was used. This compound has a tertiary amine functionality. Thus, as aforedescribed, it can replace the tertiary amine (used to speed up the cure rate) partially (Example 38) or entirely (Example 39). This compound also has reactive ethylenically unsaturated functionality (acrylate) and therefore acts as a reactive monomer. Its use affords a coating : , ., - .
-: , . . . . :
.. .. .
lQ~S~5;
~ composition having improved rheology, as evidenced by better flow ; characteristics, and the cured coatlng has improved adhesion to metal substrates. The addition of benzophenone to the coating composition (Example 39) improves the gloss of the pigmented finish.
Other well known adju~ants may be added to the coating composition such as flow control agents and waxes. waxes, if used, are added as slurries or emulsions of petroleum (paraffin) wax, `~ natural waxes such as montan wax, beeswax, and carnauba wax, or 10 synthetic waxes such as polyethylene wax.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications ` and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.
.,''~ .
,.
, , - ~ :
.
" .
, , . . . . . . : , . :
Claims (10)
1. A UV light curable coating composition that comprises 10-30 weight percent of an adduct of acrylic acid and an epoxy resin, 40-60 weight percent of a monofunctional ester of acrylic acid, 0.1-2.0 weight percent of 2-chlorothio-xanthone, 0.1-2.0 weight percent of a phenyl ketone, 0.5-6 weight percent of a tertiary amine, and a pigment.
2. The coating composition of claim 1, wherein said adduct is modified with an anhydride.
3. The coating composition of claim 1, wherein said adduct is a diacrylate of a diglycidyl ether of bisphenol A
and said pigment is titanium dioxide.
and said pigment is titanium dioxide.
4. The coating composition of claim 2, wherein said adduct is a diacrylate of a diglycidyl ether of bisphenol A
and said pigment is titanium dioxide.
and said pigment is titanium dioxide.
5. The coating composition of claim 3, wherein said adduct is modified with maleic anhydride.
6. The coating composition of claim 1, wherein said ester of acrylic acid is hydroxypropyl acrylate, said phenyl ketone is benzophenone, and said tertiary amine is methyldiethanolamine.
7. The coating composition of claim 2, wherein said ester of acrylic acid is hydroxypropyl acrylate, said phenyl ketone is benzophenone, and said tertiary amine is methyldiethanolamine.
8. The coating composition of claim 3, wherein said ester of acrylic acid is hydroxypropyl acrylate, said phenyl ketone is benzophenone, and said tertiary amine is methyldiethanolamine
9. The coating composition of claim 4, wherein said ester of acrylic acid is hydroxypropyl acrylate, said phenyl ketone is benzophenone, and said tertiary amine is methyldiethanolamine.
10. The coating composition of claim 5, wherein said ester of acrylic acid is hydroxypropyl acrylate, said phenyl ketone is benzophenone, and said tertiary amine is methyldiethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA324,466A CA1078095A (en) | 1974-05-20 | 1979-03-29 | Radiation curable coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47137574A | 1974-05-20 | 1974-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1065085A true CA1065085A (en) | 1979-10-23 |
Family
ID=23871388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA222,006A Expired CA1065085A (en) | 1974-05-20 | 1975-03-13 | Radiation curable coating |
Country Status (2)
| Country | Link |
|---|---|
| US (2) | US4070262A (en) |
| CA (1) | CA1065085A (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS586289B2 (en) * | 1975-02-25 | 1983-02-03 | 新日本製鐵株式会社 | Denki Tetsupanno Zetsuenhimakkeiseihouhou |
| FR2403364A1 (en) * | 1977-09-16 | 1979-04-13 | Commissariat Energie Atomique | COMPOSITE MATERIAL BASED ON FIBERS PRESENTING A HIGH TRACTION MODULE |
| US4357219A (en) * | 1980-06-27 | 1982-11-02 | Westinghouse Electric Corp. | Solventless UV cured thermosetting cement coat |
| US4317858A (en) * | 1980-06-27 | 1982-03-02 | Westinghouse Electric Corp. | Ultraviolet curable solvent-free wire enamel blends |
| US4454219A (en) * | 1981-04-27 | 1984-06-12 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition comprised of a polymer obtained from an aliphatic amino group-containing monomer as a comonomer |
| US4649062A (en) * | 1983-01-05 | 1987-03-10 | Ciba-Geigy Corporation | Ultraviolet radiation curable vehicle for ceramic colors, composition and method |
| US4772538A (en) * | 1985-08-02 | 1988-09-20 | American Hoechst Corporation | Water developable lithographic composition |
| US4895788A (en) * | 1985-08-02 | 1990-01-23 | Hoechst Celanese Corporation | Water developable lithographic composition |
| US4753997A (en) * | 1985-11-27 | 1988-06-28 | The Standard Oil Company | Process for grafting maleic anhydride or styrene-maleic anhydride onto polyolefins |
| US4789620A (en) * | 1986-03-03 | 1988-12-06 | Mitsubishi Rayon Co. Ltd. | Liquid photosensitive resin composition containing carboxylated epoxy acrylates or methacrylates |
| US5492733A (en) * | 1990-03-05 | 1996-02-20 | International Paper Company | High gloss ultraviolet curable coating |
| DE4007519A1 (en) * | 1990-03-09 | 1991-09-12 | Rheydt Kabelwerk Ag | UV-cured resin mixts. for coating optical fibres - contain acrylic] oligomers, acrylate] monomers, initiator, dye, water-repellent components, lubricants, stabilisers, coupling agents, etc. |
| DE4413242A1 (en) * | 1994-04-16 | 1995-10-19 | Basf Lacke & Farben | Process for the production of objects with a three-dimensional surface structure and objects produced by this process |
| AU5635796A (en) * | 1995-05-10 | 1996-11-29 | Avery Dennison Corporation | Pigmented, uv-cured, acrylic-based, pressure sensitive adhes ives, and method for making same |
| JP2002502056A (en) | 1998-01-30 | 2002-01-22 | ファースト・ケミカル・コーポレイション | Photopolymerizable composition containing maleimide and method of using same |
| US6211262B1 (en) | 1998-04-20 | 2001-04-03 | Spectra Group Limited, Inc. | Corrosion resistant, radiation curable coating |
| US20030001108A1 (en) * | 1999-11-05 | 2003-01-02 | Energy Sciences, Inc. | Particle beam processing apparatus and materials treatable using the apparatus |
| US7026635B2 (en) * | 1999-11-05 | 2006-04-11 | Energy Sciences | Particle beam processing apparatus and materials treatable using the apparatus |
| US7279205B2 (en) * | 2001-02-07 | 2007-10-09 | Sonoco Development, Inc. | Packaging material |
| US20040244907A1 (en) * | 2003-06-06 | 2004-12-09 | Huffer Scott W. | Methods of making printed labels and labeling articles |
| US7032492B2 (en) * | 2003-09-11 | 2006-04-25 | Milton S. Meshirer | Ammunition articles comprising light-curable moisture-preventative sealant and method of manufacturing same |
| US20050250039A1 (en) * | 2004-05-05 | 2005-11-10 | Xerox Corporation | Overprint compositions for xerographic prinits |
| US7166406B2 (en) * | 2004-05-05 | 2007-01-23 | Xerox Corporation | Prevention or reduction of thermal cracking on toner-based prints |
| US7279506B2 (en) * | 2004-05-05 | 2007-10-09 | Xerox Corporation | Ink jettable overprint compositions |
| US20050256278A1 (en) * | 2004-05-14 | 2005-11-17 | Crump L S | Tack-free low VOC vinylester resin and uses thereof |
| JP4456440B2 (en) * | 2004-08-31 | 2010-04-28 | 本田技研工業株式会社 | Rust prevention composition |
| US20060160016A1 (en) * | 2004-10-12 | 2006-07-20 | Presstek, Inc. | Inkjet-imageable lithographic printing members and methods of preparing and imaging them |
| US7538145B2 (en) * | 2005-11-30 | 2009-05-26 | Xerox Corporation | Curable phase change compositions and methods for using such compositions |
| US7578587B2 (en) * | 2005-11-30 | 2009-08-25 | Xerox Corporation | Curable overcoat for wax-based inks |
| US7939176B2 (en) | 2005-12-23 | 2011-05-10 | Xerox Corporation | Coated substrates and method of coating |
| US7462401B2 (en) * | 2005-12-23 | 2008-12-09 | Xerox Corporation | Radiation curable composition |
| EP2033949B1 (en) * | 2007-09-04 | 2017-04-19 | Agfa Graphics N.V. | Radiation curable compositions for food applications |
| US8067142B2 (en) | 2007-12-20 | 2011-11-29 | Xerox Corporation | Coating, system and method for conditioning prints |
| US7970333B2 (en) | 2008-07-24 | 2011-06-28 | Xerox Corporation | System and method for protecting an image on a substrate |
| US9365980B2 (en) | 2010-11-05 | 2016-06-14 | International Paper Company | Packaging material having moisture barrier and methods for preparing same |
| US9358576B2 (en) | 2010-11-05 | 2016-06-07 | International Paper Company | Packaging material having moisture barrier and methods for preparing same |
| US9598607B2 (en) | 2012-02-21 | 2017-03-21 | Kegel, Llc | VOC-free, low viscosity, LED-curable coating and method of application |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3676398A (en) * | 1968-11-25 | 1972-07-11 | Ppg Industries Inc | Polymerizable crosslinkable esters of polyepoxy compounds |
| US3759807A (en) * | 1969-01-28 | 1973-09-18 | Union Carbide Corp | Photopolymerization process using combination of organic carbonyls and amines |
| US3661576A (en) * | 1970-02-09 | 1972-05-09 | Brady Co W H | Photopolymerizable compositions and articles |
| US3719728A (en) * | 1970-02-12 | 1973-03-06 | Brien Corp O | Radiation curable compositions |
| US3776729A (en) * | 1971-02-22 | 1973-12-04 | Ibm | Photosensitive dielectric composition and process of using the same |
| US4004997A (en) * | 1972-01-30 | 1977-01-25 | Seiko Shimada | Process of curing a polymerizable composition containing a magnetized powered ferromagnetic material with radioactive rays |
| US3804735A (en) * | 1972-04-10 | 1974-04-16 | Continental Can Co | Photopolymerizable compositions prepared from beta-hydroxy esters and polyitaconates |
| US3714006A (en) * | 1972-05-15 | 1973-01-30 | W Anderson | Cyclopentadienylmanganese tricarbonyl compounds as a catalyst for the radiation curing of polyepoxides |
| US3787212A (en) * | 1972-08-04 | 1974-01-22 | Monsanto Co | Polymeric photosensitive compositions and methods using same |
| US3878075A (en) * | 1973-03-30 | 1975-04-15 | Scm Corp | Photopolymerization of pigmented binders using combinations of organic carbonyls and halogenated naphthalenes |
-
1975
- 1975-03-13 CA CA222,006A patent/CA1065085A/en not_active Expired
-
1976
- 1976-10-06 US US05/730,112 patent/US4070262A/en not_active Expired - Lifetime
- 1976-12-23 US US05/753,755 patent/US4071425A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4070262A (en) | 1978-01-24 |
| US4071425A (en) | 1978-01-31 |
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