JPS59224840A - Manufacture for printing plate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing printing plates from radiation-curable compositions.

Photopolymerizable systems using acrylate end components have in the past suffered from poor stability and a tendency to air inhibition.

Unexpectedly, according to the present invention, these 3- disadvantages can be solved based on the composition of (1)-shells with 1 +1
˜80 weights X1 preferably 40 to 60 weight percent acrylic or methacrylic terminated urethane-containing polyene, (2) a water-insoluble vinyl monomer diluent, preferably an acrylate or methacrylate momer diluent, (3) generally 0.1 to 35% by weight, preferably 2-10
It has been discovered that this can be overcome using a photocurable system consisting of a polythiol containing at least 2 1,000-ol groups per molecule in wt. .

The composition cures to a solid polythioether when exposed to radiation, such as a radiation source.

The acrylic- or methacrylic-terminated urethane-containing polyene component is prepared by reacting a 1,77-cyisocyanate with an ethylenically unsaturated alcohol in an amount such that one stoichiometrically dispersed free incyanate groups remain in the reaction product; The free isocyanate group 4- is converted into a polyhydric alcohol, preferably in polyethylene glycol or polypropylene glycol of the formula % where n is from 1 to 100 and R is hydrogen or a methyl group. It can be produced by reacting with the hydroxyl group of the target. Examples of suitable twincyanates are: aliphatic, aromatic and heterocyclic diisocyanates, such as 1,5-7talene diisocyanate; cumene-2,4-diisocyanate; 4-methoxy-1゜3-Phenylene゛isocya＊-
1-:4. -Rerylow 1°: (-phenylene diisocyanate; 4-bromo-1°3-phenylene diisocyanate; 4-ethoxyl.

3-phenylene diisocyanate: 2,71'-diisocyanato 7 phenyl ether; 5,6-dimethyl-1°3-phenylene diisocyanate; 2,4-dimethyl-
1,3-phenylene diisocyanate; 4.4'-)5
- Isocyanato diphenyl ether; bennonone diisocyanate); 4,6-dimethyl-1,3-phenylene diisocyanate; 9,10-anthracene diisocyanate); 4,4'-diisocyanatobenzyl;3.3'
-Dimethyl-4,4'-noisocyanatonophenyl;
2,4-diisocyanatostilbene;313'-dimethyl-4,4-diisocyanatophenylmethane;3,3'
-nomethoxy4,4'-noisocyanatodiphenyl;
1,4-anthracene isocyanate: 2,5-fluorene diisocyanate; 1. Amylbenzene-2,4-diisocyanate; Hexylbenzene-2,4-diisocyanate; Dodecylbenzene-2,4-diisocyanate; Butylbenzene-2,4
-Diisocyanate; polymethylene diisocyanate,
For example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate; cycloalkylene diisocyanate, such as =6-cyclohexylene-1,1 fincyanate; 4°4'
-methylene bis(cyclohexyl isocyanate); isophorone diisocyanate; heterochain noisocyanates, for example (0=C=NCILCIL).

0゜Appropriate ethylene layer 1. Unsaturated alcohols are polymerizable acrylate or methacrylate esters having hydroxyl groups; examples thereof are: 2-hydroxyethyl; 2-hydroxypropyl; 2-hydroxybutyl; 2-hydroxyoctyl; 2
-Hydroxydotepacanil; 2-hydroxy-3-chloropropyl; 2-hydroxy-3-acryloxypropyl; 2-hydroxy-3-methacryloxypropyl;
2-hydroxy-3-allyloxypropyl; 2-hydroxy-3-cinnamylpropyl; 2-hydroxy-3
-phenoxypropyl; 2-hydroxy-3-(0-chloro7e/xy)propyl: 2-hydroxy-3-(+
)-chloro7e7xy)propyl; 2-hydroxy-3
-(2,4-dichlorophaenoxy)propyl; 2-hydroxy-3-acetoxypropyl; 2-hydroxy-3-propiotskidipropyl: 2-hydroxy-3-chloroacetoxypropyl;
2-hydroxy-3-7 taloloacetquinbropyl; 2
-Hydroxy-3-trichloroacetoxypropyl; 2
-Hydroxy-3-benzoxypropyl; 2-hydroxy-3-(o-chlorobenzoxy)propyl; 2-hydroxy-3-(p-chlorobenzoxy)propyl; 2-
Hydroxy-3-(2,4-dichlorobenzoxy)propyl; 2-hydroxy-3-(3,4-dichlorobenzoxy)propyl; 2-hydroxy-3-(2°4.6-
)lichloro-7/xy)propyl; 2-hydroxy-3
-(2,,1,,5-trichlorophenoxy)propyl; 2-hydroxy-3-(o-chlorophenoxyacetoxy)propyl; 2-hydroxy-3-7e/xyacetoxypropyl; 2-hydroxy-3-(o-chlorophenoxyacetoxy)propyl; -(p-chloro7
E7xyacetoxy)propyl; 2-hydroxy-3-
(2,4-dichloro7ethoxyacetoxy)propyl;
2-Hydroxy-3-(2,4,5-)ly8=chlorophenoxyacetoxy)propyl; 2-hydroxy-3-crotonoxypropyl and 2-hydroxy-
3-cinnamyloxypropyl acrylate; and methacrylate.

The production of polyenes of this type is well known and is described, for example, in US Pat.

Examples of water-insoluble acrylate or methacrylate monomer diluents are: bisphenol and diethylene glycol diacrylate and dimethacrylate; ethylhexyl acrylate and methacrylate): 1,6-hexaneol and Pentyl glycol diacrylate and methacrylate; pentaerythritol tetraacrylate and triacrylate; polyethylene glycol, tetraethylene glycol and triethylene glycol noacrylate and dimethacrylate and trime 9-acrylate. Examples of other water-insoluble vinyl monomer diluents are vinyl acetate; vinyl propionate; N-vinylpyrrolidone; diallyl adipe-1; diallyl maleate and diallyl maleate.

These diluents are photocurable]-reactive in the culm;
Can be added separately or as a mixture. Additionally, acrylate mole 7-diluent can be added to compositions containing methacrylate-terminated polyenes (4) and vice versa. Generally, 5 to 8 of the composition.
It is added in an amount of 0% by weight, preferably 20-60% by weight.

Generally, the polyene must contain two or more terminally reactive unsaturated carbon-to-carbon bonds/molecules and 70°
It has a viscosity of 0 to 2 (I X i ('l' poise) at C.
Includes materials with odor and viscosity within the above range. The polyenes and diluents that can be used are generally those with a molecular weight of F+ C1-2 f'l, l'+
+)('l, preferably 1 (10C1~5 +)('
l (1. Polyene and reactive dilute [polythiol-
The word 1 has an average of 1 molecule V)'! Refers to simple or complex organic compounds with 4/number of pendant or terminally located −8 + −1 functional groups. In other words, it must contain -SII groups/molecules of "polythiol-1 is 2 or more". Polythiols typically have a viscosity measured at 70'C with a Brookfield viscometer of -1-2 centipoise (cr+s) more or less than O. As used herein, polythiol 1 has a 7(
')' Materials having a viscosity within the range described in C are included. Polythiol usually has a molecular weight of about 94~2.
n, (1f) 0 or more, preferably about 100 to about 10
,000.

Suitable polythiols can be exemplified by the general formula: RT+-8■I)11, where 11 is at least! J2, and F<8 is a "multivalent organic moiety containing no reactive one-carbon to carbon unsaturation. Thus, R8 is a cyclic group and a small amount of heteroatoms, e.g., N, S1P or (-)
can contain carbon-hydrogen, carbon-oxygen or silicon-carbon-hydrogen, carbon-oxygen or silicon-
Oxygen-containing Il′i 4. ' Contains a combination.

One class of polythiols that form essentially odorless cured polythioether coatings and relief images has the general formula: thiol-containing acid (which is an organic moiety that does not contain saturation) and general structure: R1-size-01
-1) n (wherein R10 is an organic moiety containing no reactive 1-carbon unsaturation, and n is 2 or more) is an ester with a polyhydroxy compound. These components will react under appropriate conditions to give a polythiol having the -shell structure: R17-0C-R8-8It)n.

Certain polythiols, such as aliphatic monomeric polythiols (e.g. ethanediol, hexamethylenethiol, decamethylenethiol and toluylene-2,4-dithiol) and some polymeric polythiols, e.g. The use of thiol-terminated ethylcyclohexylcyclobutane polymers (preferably polythiols having 111 mercaptans and little or no odor) which are readily available and commonly synthesized on an industrial scale. You can also do that.

Examples of preferred polythiol compounds due to their relatively low odor and fast curing rate are: thioglycolic acid (MS-CH2Cool-1), α-mercaptopropionic acid (HS-CH(CT-T3)). -CO
OH) and β-mercaptopropionic acid (H6-CI
-T2CH2COOH) and polyhydroxy compounds, 13
- For example monomers with glycols, triols, tetraols, pentaols and hexaols. Specific examples are: ethylene glycol bis(thioglyflate), ethylene glycol bis(β-mercaptopropionate trimethylolpropane tris(thioglyflate), trimethylolpropane tris(β-mercaptopropionate),
- mercaptopropionate), pentaerythritol tetrakis (thioglyflate) and pentaerythritol tetrakis (β-mercaptopropionate),
All of these are commercially available. A preferred polymeric polythiol is polypropylene ether glyfur bis(β-mercaptopropionate), which is similar to polypropylene ether glyfur (e.g., Plur
acol P 2 n 1 0, Wyandol. -t
．． e Chemical Corp.) and β-mercaptopropionic acid by esterification.

The curing reaction can be initiated by ultraviolet light or high energy ionizing radiation. Ultraviolet rays are sunlight or -14 = 1 to skin length or about 2,000 to 4. It is possible to source special light that emits a significant amount of ultraviolet light having a wavelength on the order of O(14) angstroms lit. Either type of actinic radiation can be used. For liquid photocurable compositions, the light is preferably emitted from a single point source or in the form of parallel beams, but it is also possible to use diverging beams of light.

Examples of suitable actinic radiation are carbon arcs, mercury arcs, fluorescent lamps with special ultraviolet-emitting phosphors, xenon arcs, solar radiation, tungsten halide lamps, argon glow lamps, photographic 7-rad lamps and laser beams. It is.

When ultraviolet light is used for curing reaction, rl, (1(l 0
A dose of 7 cm2 (4.-60 watts) is commonly used.

When UV radiation is used for curing, a photoinitiator is added to the compact to increase the reaction rate.

Suitable! 11 photoinitiators are well known in the art,
Examples are: benzene, acetophenone, acenaphthenequinone, methyl ethyl ketone,
Hull mouth 7-7n, hexa7-phenone, ff-phenyl phthiro7-en/n, 0-morphora/propiophenone, dibenzosuberone, 4-morpholifbenzo7-en/n, 4'-
Morphorife deoxybenzoin, p-diacetylbenzene, 4-ami7benzo7ene, 4'-methoxyaceto7ene, benzaldehyde, α-tetralone, 9-7
Cetyl 7-enanthrene, 2-7 cetyl 7-enanthrene,
10-thioxanthenon, 3-a7tylphenanthrene, 3-acetylindole, 9-fluorene, 1-indanone, 1,3.5-'p-lyacetylbenzene, thioxanthin-9-one, xanthine-9-one , benzoin isobutyl ether, taloloxanthone, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin isopropyl ether 7-one, 1-su7toaldehyde, i, 4'-bis(dimethylamino)penzophene, fluorene-
9-one, 1'-acetonaphthone, 2'-7 setona7ton, 0-meth)oxybenzo7ene/one, triphenylphosphine, triphenylphosphine, tri-tolylphosphine, benz[α]anthracene-7.

12-dione, 2,2'-jethoxyacet7ene,
2,2-dimethoxy-2-phenylacetophene and 2,3-butanedione and mixtures thereof; these greatly reduce exposure times and can therefore be used in conjunction with various forms of energy radiation; This results in an extremely rapid commercially practical time cycle.

A preferred aspect of using ionizing radiation for curing is treatment with energetic particles, gamma rays or X-rays. Positive ions (eg protons, alpha particles and deuterons), electrons or neutrons can be used. Charged particles are generated by the divine voltage gradient mechanism, such as Van de Gler 7 electromotive machine, cyclotron, Kotsukuro 7 Twarton addition>
mB, resonant air accelerator, betatron, (';.P
:． It can be accelerated to high 17-velocities by resonant transformers or synchrotrons. Furthermore, particle irradiation can also be provided by radioisotopes or from nuclear reactors. Gamma or X-rays can be obtained from radioactive isotopes (eg, cobalt-60) or by particle bombardment of a suitable target material (eg, bombardment of high-energy electrons onto a gold target).

The radiation dose rate capable of curing the coating in the present invention is generally 0.00001 to 100 (17 gal/sec).

The fecal dose of ionizing radiation can be varied within wide limits. For electrons, from less than 1 Megarad to more than 107 Galad.
A radiation dose of up to 2 is appropriate, preferably 0.02~
Uses 5 meters of absorbed energy. For manga rays or X-rays, radiation doses in the range of absorbed energy of 0,0001 to 5.07 ra are suitable.

The irradiation step is usually carried out under ambient temperature conditions, but at temperatures below room temperature or, e.g., up to 90'C. Example 18 - When using an ionization beam, the penetration depth depends on the density of the material to be penetrated. Depends on. When the M-law during ionization is in the electronic form, 0.2 to 12 million electron pol) (+nev) is usually used. When using gamma rays or X-rays, (+
, fl 1 to 5.0 million electron volts are commonly used. If such transmission is insufficient to cure the coating to the full desired depth when directing the radiation from only one direction, beams from multiple radiant sources may be applied simultaneously or intermittently from diametrically opposite sides of the coating. can be used. Additionally, a shield can be used to increase transmission through the coating on the side far from the radiation source.

The composition of the present invention may optionally contain antioxidants, inhibitors, activators, fillers, pigments, dyes, antistatic agents,
Additives such as fuel agents, thickeners, thixotropic agents, surfactants, viscosity modifiers and plasticizers can be included. Such additives are generally precompounded with the polyene or polythiol prior to formulating the photocurable composition. The additives can be added to the radiation curable composition (up to 10 parts by weight, preferably up to 1 part by weight, preferably up to 1 part by weight),
fil'l (IF) can be present in amounts from 1 to 300 parts by weight. The additive Mi and concentration are carefully selected so that the final parabolite remains radiation curable under the exposure conditions.

The curing period can range from, for example, less than 1 minute to, for example, 3 minutes.
It can be delayed or accelerated from 0 to -1.

Examples of common cure inhibitors or retarders that can be used to stabilize ingredients or cure+1 compositions to prevent premature cure are hydroquinone; p-1,-butylcatechol; i-Butyl-1-tomethylphenol; 7eth7thiazine; N-phenyl-2-7thylamine; phosphoric acid and pyro are rolls.

Examples of common reactions that speed up the curing reaction rate and extend the wavelength range of available light are trimethyl phosphite, triethyl phosphite, triphenyl phosphite, rose bengal and acetone.

A common method for forming printing plates from the compositions of the present invention is to
Image-bearing line or halftone stencils or positive or Place Kene's transparent body. The image-bearing transparency and the surface of the photocurable composition can optionally be in contact or have an air gap therebetween. The photocurable layer is exposed through the transparency to a source of actinic radiation to cure the photocurable fr layer to the stage where it is insoluble in the exposed areas. In such a method, the ultimate relief thickness can be adjusted by varying the layer thickness of the photocured +1/11 composition. The plates thus produced can then be imaged and developed.

Development can be carried out by conventional means, eg, by removing the uncured portions of the curable composition with a suitable solvent or liquid, eg water or a detergent. Additionally, the uncured portions may be removed by an air knife, such as a mechanical device moving across the plate that emits a blast of pressurized air that blows the uncured liquid composition away from the plate.

In the production of printing plates, it is essential that the exposure be sufficient to cure the curable composition in the exposed image without significant curing in the non-image areas. In addition to exposure time and light intensity, the degree of exposure depends on the thickness of the photocurable layer, the curing temperature, the polyenes and polythiols used, the photoinitiators, diluents, and the amount of light-absorbing pigments or pigments in the photocurable composition. It depends on the presence of dye and the characteristics of the image to be reproduced.

Generally, the thicker the outer layer to be cured, the longer the exposure time. Curing was observed to begin at the surface of the photocurable composition closest to the light source and progress downward toward the support. If the exposure is insufficient, the layer will harden hard on the surface but will lack overall hardening and the relief will be removed when the unexposed areas are removed. While cure rate normally increases as temperature increases, exposure may be less at 22-degree temperatures than at room temperature. Therefore, heat-emitting UV sources are more efficient than cold UV sources. However, care must be taken to ensure that the humidity is not too high during photocuring, since high temperatures can, in some cases, cause thermal expansion of the photocured F day product, resulting in distortion of its viscous image. Therefore, the photocuring is approximately 2 +
)'C to about 7 I)'C. Because there are many variables that affect exposure time, optimal results are best determined by trial and error, eg, by gradual exposure with characterization after each exposure.

Although contact is possible, it has been found that it is preferable to maintain an air gap between the photocured F-eye composition and the image-supporting transparency. Such an air gap may be, for example, 0
．． 1 mil to 250 mil (+1, Of'+2', r
4 ・-6,35m+m)l: Moon- can be. The air gap facilitates the intact removal of the cured composition from the vicinity of the cured composition after exposure of the image-bearing transparency to light. plate pressure printing frame,
It is used to maintain contact between the image-bearing transparency and the photocurable composition. Optionally, separation of the image-bearing transparency from the cured composition is accomplished by adding a separating layer, such as a thin petrolatum or silicone film coated onto the surface of the transparency, or the transparency and the photocurable composition after exposure. This can be facilitated by introducing a thin transparent film, such as cellulose esters or regenerated cellulose, including cellulose acetate, cellulose propionate, and polyethylene terephthalate, between the two. After exposure, the transparency can be removed from contact with the cured layer or split layer and reused, if desired.

Generally, the thickness of the layer to be photocured and used as a printing plate is between 0.1 and 5 (10S mils or less).For lithographic printing plates, the thickness of the layer is generally 0.1 = 5 mils (+1. (Lf1254-('1.127mm) Ni letter set (dry offset) version-], usually 5 ~
25 mils (0,127 to f1.635 mm); for letterpress printing plates, 15 to son mils (0,38] =
+2,7+nm) thickness is common. For letterpress newspaper or magazine printing plates, the thickness of the photocured scrap is typically 10 to 50 mils ((1,2!') 4
= L27mm). In intaglio, the depth of the recessed holes is, for example, 0.1 to 5 mils (('1.0025/
1 to (1,127 mm). 7 Thick layers are sometimes used in lexo printing designs, and relatively large areas are used in letterpress printing plates.

The support used can be any natural or synthetic product, which can be in the form of a sheet or board, and can be flexible or rigid, smooth or glossy? +V and can be reflective or non-reflective to actinic radiation. It is preferable to use metal because it is strong. However, if weight is a constraint, plastic, paper, or rubber can be used. Furthermore, the support layer can itself be a photocurable composition.

That is, a portion of the photocurable composition is poured into a mold,
- Direct exposure to actinic radiation to photocure /1/11 compositions;
? One layer can be solidified. After assimilation, the first and second layers serve as a support for an additional amount of photocuring +i condensate, which is poured onto the -1 part of this support, and after exposure through the image-bearing transparency, the relief is transferred to the -1 part of this support. − can be formed. Again, the photocurable composition can be cast onto a transparent plate, such as a glass plate or a plastic plate. This layer can be exposed non-imagewise from one side to form a base for assimilation and exposed imagewise through a transparency from the other side to form a relief image. Exposure of these two scales can be carried out simultaneously or sequentially, if desired.

If a rotary press plate is desired, the support material can be used to form a flat relief plate which can then be shaped into the desired shape. Such rotary press plates also use various types of cylindrical support plates that support the curable composition and expose them directly to actinic radiation through a concentrically arranged image-supporting transparency. It can be produced by exposure to.

26- Examples of suitable metal supports are steel, aluminum, magnesium, copper and chromium. Examples of suitable film-forming plastics are: addition polymers, vinylidene polymers, such as vinyl chloride, copolymers of vinylidene chloride with vinyl chloride, vinyl acetate, styrene, isobutylene and acrylonitrile); copolymers of vinyl chloride with the latter polymerizable moles; linear condensation polymers, such as polyesters, such as polyethylene terephthalate; polyamides, such as polyhexamethylene sebamide; and polyester amides, such as , polyhexamethylene adipamide/Ambate. Fillers or pond reinforcements can be present in synthetic resin or polymeric supports, examples of which include various fibers (synthetic, modified or natural), such as cellulose e! AI
E, such as cotton, cellulose acetate, viscose rayon and paper; glass wool; and nylon. These reinforced substrates can be used in the form of laminates.

The invention is further illustrated by the following examples.

Examples 1 and 2 describe the production of acrylate prepolymers. All parts and percentages are by weight unless otherwise specified.

Example 1 375 g of commercially available luennoisocyanate was added to a 3I glass resin bottle along with 1.295 g of stannous octoate. The acrylate was added at a constant rate. After the addition was complete, the reaction mixture was
C. for 1 hour, then further addition of f'l, 31 g of stannous octoate. Then the molecular weight is about 100 r
) of polypropylene glycol (LlnionCarl
] ide's "PPG 1025") (1288, 2g
) and 6+' until the NGO content is completely reduced.
) 'Heating at C was continued for 3 hours. Stabilizer, 1.
97 g of 2,6-di-L-butyl 7er7-er were then added.

The methacrylate-terminated polyene thus produced is hereinafter referred to as Prepolymer A.

Example 2 - 12 pounds of commercially available toluene isocyanate into a 30 gallon (1141) glass reactor;
Added along with 15.0 g of stannous octoate. 16
Add 3FK triphenyl phosphite, then 31.
4 Bond hydroxypropyl acrylate? The temperature was added at a rate that did not exceed 60'C each time. A second addition of stannous octoate (17°0 g) was then made, followed by 133 lbs of polypropylene glycol (“P
PG10025゛) was added.

The reaction mixture was heated at 60° C. until no unreacted isocyanate was detectable. The azirylate-terminated polyene thus produced is hereinafter referred to as prepolymer B.

Example 3 8 (1,'1 part of Prepolymer A from Example 1, 2
8? plS's Diethylene Glycol ν〆Taclyre~2
9-t, 8.7 parts of triphenyl phosphite, 10°9 parts of 2,2-dimethoxy-2-phenylacetophenone,
2.2 parts of 2,6-di-1-butyl 7-ethyl and 5
4 parts of trimethylolpropane tris (3-mercaptopropionate). This mixture was then mixed with 60
Heated at °C for 1 hour.

A 20 mil (0,S ('l 8m+n) thick layer of this formulation was then applied with a 10 mil (0,S ('l 8m+n) thick layer) coated with an adhesion promoting layer.
+1.254. mm) aluminum sheet-1 was coated with a knife. This polymer was exposed to an ultraviolet source for a short period of time (5, 8
8 seconds) exposed. A one-vane negative of newspaper was then held precisely above the photopolymer layer to form a 15 mil air gap between the two sheets. Then a second exposure (4
5 seconds) was performed through the negative using the same UV a source. The imaged plate was then etched with a blast of compressed air, leaving a relief image with excellent fidelity suitable for printing.

Example 4 307 hog (139 kg) Example 2 empty pre-30
- The polymer was mixed with 69 bond (31, R kg) of noethylene glycol no methacrylate, 5.5 bond (2,5
kg) of benzoin isobutyl ether and 627.kg) of benzoin isobutyl ether.
5[? of triphenyl phosphite. The mixture was heated at 60°C for 1 hour, then 7.2% of the tetramercaptopropionate ester of pentaerythritol was added, based on the total overlay in the reactor, and then 0.2% of the tetramercaptopropionate ester of pentaerythritol was added.
Total % octadecyl-β-(7I-hydroxy-3,
! 'i-]-1-butylphenyl)propionate t9
and 0.1% by weight of 2°6-No! -Butyl-.1-methylphenol was added.

This material was used to produce printing plates as described in Example 3. A clear relief image with excellent fidelity.

Example 5 100 g of prepolymer B from Example 2 was added to 8 f'l
diethylene glycol acrylate. then 0.4.8g triphenylphosphite,
fi, 2f) H no G! -Ptylpher 7-, 5゜0g
benzophenone, 1. Og of methyljetanolamine was added and the supernatant was heated at 60° C. for 3 minutes. Then 10 Fi of trimethylolpropane (trimercaptopropione) ester was added to 10 Fi of N-
It was added along with vinyl-2-pyrrolidone.

This material was then coated as a thin film onto a conventional white basecoat of steel can stock-1. This coating is applied to Radiant, Pro
-ducl, s) using three 200 watts/inch (78,7 watts/cm) mercury lamps at + S f'l fee 17 minutes (4,5,7 m/min) in an ultraviolet oven. Hardened. The cured coating had excellent gloss, abrasion resistance and adhesion and did not form cracks when stamped and formed from metal.

The radiation curable compositions of the invention can be used on a variety of substrates, such as glass, ceramic, concrete, metal, plastic, astragalus, paper, cardboard, wood and resilient flooring materials, such as vinyl and vinyl-asbestos tiles and vinyl sheets. Can be used as a coating on products. Suitable coating thicknesses are (), 5-250 mils (+), 0127-6
, 3.5 mm).

Patent Applicant Gubri I. R. Brace &amp;
Company=33-279

Claims (1)

[Claims] 1. (1) 10 to 80% by weight of acrylic or methacrylic terminated urethane-containing polyene, (2) 5 to 8
0% by weight of water-insoluble vinyl monomer as diluent, (3) 0.1-35% by weight of polythiol and (
4) A liquid radiation-curable composition comprising 0.01-10% by weight of a photoinitiator and capable of forming a solid, cured polythioether upon exposure to actinic radiation or high-energy ionizing radiation, to support the image. printing characterized in that it is exposed to actinic radiation projected through a transparent body for a time sufficient to insolubilize the exposed portions of the composition, and then the unexposed composition is removed. How to make the plate. 2. The method of claim 1, wherein the composition is adhered to the support during exposure. 3. The method according to claim 1 or 2, wherein an air gap of 11.1 to 250 mils (0,+1 (254-6,35+ nm)) is maintained between the image-bearing transparency and the composition during exposure. Process: 4. The polyene is prepared by reacting a diisocyanate with an ethylenically unsaturated alcohol in an amount such that approximately one stoichiometric equivalent of incyanate groups remains in the reaction product, and then converting the free incyanate groups into polyvalent 4. The method according to claim 1, wherein the diisocyanate is toluene diisocyanate. The introduction product according to claim 4. 6. The introduction product according to claim 4 or 5, wherein the ethylenically unsaturated alcohol is hydroxypropyl methacrylate-Y. 2-7. The alcohol has molecules @1g (1('l O
7. A composition according to any one of claims 4 to 6, which is a polypropylene glycol having a polypropylene glycol of .about.2.degree.()00. 8. The method according to any one of claims 1 to 7, wherein the vinyl monomer is noethylene glycol dimethacrylate-1 or diacrylate. 9. The knn according to any one of claims 1 to 8, wherein the polythiol is trimethylolpropane tris(3-mercaptopropionate) or pentaerythritol te)ramelcabutobrobionate ester.
first fruit