JPS5813085B2 - Radiation curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a family of fast-curing coating compositions containing highly radiation-sensitive compounds commonly known as amide acrylates.

Coating compositions containing members of this group of compounds polymerize at very high rates when exposed to ionizing or actinic radiation to form rear-resistant protective and decorative films. Form.

Curing can be accomplished under ambient atmospheric conditions since the high rate of film curing during actinic radiation is poorly inhibited by the presence of oxygen.

Irradiation of the composition with ionizing radiation in the presence of oxygen can also yield cured coatings, but not at the oxygen concentrations present in the surrounding atmosphere.

However, curing of amide acrylate-containing compositions by ionizing radiation proceeds in the presence of oxygen concentrations several times higher than those conventionally known for curing conventional acrylates.

Forming mar-resistant films at high rates without the need for a substantially oxygen-free atmosphere, such as a nitrogen atmosphere, provides high production capacity without prohibitively large capital investments. , which is a great economic advantage.

These compositions are particularly useful for forming hunis coatings on paperboard packaging materials with printed markings.

In this application, it exhibits a suitable combination of flowability, wettability and odor, giving a cured coating with high gloss, slip and transparency properties suitable for use in the paper coating industry.

Low cost, fast curing coating compositions are needed.

BACKGROUND OF THE INVENTION Protective coatings on paper or paperboard substrates on which printed indicia or pictures are printed or illustrated must pass several rather stringent and sometimes competing physical and chemical standards.

First, it is desirable that the composition have rheological properties such that it flows easily upon application of high shear stress, such as when applied to a substrate by a roll coater or printer.

After transfer to the substrate, the composition is then allowed to flow for several seconds in the absence of high shear stress to smooth the coating and
Uniform thickness should be promoted.

Good smoothing performance is also dependent on the opposing forces resulting from the viscosity of the composition, surface tension, elasticity, and gravity, each of which acts on the composition in a separate manner as it spreads across the substrate. This is the result of the balance.

These special properties make it difficult to use substrates, especially substrates with printed text or heavily inked areas that typically impede the spread and adhesion of face coatings onto the substrate.
must be balanced against the composition's ability to "wet".

Secondly, the composition obtains the highest gloss achievable and
It must have chemical properties that promote rapid curing into a mar resistant film.

One requirement for overprint varnish coatings is that the composition be relatively thin, i.e. 0.002-0.0
It is to be applied as a layer in the range of 10 mm.

This thinly applied composition must cure extremely quickly in order to meet price/performance requirements that dictate that product processing speeds are limited only by the mechanical processing equipment used in the UV processing industry.

It has been surprisingly discovered that very thin face coatings cure slower than thicker coatings, especially when applied onto heavily inked substrates.

One explanation for this phenomenon is that the optical density of the thin film is
This means that a significant amount of radiant energy passes through the film and is reflected back from light-colored substrates, but is absorbed by dark-colored substrates.

The reflected energy clearly contributes to the hardening of the film.

Therefore, one chemical property that a varnish coating composition must possess is rapid curing when applied as a thin film onto a dark substrate.

A group of amide acrylate compounds that provide the above benefits generally have the formula [wherein X, Y, and Z are each independently hydrogen alkyl, aryl, or acryloxyalkyl acrylyloxy aliphatic ester (in the molecule of a hydroxycarboxylic acid (formed by the reaction of an aliphatic ester-containing intermediate terminated with a hydroxyl group formed by the reaction of an ester with an amino alcohol and an acrylating substance), or an acryloxyaliphatic ether, with the exception of X, Y,
Z together have two, three or four acryloxy groups.

Generally, use of the term "amide acrylate" is intended to include substituted derivatives of acrylyloxy groups, such as methacrylyloxy groups.

A preferred compound is bis(acrylyloxyethyl)formamide.

Another preferred compound is N-N-bis(2-acrylyloxyethyl)-4-acrylyloxybutyramide.

Other preferred acrylyloxy-containing compounds within the group represented by the general formulas include compounds represented by formulas (IV) to (XIV).

The amide acrylate compound shown above is produced by first reacting a compound selected from the group consisting of carboxylic acids, esters of carboxylic acids, hydroxy acids, and intramolecular esters of hydroxycarboxylic acids with an amino alcohol to form an amide-containing hydroxy group-terminated intermediate. It can be manufactured by forming.

This intermediate is then reacted with a compound having acrylic functionality and having a functional group reactive with the hydroxy groups of the intermediate to produce an acrylate-terminated amide-containing compound.

Suitable starting carboxylic acid compounds for the preparation of amide-containing hydroxy-terminated intermediates include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, benzoic acid, toluic acid. ortho, meta and para isomers of phthalic acid and 2-ethylhexanoic acid.

Particularly preferred carboxylic acids are formic acid, benzoic acid and 2-ethylhexanoic acid.

Ester analogs of the above carboxylic acids are also suitable as a group of starting materials.

Particularly preferred carboxylic acid esters include methyl formate and ethyl acetate.

A third group of useful starting materials consists of hydroxy groups.

Preferred compounds of this group include α-
Contains hydroxy acids.

A preferred aromatic hydroxy acid is obtained by the reaction of phthalic anhydride with diethylene glycol.

A fourth group of useful starting materials consists of intramolecular esters of hydroxycarboxylic acids, such as gamma-butyrolactone, gamma-valerolactone, epsilon-caprolactone.

Suitable aminoalcohol compounds for reacting with the above starting materials to produce amidohydroxy-containing intermediates include ethanolamine, diethanolamine, N-methylethanolamine, N-phenylethanolamine,
-amino-1-butanol, 4-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, 6-amino-1-hexanol, 2-amino-2-
(Hydroxymethyl)-1,3-propanediol, 2
-amino-3-methyl-1-butanol, 3-amino-
3-methyl-1-butanol, 2-amino-4-methyl-1-pentanol, 2-amino-2-methyl-1.3
-Propanediol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 1-amino-2-propanol, 3-amino-1- Included are hydroxyalkylanilines such as propanol and p-aminobenzyl alcohol.

The intermediate product formed from the above starting materials contains one amide group and one or more reactive hydroxyl groups.

The amide hydroxy-containing product is reacted with a compound having acrylic functionality and a functional group reactive with the hydroxyl group of the amide intermediate.

Suitable acrylating materials for reacting with the amide intermediate include compounds having an acrylyl group or an alpha monosubstituted acrylyl group such as methacrylyl, ethacrylyl and alpha-chloroacrylic.

These compounds must also contain functionality reactive with the amide intermediate hydroxyl group.

Suitable special acrylating materials include acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid and acrylyl chloride and mixtures of these materials.

Preferred compounds are acrylic acid and methacrylic acid.

Amide acrylate compounds of the type represented by the general and specific formulas above can generally be prepared by reacting a starting material selected from the group listed above with approximately equimolar amounts of an amino alcohol.

When the reaction components are heated under reflux conditions, an azeotrope typically forms.

Depending on the choice of reaction components, volatile products produced by the reaction, such as water, ethanol, methanol or others, are collected and removed from the reaction mixture in the usual manner.

This hydroxyl-containing amide intermediate is then reacted with a suitable acrylating material to form an amide acrylyloxy-containing compound.

Although it is generally preferred to mix an amount of acrylated compound with the intermediate that is stoichiometrically equivalent to the reactive hydroxyl group functionality of the intermediate, any excess or deficiency of acrylated compound is not detrimental.

Generally, as noted above, the amide acrylate monomers produced are characterized by having only one amide group per monomer molecule.

However, the monomers can have 1, 2, 3 or 4 acrylate functional groups per molecule, with a portion of the acrylate groups providing acrylyloxy groups.

Amidodiacrylate monomers are represented by formulas ■, ■, ■, ■ and XIV.

Formulas ■, ■, ■, ■ and M represent amide triacrylate.

Formula X■ represents amidotetraacrylate.

The amide acrylate compounds described above are useful as radiation-curable components of film-forming coating compositions, and the amide acrylate compounds can be present in the compositions in amounts ranging from about 1 to 99% by weight of the composition.

Typically, the concentration of amide acrylate is from about 20% to about 80%.

When the coating composition of the present invention consists of 99% or less of an acrylate compound, other acrylate compounds may contain a portion of the monomers that can be copolymerized or interpolymerized with one or more amide acrylate compounds. Can be configured.

Typically, other monomer components include alkyl acrylate compounds consisting of esterification or partial esterification reaction products of lower alkyl polyhydric alcohols and acrylic or methacrylic acids.

Examples of preferred lower alkyl polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexanediol, glycerin, neopentyl glycol, pentaerythritol, trimethylolethane, trimethylolpropane and 2. 2-dimethyl-3
-Hydroxypropyl 2,2-dimethyl-3-hydroxypropionate.

Epoxy acrylates can also be included as additional polymeric components in amide acrylate compositions.

Useful epoxy acrylates include the reaction products of acrylic and methacrylic acids with alkyl or aryl polyfunctional epoxides.

Typical alkyl epoxides include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.

Typical aryl polyfunctional epoxides include polyglycidyl ethers of polyphenols, such as bisphenol A diglycidyl ether.

Other useful epoxy acrylates include U.S. Pat. No. 3,874,906.

If a mixture of amide acrylate and alkyl or epoxy acrylate is desired, the hydroxy-containing amide intermediate can be acrylated and the hydroxy-containing compound simultaneously reacted with an acrylating agent or mixture of acrylating agents, e.g. , bis(hydroxyethyl)formamide is acrylated to form a compound of formula partially acrylated or triacrylate monomers can be produced.

This acrylate mixture can then be exposed to curing conditions to produce an interpolymerized acrylate polymer film.

Mixtures of one or more amide acrylate compounds and one or more of the above alkyl or epoxy acrylate monomers can also be utilized as polymerization components of the film-forming composition.

However, the main polymerizable component of the resin consists of an amide acrylate compound or a mixture of amide acrylate compounds.

Coating compositions having amide acrylate compounds of the type described above offer unique advantages.

Generally, these amide acrylate materials have a relatively low viscosity, thus providing the coating composition with the ability to be easily applied, processed and handled.

Another benefit resides in the remarkable rapid curing of the compositions having the above-described amide acrylate compounds when the compositions are irradiated with radiation.

Fast curing, particularly promoted by UV radiation in an ambient atmosphere, is a fast curing process that is useful for substrates to be covered by paper or paperboard typically used for packaging goods where the price of the packaging must be low relative to the price of the goods. There are significant benefits when it comes to wood.

Another desirable property exhibited by amide acrylate-containing coating compositions, particularly paper coating compositions, is improved flexibility of the cured film coating.

This improved flexibility is an unexpected property for an amide acrylate-containing coating since compositions with amide functionality are commonly known as "hard segments" and typically impart stiffness to film coatings.

Certain combinations of the above starting materials tend to produce products that do not provide compositions that cure quickly into mar-resistant films.

For example, diamide acrylates are known to form rather poor films.

In general, the monoamide acrylate monomers of the above formula, and especially the monoamide acrylate monomers shown in the examples below, are highly suitable for use in fast curing coating compositions that form flexible, mar-resistant film coatings.

When one of the above alkyl or epoxy acrylate compounds is present in the composition, it can constitute a major or minor component of the total amount of polymerizing components employed in the coating composition, and thus about 1% of the total amount of polymerizing components employed in the coating composition. It can be present in an amount of up to about 99% by weight.

These alkyl and epoxy acrylate compounds are relatively low cost and light colored, and exhibit a high degree of chemical resistance and good thermal stability.

These compounds are thus useful in increasing the crosslink density of the cured film without substantially interfering with the fast curing properties provided by the amide acrylate component, yet at the same time imparting desirable properties to the cured coating.

If the coating composition of the present invention consists of less than 99% amide acrylate monomer or a mixture of various amide acrylate monomers, or amide acrylate monomer mixed with the alkyl or epoxy acrylate compounds mentioned above, radiation curing A copolymerizable reactive solvent selected from any of the conventional ethylenically unsaturated monomeric materials can constitute a major or minor component of the film-forming composition.

Common groups of such reactive functional monomers include styrene, vinylamide, esters of vinyl alcohol, acrylic esters, maleic esters, fumaric esters.

The amount of functional monomer in the composition can vary from about 1% to about 99% by weight of the composition.

Usually the amount of monomer will range from about 1 to 50%. In place of, or in addition to, the reactive solvents described above, substantially non-reactive volatile solvents can also be present in the composition.

Examples of such volatile solvents include xylene, toluene,
Includes chloride, 2-methoxyethanol, methyl isobutyl ketone and isopropyl alcohol.

One or more of such fluids can be present in the composition in amounts ranging from trace amounts up to about 20% by weight of the amide acrylate component.

Generally, these volatile solvents are used during the manufacture of the compositions, but the solvent stripping methods described in the examples below (
solventstrlpping process)
is substantially removed from the final composition by.

Another component that may be present in small amounts in the composition is a urethane-acrylate cocuring agent.

These co-curing agents are typically derived by stepwise reaction of three components: a prepolymer component, an isocyanate-containing compound, and a polyfunctional compound having both functional groups reactive with incyanato groups and ethylenic functionality. be done.

The prepolymer component is further characterized as having a molecular weight range of 300 to 3000 and having more than one reactive hydroxyl functionality.

Examples of suitable prepolymers include polyester polyols, polyether polyols, and poly(hydrocarbylsiloxane) compounds containing hydroxyl functionality pendant to the siloxane backbone.

A preferred family of polyester polyols of molecular weight from about 500 to about 1300 are derived by the reaction of various polyglycols with ε-cabrolactone, such as sold under the trade name Union "NIAX" polyol.

The isocyanate-containing compound can be chosen from a wide group of isocyanates having more than one isocyanate functional group, such as aliphatic polyisocyanates and aromatic polyisocyanates, with bis(4-isocyanatocyclohexyl)methane being particularly preferred. It is an isocyanate-containing compound.

The functional group of the polyfunctional compound that is reactive with the isocyanate group is typically a hydroxyl group.

Examples of useful polyfunctional compounds for making co-curing agents are acrylic acid and hydroxyl-containing acrylic esters, with 2-hydroxyethyl acrylate being a particularly preferred polyfunctional compound.

Some of these co-curing agents, particularly those made from prepolymer components having a siloxane backbone, have been found to improve the flow properties of face compositions.

Many of these compounds also impart "slip" to the cured film coating when co-cured with an amide acrylate compound or a mixture of an amide acrylate and an alkyl acrylate or an epoxy acrylate;
Moreover, it does not interfere with the curing speed of the composition.

A preferred co-curing agent having the properties described above is produced by reacting a polydimethylsiloxane containing alcohol functionality pendant to the siloxane backbone with a diisocyanate such as inphorone diisocyanate to form an intermediate. Polysiloxane urethane acrylates are derived by subsequently reacting the intermediate with 2-hydroxyethyl acrylate to obtain an acrylate-functional urethane siloxane.

Suitable useful polydimethylsiloxane starting materials include:
Included are "silicone polycarbinols" sold by Dow Corning under the trade names "Silicone Q4-3557" and "Silicone DC193."

The amount of co-curing agent present in the composition generally comprises about 0% of the composition.
．． 1 to about 50% by weight, usually about 0.1 to about 2% by weight.
Exist in the range of 0%.

Other substances that may be present in the composition include viscosity modifiers to increase or decrease the viscosity of the composition for use as a varnish coating.

In some cases, viscosity modifiers are necessary to enable a uniform film of the composition to be applied to the substrate without tears or discontinuities by a conventional press or roller coater.

For example, dry lithography
cpress processes), a relatively high viscosity, e.g.
A varnish composition of s or more is required.

In contrast, gravure or offset gravure printing processes require relatively low viscosity compositions, eg, less than 2560 cps.

Examples of such viscosity modifiers are cellulose acetate butyrate, carboxymethylcellulose, microcrystalline cellulose, fumed silica, castor oil based compositions [e.g. Thicatrol from Baker Castor Oil Co.
ol), 12-hydroxystearic acid, alkyd polymer, “acryloid (Ac
thermoplastic polymers of acrylic and methacrylic esters, such as the esters sold under the trade name "ryloid", and modified clays.

These materials, when used, typically make up about 0% of the composition.
．． Present in an amount ranging from 5 to about 15% by weight.

One or more surface tension reducing agents may also be present in the composition.

Substances that lower the surface tension of these compositions improve their ability to be applied without "hanging up" on the coater when the composition is applied onto the coater with a roller coater.

These surface tension reducing agents also improve the leveling or flow of the composition over the substrate, allowing the formation of void-free coating films of uniform thickness.

Preferred surface tension reducing agents include Andhas'"Modaflow" flowage
nt)].

Other surface tension reducing agents include fluorocarbons and nonionic alkyl ester surfactants as a group;
Ethoxylated alkyl ester surfactants and ethoxylated phenolic surfactants, such as “
900 Series Surfactants
These include surfactants sold under the trade name "Surfactants".

The surface tension reducing agent, if used, accounts for about 0.1 of the composition.
It can be present in a range of up to about 10% by weight.

Another component often present in the composition is a slip-aid agent that improves the desired slip properties of the cured film coating.

Slip aids include fatty acids and waxes consisting of fatty acid esters and esters of long chain monohydric alcohols and long chain fatty acids, such as those sold by Witco Chemical.

The term "long chain" refers to generally chain-like compounds having from 11 to 25 carbon atoms in the chain.

Examples of these waxes include esters formed by the reaction of aliphatic alcohols such as cetyl alcohol and stearyl alcohol with fatty acids such as stearic acid, palmitic acid and myristic acid.

Preferred waxes include those comprising mixtures of cetyl palmitate and related fatty acid esters, with spermaceti being a particularly preferred example.

When a slip aid is used in the composition, it is usually present in an amount ranging from about 0.01% to about 10% by weight of the composition.

The compositions of the present invention can be cured as protective and decorative film coatings in the presence of ionizing or actinic radiation as defined below.

If the coating composition is to be cured by UV radiation, a photocatalytic system consisting of a photosensitizer, or a photoaccelerator, or a photoinitiator, or a mixture of two or all three of these components, is usually present. do.

A photoinitiator is a compound that absorbs a photon and obtains energy to generate a radical pair, at least one of which initiates addition polymerization of an acrylic or methacrylic group in a known manner.

Photosensitizers are compounds that are good photon absorbers but themselves poor photoinitiators.

The photosensitizer absorbs photons to produce excited molecules, which in turn interact with a second compound to produce suitable free radicals for initiation of addition polymerization.

The second compound may be a monomer, a polymer, or an added initiator.

Examples of photoinitiators are benzoin, methyl benzoin ether butyl benzoin ether, isobutyl benzoin ether, α, α-diethoxyacetophenone α, α-dimethoxy α-phenylacetophenone, α-chloroacetophenone and methyl phenylglyoxylate. It is.

Examples of photosensitizers are benzyl, 1-naphthaldehyde, anthraquinone, benzophenone, 3-methoxybenzophenone, benzaldehyde and anthrone.

Photopromoters are compounds that do not absorb photons, but improve the effectiveness of photopromoters and photoinitiators by acting as very good hydrogen donors.

Amines as a group are good photoaccelerators, and special amines such as tertiary alkylamines, tertiary alkanolamines, and diamines include particularly good photoaccelerators.

The amount of photosensitizer, photoaccelerator, or photoinitiator, or a mixture of two or three of these compounds, present in the radiation-curable coating composition can vary over a wide range.

If any of these materials are present, the amount usually ranges from about 0.01 to about 0.01 to about 0.01 of the polymerizable compound of the coating composition.
In the range of about 20% by weight, most often in the range of about 0.1 to about 5%.

These substances are usually removed from the coating composition when the coating is cured by ionizing radiation;
May exist.

Extender pigments may also be present in the composition, and when ultraviolet light is used to cure the film, it is preferred that the extender pigments be substantially transparent to ultraviolet light.

Examples of extender pigments that are transparent to ultraviolet light are silica, calcium carbonate, barium sulfate, talc, aluminum silicate,
Sodium aluminum silicate and potassium aluminum silicate.

Hiding and/or coloring pigments may also optionally be present.

If the pigment is of the UV-absorbing type and the coating composition is to be cured by UV radiation, the pigment should be used in an amount that does not interfere with the internal curing of the coating.

Examples of hiding pigments are titanium dioxide, antimony oxide, zirconium oxide, zinc sulfide and lithopone.

Examples of coloring pigments are iron oxide, cadmium sulfide, carbon black, phthalocyanine blue, phthalocyanine green, indanthrone blue, ultramarine blue, chromium oxide, burnt umber, benzidine yellow, toluidine red and aluminum powder.

It is also possible to use individual pigments or mixtures of hiding and/or coloring pigments.

Mixtures of extender pigments, hiding pigments and/or coloring pigments can also be used.

Dyes can also be present in the coating composition in amounts commonly used.

Pigmentless or "clear" radiation-curable coating compositions of the present invention are typically prepared simply by mixing a solution of the polymerizable compound dissolved in a reactive solvent with such other ingredients as may be present. be done.

If a pigmented composition is desired, Cowl's
es), it may be necessary to disperse the pigment into the composition using conventional high speed dispersion techniques such as those used in ball mill or sand mill mixing equipment.

Radiation curable coating compositions are used to form a cured adherent coating on a substrate.

Coating the substrate with the coating composition is accomplished using any method known in the art.

Coating methods include spraying, curtain coating, dip coating, direct roll coating, reverse roll coating, painting, brushing, printing, drawing and extrusion.
on).

The coated substrate is then irradiated with radiation of sufficient intensity for a sufficient period of time to crosslink the coating.

The duration and intensity of the radiation applied to the coating composition can vary within a wide range.

In general, irradiation should continue until a hard, solvent-resistant film is obtained; however, in some applications it may be desirable to continue curing only until a gel stage is obtained. The substrates that can be used have a wide range of properties.

Organic substrates such as wood, fibreboard, particleboard, hardboard, paper, cardboard, and various polymers such as polyester polyamides, cured phenolics, cured aminoplasts, acrylics, polyurethanes, rubber, etc. Can be used.

Inorganic substrates are represented by glass, quartz and ceramic materials.

Many metal substrates can also be coated.

Typical metal base materials are iron, steel, stainless steel, copper, brass,
Bronze, aluminum, magnesium, titanium, nickel, chromium, zinc and alloys.

Particularly suitable substrates are paper or paperboard with printed or decorative markings on which fast-curing protective transparent or pigmented films are formed from the amide acrylate-containing compositions of the present invention.

The compositions of the invention can also be used as fillers for porous materials such as wood, and for vinyl overlays and free vinyl overlays.
) is also suitable as a top coat.

Cured coatings of radiation curable coating compositions typically range in thickness from about 0.001 to about 3 mm.

Thicknesses more often range from about 0.002 mm to about 0.3 mm, with coatings ranging from 0.002 mm to 0.10 mm being most preferred.

The coatings of the present invention can be cured by irradiation with ionizing radiation.

The dose unit for ionizing radiation is "rad", and "rad" is the energy 10 absorbed from ionizing radiation per 12 irradiated objects.
Equals 0 ergs.

As used herein and in the claims, dose is defined as dose, regardless of the identity of the irradiated coating composition.
A bleached calibrated blue cellophane film is used as a reference standard.

The coatings of the invention can also be cured by irradiation with actinic radiation.

As used herein, actinic radiation is defined as having a wavelength of 70 nm or more, capable of directly or indirectly generating free radicals capable of initiating addition polymerization of the coating compositions of the present invention.
It is an electromagnetic radiation of 0 nm or less.

To absorb photons and generate free radicals, a photoinitiator, photosensitizer, photoaccelerator or mixture of these components is usually present, although in some cases these substances may not be necessary .

Actinic radiation has insufficient energy to produce ions in a medium of common elements such as air or water, and thus has an energy of about 10 eV or less.

The most commonly used form of actinic radiation is ultraviolet radiation, or about 1
Electromagnetic radiation has a wavelength in the range of 80 to about 400 nm, although longer or shorter wavelength actinic radiation can also be used effectively.

Any suitable source of ultraviolet radiation can be used in the practice of this invention.

A suitable UV source is Gierardo W. No. 4,017,652 to Gruber.

The duration and intensity of the actinic radiation applied to the coating composition can vary over a wide range.

Observing the general principles mentioned above, irradiation with actinic radiation should normally be continued until a C-stage is obtained.

However, in some applications, irradiation may be stopped when stage B is reached.

The following examples show specific reaction component amounts and reaction conditions,
Several additives such as catalysts, diluents, surfactants, etc. are specified for the preparation of amide acrylate compounds for use in the present invention.

All parts and percentages are by weight unless otherwise noted.
All viscosity values were measured on the Gardner-Bolt viscosity scale on undiluted samples.

However, these examples should not be considered limiting as many variations and modifications are possible.

Examples 1 to 18 described below show examples of producing the amide acrylate component contained as an effective radiation-curable component in the composition of the present invention, and Example 19 shows the production of the urethane acrylate co-curing agent component used in the present invention. Examples 20 to 25 show examples of manufacturing the highly radiation-sensitive composition of the present invention and application examples thereof.

Example 1 A reactor is equipped with a stirrer, a heater, a cooling system, a thermometer, and a condensing system designed for azeotrope reflux, commonly known as a Dean-Stark trap.

In this reactor, 544 parts of an intermediate reaction product produced by the reaction of equimolar amounts of formic acid and diethanolamine,
233 parts of 1,1,1-trimethylolpropane, 785 parts of glacial acrylic acid, 86 parts of a 0.1% toluene solution of phenothiazine, butylstannoic acid
0.7 parts of hydroquinone and 386 parts of toluene are added.

The Dean-Stark trap is filled with toluene to aid in the separation of the water component from the water-toluene azeotrope.

With the apparatus set at maximum agitation and maximum azeotropic reflux, the reaction mixture is heated to about 107°C for 20 minutes and to about 110°C for the next hour.

During the initial 1 hour and 20 minute heating period, approximately 32 parts of reaction water is separated from the volatile azeotropes and collected in the Dean-Stark trap.

The reaction mixture is then heated to 110-121°C for 8 hours and 30 minutes, being careful not to allow the temperature to exceed 127°C.

At the end of this heating period, approximately 168 parts of water are collected from the reactor.

The reaction mixture is then cooled to 49-52°C and filtered through a nylon bag into a storage container.

Approximately 181 parts of the reaction product is added from the storage vessel to an airtight reactor equipped with a stirrer, heater, cooler, thermometer and vacuum distillation apparatus.

The reactor is evacuated to 20-23 mm Hg absolute and the reaction product is heated to about 77° C. for 2 hours and 30 minutes.

Approximately 34 parts of distillate, consisting primarily of toluene, is collected during this initial heating period.

The reaction product is then heated at about 80° C. for a further 1 hour under 18 mm vacuum.

The amount of distillate remained at 34 parts, indicating that most of the volatile solvent was thus removed from the reaction product.

The product is then cooled to about 52°C and strained through a 10μ GAF filter into a storage container.

Example 2 A reactor equipped with a stirrer, heater, cooler, thermometer, and condenser is charged with 134 parts of diethanolamine and the contents are heated to about 67° C. under a nitrogen blanket for about 3 hours.

While maintaining the temperature of the reactor at about 67°C, 115 parts of γ-butyrolactone is gradually added to the contents over about 1 hour.

The reaction mixture is then kept at 65-68° C. for 7 hours, after which the viscosity reaches Y+.

The reaction product, identified as N.N-bis[2-hydroxyethyl-(γ-hydroxybutyramide)], was then diluted with ca.
Cool to 2°C and strain through a nylon bag into a storage container.

In another reactor equipped as before and having a Dean-Stark trap, 95 parts of the above reaction product was charged at 97%.
It was added together with 2 parts of formic acid.

The reaction mixture was then stirred for 15 minutes and the reactor was charged with approximately 1
At a temperature of 0°C, 2 parts of butyl stannic acid, 0.0 phenothiazine
18 parts, di-t-butyl-p-cresol (“Ionol” inhibitor, manufactured by Shell Oil Co.) 0.9
5 parts, 0.068 parts of hydroquinone, 92 parts of glacial acrylic acid and 29 parts of toluene.

The reaction mixture is then heated to about 121° C. for about 90 minutes;
At this point the apparatus is set to maximum agitation and maximum azeotropic reflux.

The reaction mixture is maintained at a temperature of 116-139°C for about 12 hours.

During this time, maintain maximum reflux conditions.

During this reflux period, the acid number of the reaction mixture (measured in milliequivalents of titrated KOH per 17 samples) and the amount of by-product water obtained from the azeotropic distillation are measured approximately every 30 minutes.

At the end of the reflux period, the acid number is 28.9 and about 22 parts of water have been collected.

The reaction mixture was then cooled to about 52°C, followed by 50μ of G
Strain through the AF filter into a storage container.

The unstripped resin-solvent mixture prepared above about 19
5 parts are placed in a reactor equipped with a heating device and a vacuum distillation device.

The mixture is heated and at the same time a vacuum is created in the reactor.

After maintaining the temperature at 60-63° C. for about 2 hours under vacuum conditions, about 18 parts of volatile distillate are collected.

Example 3 104 parts of ε-caprolactone are placed in a reactor equipped with a stirrer, heater, cooling device, thermometer and condensing device,
Heat to about 52° C. for 30 minutes under a nitrogen blanket.

Next, diethanolamine 9, which has been preheated in this reactor,
Add 5 parts gradually over 50 minutes, taking care during the exothermic reaction to ensure that the temperature of the reaction mixture does not exceed 57°C.

The temperature of the reaction mixture is then raised to 60-63°C and maintained at this temperature for approximately 2 hours and 40 minutes.

A further 17 parts of ε-caprolactone are then added to the reaction mixture with gradual heating over 1 hour to raise the temperature to 68-71°C.

After keeping the reaction mixture at 68-71°C for 4 hours, the base number (
A base value of 18.2 (expressed in milliequivalents of back-titrated KOH per gram of sample) was obtained.

The amidetriol intermediate product is then cooled to room temperature.

In another reactor equipped as before and having a Dean-Stark trap to remove water from the azeotrope, 109 parts of the above intermediate product were mixed with 9 parts of glacial acrylic acid.
8 parts of butyl stannic acid, 2 parts of phenothiazine, 0.013 parts of phenothiazine, 0.2 parts of hydroquinone and 39 parts of toluene.

The reaction mixture is then heated to about 114° C. for about 45 minutes, at which point the apparatus is set to maximum agitation and maximum azeotropic reflux.

The reaction mixture is maintained at a temperature of 111 DEG -126 DEG C. for about 10 hours, during which time maximum reflux conditions are maintained.

During the reflux period, the acid number of the reaction mixture and the amount of by-product water obtained from the azeotropic distillation are measured approximately every hour.

At the end of the reflux period, the acid number was 48.7 and about 19 parts of water had been collected.

The reaction mixture was then cooled to about 52°C and then
Strained through a GAF filter into a storage container.

The above-produced stripping resin-solvent mixture about 22
7 parts are placed in a reactor equipped with a heating device and a vacuum distillation device, heated and at the same time a vacuum is created in the reactor.

After maintaining the temperature at 77-81°C under vacuum for about 33/4 hours, about 29 parts of volatile distillate are collected.

The hydroxyl value of the produced amide acrylate compound was 61, and the equivalent weight per double bond was 244.

Example 4 Into a reactor equipped as in Example 1, 88 parts of 90% formic acid are added together with 130 parts of N-methylethanolamine.

The mixture was refluxed in the conventional manner to collect approximately 33 parts of water.

In this reactor, 135 parts of glacial acrylic acid and 2.5 parts of butyl stannic acid were added.
1 part and 6 parts of hydroquinone were added and the mixture was heated and reacted under the same conditions as in Example 1, with 27 parts of water being collected after the reaction.

2 parts of sodium acetate are then added and the mixture is stirred for about 1 hour before the volatile solvent is removed from the reaction mixture as in Example 1 by the stripping method described above.

The hydroxyl value of the produced amide acrylate compound was 19, and the equivalent weight per double bond was 218.

Example 5 Into a reactor equipped as in Example 1, 207 parts of triolamide having a molecular weight of 207 (Eastman Kodak Company) are placed.

To this reactor were added 230 parts of glacial acrylic acid and 6.0 parts of hydroquinone.
6 parts, 0.7 parts of di-t-butyl-p-cresol, 4.4 parts of butyl stannic acid and 100 parts of toluene are also added.

After reacting for 7−+ hours under the same conditions as above, about 5
Three parts of water was collected.

The reaction mixture is neutralized with an ion exchange resin, filtered and the solvent removed by the stripping method described above.

The hydroxyl value of the produced amide acrylate compound was 8, and the equivalent weight per double bond was 186.

Example 6 Into a reactor equipped as in Example 1, 105 parts of diethanolamine, 120 parts of 70% glycolic acid and 100 parts of toluene are added.

This mixture is refluxed for 4 hours under conditions similar to those described in Example 1, with approximately 54 parts of water collected at the end of reflux.

In this reactor, 237 parts of glacial acrylic acid and 4.1 parts of butyl stannic acid were added.
1 part, 6 parts of hydroquinone, 1 part of di-t-butyl-p-cresol and 150 parts of toluene.

After the mixture is then refluxed for 5 hours, the reaction mixture is diluted with toluene to a solids content of 30% and filtered with suction using 20% sodium hydroxide.

Then 0.1% hydroquinone is added and the volatile solvent is spun from the mixture as before.

The hydroxyl value of the produced amide acrylate compound is 32.
2, and the equivalent weight per double bond was 148.

Example 7 In a reactor equipped as in Example 2, diethanolamine 1
0.05 parts, 134.2 parts of benzoic acid and 100 parts of toluene.

After the reaction mixture is refluxed under a nitrogen blanket for 41/2 hours under the conditions indicated above, 18 parts of water are collected.

Next, 158 parts of glacial acrylic acid, 3.7 parts of butyl stannic acid, 5 parts of hydroquinone, 0.7 parts of di-t-butyl-p-crenol, and 150 parts of toluene are added to the reactor.

After the mixture is refluxed for about 5 hours, 38 parts of water are collected.

The product was then diluted with toluene to 50% solids and 2
Dry over 0% sodium hydroxide sulfate and filter with suction.

The volatile solvent is removed from the product using the stripping method described above.

The hydroxyl group of the generated amide acrylate compound is 8.2
The equivalent weight per double bond was 295.

Example 8 In a reactor equipped as in Example 1, 10 mL of diethanolamine was added.
5 parts, 158.4 parts of 2-ethylhexanoic acid and 50 parts of toluene.

After the mixture has been brought to reflux under conditions similar to those given previously, 18 parts of water are collected.

Next, 158.4 parts of glacial acrylic acid, 4 parts of butyl stannic acid, 5.6 parts of hydroquinone, di-t-butyl-p
- Add 1 part of cresol and 150 parts of toluene.

After the mixture is refluxed according to the conditions given above, it is diluted to 30% solids with toluene, washed with 20% sodium hydroxide, dried over sodium sulfate, and filtered with suction.

After adding 0.1% hydroquinone to the product, the volatile solvent is stripped as before.

The hydroxyl value of the generated amide acrylate compound is 3.8
The equivalent weight per double bond was 272.

Example 9 To a reactor equipped as in Example 1 are added 240 parts of methyl formate and 210 parts of diethanolamine.

This mixture is refluxed for about 40 minutes under the conditions indicated above.

Then, in another similarly equipped reactor, the product from the above reaction, namely 200 parts of bis(hydroxyethyl)formamide, was mixed with 216 parts of acrylic acid and 0.2 parts of phenothiazine in 350 parts of trichloroethylene solvent and 111 parts of phenothiazine. After reacting for /2 hours, about 29 parts of reaction ice is collected.

From the reaction product, identified as bis(acrylyloxyethyl)formamide, 210 parts of volatile solvent are removed by the conventional method described above.

Next, 56 parts of triethyl orthoformate are added to the reaction product with an initial thickening value of 150.

This mixture is then heated at 60-70°C for 1 hour, giving the mixture an acid number of 102.

Example 10 In a reactor equipped as described in Example 1, 133 parts of bis-2-hydroxyethylformamide, 220 parts of triethylamine, 0.015 parts of di-t-butyl-p-cresol, 0.015 parts of of phenothiazine and 200
of toluene solvent.

The reaction is allowed to proceed by gradually adding 181 parts of acrylyl chloride over a period of 3 hours while stirring and maintaining the temperature at about 25° C. with a cooling means.

After the addition is complete, stirring is continued while maintaining the temperature at about 25° C., followed by filtration and removal of the solvent by conventional stripping techniques.

The hydroxyl value of the produced amide acrylate compound was 58, and the equivalent weight per double bond was 158.

Example 11 Into a reactor equipped as described in Example 1, 75 parts of N-methylethanolamine are added.

Add 176 parts of ethyl acetate to the reactor dropwise, taking care to control the exothermic reaction.

85 while heating the reaction mixture and collecting the ethanol distillate.
After refluxing for 15 minutes at ˜87° C., a base number of 149 is obtained.

Next, 100 parts of ethyl acetate is added to this reaction mixture, and reflux is continued for an additional 3 hours to obtain a base number of 83.

After further refluxing for 3 hours, the base number of the reaction mixture decreased to 67.
become.

Reflux is then continued until the temperature reaches 94°C, at which time another 100 parts of ethyl acetate is added.

After continuing reflux for a further 3 hours, a base number of 49 is obtained.

The volatile solvent is removed from the reaction mixture in a conventional manner.

Into a reactor equipped as before, 94 parts of the reaction product obtained above were charged with 58 parts of acrylic acid, 0.03 parts of 0.
．． Add 1% phenothiazine solution, 0.02 parts of hydroquinone, 200 parts of methyl isobutyl ketone and 100 parts of toluene.

After the reaction mixture was refluxed at 114-117° C. for 51/2 hours, 11 parts of reaction water were collected.

The mixture is then cooled and left overnight.

Next, refluxing was further continued at 117-119°C for about 6 hours, and then an additional 3 parts of reaction water was collected.

Example 12 To a reactor equipped as in Example 1 are added 148 parts of phthalic anhydride, 140 parts of diethylene glycol and 200 parts of toluene.

The reaction mixture is gradually heated to 60° C., taking care to control the exothermic reaction.

The mixture is held at about 60°C for 30 minutes and then at about 80°C for an additional 90 minutes.

To this mixture at about 89° C. 105 parts of diethanolamine are added dropwise over a period of 10 minutes.

The mixture is then refluxed for about 5 hours while increasing the temperature to about 111°C.

Approximately 176 parts of xylene is then added to the reaction mixture to replace the approximately 132 parts of toluene that is removed during reflux.

The mixture was then refluxed at 125-130°C for 8 hours, after which
216 parts of acrylic acid are added to the reaction mixture together with 0.02 parts of hydroquinone, 3 parts of butyl stannic acid and 20 ml of 0.1% phenothiazine solution.

After continuing to reflux for 4 hours at 126-136°C, approximately 48 parts of reaction water is collected.

The hydroxyl value of the produced amide acrylate compound was 45, and the equivalent weight per double bond was 263.

In addition, the reaction products were analyzed and confirmed by infrared absorption spectroscopy.

Example 13 A reactor equipped as in Example 1 is charged with 150 parts of N-methylethanolamine and heated to about 50°C.

Then 250 parts of ε-caprolactone are added dropwise to the reaction mixture over a period of 2 hours.

After keeping the temperature of the reaction mixture at about 50°C for 1 hour, about 60°C
Keep at ℃ for 2 hours.

The base number of this reaction mixture was 42.

A further 15 parts of ε-caprolactone are then added to the reaction mixture.

The temperature of the reaction mixture is then maintained at 60° C. for 90 minutes, after which the base number is 24.9.

After keeping the mixture at 60°C for another hour, it was again heated to 24.9°C.
A base value of .

Next, while maintaining the temperature at 60°C, add an additional 15 parts of ε-
After adding caprolactone to the reaction mixture, a base number of 19.9 was obtained.

The reaction mixture was then cooled and 288 parts of acrylic acid, 77%
Add 10 parts of formic acid, 25 parts of 0.1% phenothiazine solution, 4 parts of butyl stannic acid, 0.03 parts of hydroquinone, and 250 parts of toluene solvent to the reactor.

The reaction mixture was then refluxed for 8 hours and 60 parts of water of reaction was collected.

The mixture is then filtered to remove volatile solvents by conventional stripping techniques.

The hydroxyl value of the produced amide acrylate compound was 37, and the equivalent weight per double bond was 206.

In addition, the reaction products were analyzed and confirmed by infrared absorption spectroscopy.

Example 14 Into a reactor equipped as in Example 1, 134 g of dimethylolpropionic acid, 0.5 part of methanesulfonic acid and 400 parts of methanol are added.

After refluxing the reaction mixture for 15 hours, an acid number of approximately 14.5 is obtained.

Next, 200 parts of toluene, 105 parts of diethanolamine and 8 parts of sodium methoxide (25% in methanol)
part to the reaction mixture.

After refluxing the mixture for about 1 hour while increasing the temperature of the mixture from 70°C to 150°C, about 2/3
Approximately 475 parts of volatile solvent consisting of 1/3 methanol and about 1/3 toluene are collected.

The base number of this reaction mixture is 244. About 176 parts of toluene was added to the reaction mixture, and the temperature was about 113-134°C.
After continuing to reflux for another 3 hours and 40 minutes, the base number reached 177.
was gotten.

The reaction mixture is then refluxed for an additional 5+ hours.

Next, 210 parts of acrylic acid, 5 parts of butyl stannic acid,
Add 0.03 parts of phenothiazine solution, 0.2 parts of hydroquinone and 87 parts of toluene.

The reaction mixture was then refluxed for 8 hours, after which 31 parts of reaction water was collected.

The volatile solvent is then removed from the reaction mixture in a conventional manner.

Example 15 To a reactor equipped as in Example 1, 10 parts of aminobenzyl alcohol are added together with about 175 parts of toluene.

12 parts of ε-caprolactone are then added dropwise to this reaction mixture over a period of 10 minutes at a temperature of about 55°C.

After allowing the reaction to proceed for 2 hours at approximately 55°C, a base number of 0.8 was obtained.

Next, this reaction mixture was added with 14 parts of acrylic acid, 0.3 parts of butyl stannic acid, 0.01 part of hydroquinone, and 0 parts of phenothiazine.
．． 002 parts were added and the reaction mixture was heated at 106-112°C for 7 hours.
After refluxing for an hour, the volatile solvent is removed in a conventional manner.

The reaction products were analyzed and confirmed by infrared absorption spectroscopy.

Example 16 In a reactor equipped as in Example 1, diethanolamine 26
Add 3 parts along with 45 parts of toluene.

136 parts of 85% formic acid are added dropwise to the reactor over a period of 30 minutes without any heating during the exothermic reaction.

The reactor is then heated and maintained at reflux for 8 hours.

The temperature during this time is 101-113°C.

Approximately 61 parts of water was collected at the end of the reflux period.

The volatile solvent is then removed from the reaction mixture in a conventional manner.

In a second reactor similarly equipped, 172 parts of methacrylic acid;
133 parts of the reaction product prepared above, 2 parts of butyl stannic acid, 0.5 part of di-t-butyl-p-cresol, 0.1 part of hydroquinone, 0.02 part of phenothiazine and 2 parts of toluene.
Add 00 copies.

The reaction mixture was refluxed for 83/4 hours at 118-126°C and 28 parts of water were collected.

The reaction mixture was then cooled, filtered and stripped of volatile solvents in a conventional manner.

The hydroxyl value of the generated amide acrylate compound is 106
The equivalent value per double bond was 147.

In addition, the reaction products were analyzed and confirmed by infrared absorption spectroscopy.

Example 17 In a reactor equipped as in Example 1, γ-valerolactone 22
0 parts and 210 parts of diethanolamine are added.

After heating the reaction mixture at about 100° C. for 2 hours and 10 minutes under a nitrogen blanket, the viscosity of the undiluted sample was determined to be L+.

The reaction mixture was cooled and left overnight at approximately 100°C.
After heating for 1 hour, the viscosity was V0.

In a second reactor similarly equipped, 14 parts of 97% formic acid are added slowly over 15 minutes to 245 parts of the 75.7% solids reaction product prepared above. 297 parts of acid, 5.4 parts of butyl stannic acid, 0.05 part of phenothiazine, 0.27 part of hydroquinone, Z-T
-2.5 parts of butyl-p-cresol and 82 parts of toluene
Add part.

After heating the reaction mixture at 123-130°C for about 2 hours,
Collect 29 parts of water.

The reaction mixture was then cooled and left overnight, after which 130-
After heating at 140° C. for about 7 hours, an additional 30 parts of water was collected.

The reaction mixture is cooled and left under ambient conditions at room temperature for about 65 hours.

Next, after heating this mixture at about 140°C for about 1 hour,
Two additional parts of water were collected.

The reaction mixture was then filtered, stripped, and refiltered in a conventional manner, and an undiluted sample of the reaction product had a viscosity of C-.

The hydroxyl value of the generated amide acrylate compound is 226
The equivalent weight per double bond was 225.

In addition, the reaction products were analyzed and confirmed by infrared absorption spectroscopy.

Example 18 842 parts of diethanolamine and 159 parts of toluene are added to a reactor equipped with a stirrer, heater, cooling device, thermometer and condensing device.

The initial temperature of the reactor contents is about 33°C, and after adding 383 parts of 97% formic acid to the reactor over 30 minutes with constant stirring, the temperature is about 94°C.

Heating was continued under reflux conditions for about 3 hours, during which time about 132
Part of the reaction water is collected and the temperature rises to 138°C.

The reaction mixture is then cooled to about 66° C. over a period of 30 minutes.

Next, 1,1,1-trimethylolpropane 5 was added to the reactor.
34 parts of acrylic acid, 1797 parts of acrylic acid, 196 parts of 0.1% phenothiazine toluene solution, 1.6 parts of hydroquinone, 32 parts of butyl stannic acid and 880 parts of toluene.

The temperature of the reaction mixture is raised to about 110° C. by heating for about 1 hour and 15 minutes, at which point reflux begins.

Refluxing was continued for 9 hours, and the temperature of the reaction mixture was gradually increased to 118
After raising to 0.degree. C., 462 parts of water were collected and the acid number of the reaction mixture (measured as milliequivalents of titrated KOH per sample 17) was 38.

The reaction product is then cooled to about 52° C. and placed in a storage container.

4600 parts of the above reaction product are placed in a reactor equipped with a heating device, a cooling device, a thermometer and a vacuum distillation device.

The initial temperature of the contents of the reactor is 37°C, and the temperature inside the reactor is 37°C.
Apply vacuum to mmHg absolute pressure.

After heating for 1 hour and 40 minutes, the temperature is approximately 77°C
The vacuum was increased to 38 mm and 890 parts of distillate, consisting primarily of toluene, were collected.

After holding the reaction product under these conditions for an additional hour and 20 minutes, the vacuum was 20 mm Hg absolute and the temperature was approximately 79° C., and a cumulative total of 947 parts of distillate was collected.

The reaction product is then cooled to about 52° C. and strained through a 10 μGAF filter bag into a storage container.

Example 19 In a reactor equipped with a stirrer, a heater, a cooling device, a thermometer and a condensing device, 1164 parts of inphorone diisocyanate,
Add 200 parts of triethylene glycol diacrylate and 0.4 parts of dibutyltin dilaurate catalyst.

Set the apparatus to maximum agitation and heat to raise the temperature of the reaction mixture to about 40°C.

Next, over a period of about 2 hours,
296 parts of polydimethylsiloxane, commercially available from Dow Corning under the trade name "Licone) Q4-3557", are added to the reactor.

The exothermic reaction occurring during this time is controlled by keeping the temperature at 40-42°C.

The reaction mixture is then heated to about 49°C over 15 minutes and then held at 49°C for about 30 minutes.

Provide an air sparge to the reaction mixture creating a nitrogen blanket over the surface of the reaction mixture.

Next, a mixture of 138 parts of 2-hydroxyethyl acrylate and 1.5 parts of di-t-butyl-p-cresol (Shell Oil's blocking agent, "ionol") is added to the reactor over a period of 30 minutes. .

Then, after keeping the reaction mixture at 49-52°C for about 5 hours,
Viscosity measurements were performed on an undiluted sample of this reaction mixture, and the viscosity was "J" on the Gardner-Holdt scale.

Then, after heating to raise the temperature of the reaction mixture to about 60°C,
Maintain temperature at 64-71°C for approximately 4 hours.

When the viscosity was measured, it was "R+".

The reaction mixture is then cooled to about 49° C. and filtered through a double layer nylon bag into a storage container.

Example 20 In a reactor equipped with a thermometer, stirrer and heating device, poly(
2-ethylhexyl acrylate) [Moda-flow, a flow agent manufactured by Rohm and Haas Co., Ltd.]
108 parts, α・α-dimethoxy-α-phenylacetophenone [IrgaCure (manufactured by Ciba Geigy)
cure) 651”] 538 parts, benzophenone 246
1 part, 65 parts spermaceti and 943 parts isopropyl alcohol.

The contents of the reactor are thoroughly mixed and heated to form a uniform “pre-
Make a “mix” solution.

In each of two further reactors "A" and "B", equipped as before, 1161 parts of the amide acrylate reaction product prepared as described in Example 18 were charged as in Example 1. Produced amide acrylate reaction product 1161
995 parts of the amide acrylate reaction product prepared as in Example 3, 86 parts of the silicone urethane acrylate reaction product prepared as in Example 19, and 597 parts of the premix solution prepared above are added.

Methyl phenylglyoxylate 23 in reactor “A” only
Add part.

Horse 3 spindle, 1 with Burtskfield LVF viscometer
Viscosity measurements at 25°C at 2 rpm revealed that the composition “
The viscosity of composition “A” is 360 cps and the viscosity of composition “B” is 38
It was 0 cps.

To determine a satisfactory cure rate, a sample of each composition was #0
16 Morest paint penetration - opacity
on-opacity) #0 on the uncoated portion of the paperboard panel.
03 wire wound drawdown bar
Apply with r).

Samples are also applied to commercially available clay coated paperboard used in the paper coating industry to evaluate the physical properties of the cured coating.

The coated panels are irradiated with one 200 watt per inch mercury lamp from a distance of 31/2 inches above a conveyor carrying the panels at various conveyor speeds.

Data regarding cure rate and physical properties are shown in Table 1.

Example 21 In a reactor equipped with a heating device, a stirring device and a thermometer,
Prepared as generally described in Example 18.

Reaction product 71 consisting primarily of amide acrylate and trimethylolpropane di and triacrylate
Include 3 parts.

While heating and stirring the contents, slowly add 37.5 parts of cellulose acetate butyrate to the reactor to ensure a homogeneous solution is produced.

In a separate reactor, 700 parts of the solution prepared above were added to Example 18.
2468 parts of the reaction product generally prepared in Example 19, 35 parts of benzophenone, 87.5 parts of diethoxyacetophenone, 87.5 parts of methyl phenylglyoxylate, silicone urethane prepared as generally described in Example 19. Add along with 7.5 parts of acrylate reaction product s and 35 parts of poly(2-ethylhexyl acrylate).

Mix these reactants thoroughly to form a homogeneous blend.

Next, 177 parts of methyl isobutyl ketone are added to 3435 parts of this blend and mixed to ensure uniformity.

A sample of this composition was applied as a coating to a paperboard substrate in the manner described in Example 20, and the coating was applied at a conveyor speed of 45.72 m/min (150 ft/min) and 5 ft/min.
8.89c at 3.34m/min (175ft/min)
It is cured by irradiation with a mercury lamp of 200 watts per inch (2.54 cm) from a distance of 31/2 inches (m).

Data regarding curing and physical properties are shown in Table 1.

Example 22 In a reactor equipped with a stirrer, a heating device and a thermometer, 146 parts of the polysiloxane urethane acrylate generally described in Example 19 were charged with 40 parts of diethoxyacetophenone,
Fatty acid ester [manufactured by Uitoko Chemical Co., Ltd., “Uitoko (
Witco) 910''] and amide acrylate reaction product 4 prepared as generally described in Example 3.
Add along with 00 copies.

Mixing of the solution: Heat these reaction components to about 37° C. under constant stirring until a homogeneous blend is obtained. Then slowly add 50 parts of penzophenone to this mixture and continue mixing to homogenize after addition. Continuing, an additional 1335 parts of the amide acrylate reaction product prepared as generally described in Example 3 are added to the reactor along with 8.8 parts of fluorocarbon (3M, "FC-430").

A sample of the composition is applied to a substrate and cured in the manner described in Example 20.

Physical evaluation is as shown in Table 1.

Example 23 Tall oil fatty acids 710
The alkyd is prepared in a conventional manner by condensing 782 parts of phthalic anhydride with 482 parts of glycerin.

Example 18 was added to 400 parts of this alkyd reaction product at 60°C.
600 parts of a reaction product consisting essentially of amide acrylate and trimethylol propane di and triacrylate, prepared in the manner generally described in , are added to a reactor equipped with heating and stirring devices for mixing and cooling. , 368 parts of the reaction product prepared above were combined with 298 parts of an amide acrylate reaction product prepared in the manner generally described in Example 3, a pentaerythritoltri and tetraacrylate blend [Ware Chemical Co., Ltd.
Chemical), “Chemlin”
32 parts of polysiloxane urethane acrylate prepared as generally described in Example 19, 2 parts of fluorocarbon (FC-430, manufactured by 3M Corporation) and 32 parts of methacrylate-terminated polysiloxane (SWS Silicone Corporation). Co., Ltd., "F-816").

Mix all ingredients to form a homogeneous blend, then add 16 parts of penzophenone and α・α-dimethoxy-α-
32 parts of phenyl-acetophenone (Ciba Geigy, "Irgacure 651") are added while constantly stirring the mixture.

The mixture is then transferred to a Cowles mixer and 12 parts of fumed silicon dioxide pigment ("Cab-O-Sil", manufactured by Cabot Corporation) is added to the mixture. .

6.5 on Hegman scale
Continue mixing until a uniform blend with a particle dispersion of ~7.0 is obtained.

A sample of this composition was applied to a substrate of the type described above with a glass rod applicator to a film thickness of about 0.006 mm, Example 2
Curing under the conditions described in 0.

Related data are shown in Table 1.

Example 24 Into a reactor equipped as in Example 1, 150 parts of formic acid are added together with 315 parts of diethanolamine in 50 parts of xylene.

The mixture was stirred and heated under reflux conditions for about 6 hours in a conventional manner, after which about 616 parts of reaction water was collected.

The volatile solvent is removed from the reaction product by conventional stripping techniques.

In another similarly equipped reactor, 133 parts of the reaction product prepared above were added together with 144 parts of acrylic acid, 0.004 parts of phenothiazine, 3 parts of butyl stannic acid, 0.7 parts of thiodiglopionic acid and 200 parts of toluene. Add.

After the mixture was stirred and refluxed for about 9 hours at a reflux temperature of 103-117°C, about 27.5 parts of reaction water was collected.

The reaction product is then filtered and volatile solvents are removed by conventional methods to obtain an off-white liquid of low viscosity.

65.3 parts of the reaction product containing bis(acryloxyethyl)formamide prepared in H above was added to Merck [Cyprus Industrial Minerals Co., Ltd.].
trialMinerals), “Mistron (M
istron) RCS”] 5.6 parts, aluminum silicate 27.5 parts, silica [Illinois Minerals (Ill.
“Imsil” manufactured by inois Minerals
sil) A-25'') and 13.8 parts of crushed marble into a Cowles type mixing apparatus.

Continue mixing until a uniform distribution of ingredients is obtained.

13 parts of benzophenone are added to the reaction mixture and then mixed to obtain a homogeneous composition.

A sample of this composition is applied with a 0.0381 mm (1.5 mil) Birddraw-down applicator onto a panel of particleboard substrate.

This coating was applied at a conveyor speed of 30.5 m/min (1
00 ft/min) and 8.89 cm (31
Cure in air under irradiation from four 200 watt per inch mercury lamps from a distance of 1/2 inch.

The cured coated panel was rubbed twice with #220 grit sandpaper and no sandpaper scratches (gummi) were observed.
Example 25 56.2 parts of the amide acrylate reaction product prepared in the manner generally described in Example 2 were charged into a reactor equipped with a heating device, a stirring device and a thermometer. 4-isocyanatocyclohexyl)methane [manufactured by DuPont, “Hylene (H
ylene) W"], 1 mole of polycaprolactone polyol (manufactured by Union Carbide Corporation, PCPO200) with a molecular weight of 530, and 0.5 mole of 2-hydroxyethyl acrylate. The urethane diacrylate reaction product is then added with an additional 8.6 parts of urethane diacrylate diluted with 2-hydroxyethyl acrylate to a final diluent concentration of 34% by weight.

In this reactor, 5.5 parts of neopentyl glycol diacrylate, polyethylene wax [Allied Chemical (All
Polymist (Pol
ymist) B-6”] 0.6 part, silica pigment (W.R.
．． “Syloid” manufactured by Grace
d) 6.1 parts of 74-X4500], 7.9 parts of 2-ethylhexyl acrylate, 2.2 parts of benzophenone and 12.8 parts of N-vinylpyrrolidone are also added.

A grind of about 4.5 on the Hegman scale.
) Continue mixing until a homogeneous blend is obtained.

Samples of this composition were prepared by conventional draw-down methods into vinyl overlay panels or from 0.1016 to 0.152 thick.
Coat on 4-6 mil (4 mm) free vinyl film.

The speed of the conveyor that transports the coated panels is 9.1.
8.89 from the panel at 4 m/min (30 ft/min)
cm (3 1/2 inch) distance to 2.54 cm (1 inch)
Ultraviolet rays are irradiated using one mercury lamp of 200 watts per inch.

The cured coated panels exhibited good surface mar resistance and a desirable low gloss suitable for a simulated wood product.

Table 1 below provides data regarding the cure rate and physical properties of the coatings applied to each of the test panels of Examples 20-23.

The present invention and what is currently considered the best example of the invention have been described in accordance with the provisions of the patent laws.

However, it goes without saying that the present invention can be implemented in ways other than those described in the main text within the scope of the claims of the present invention.

Claims (1)

[Scope of Claims] 1(a) A formula having one nitrogen atom [In the above formula, X, Y, and Z each independently represent hydrogen, alkyl, aryl, acryloxyalkyl, acryloxyaliphatic ester ( (produced by the reaction of an acrylated substance with a hydroxyl-terminated aliphatic ester-containing intermediate produced by the reaction of an intramolecular ester of a hydroxycarboxylic acid with an amino alcohol), or an acrylyloxyaliphatic ether. , however, X
, Y, Z together have 2, 3 or 4 acrylyloxy groups], and (b) alkyl acrylate, epoxy acrylate,
It is characterized by containing a copolymerizable reactive solvent, a non-reactive solvent, a urethane acrylate co-curing agent, a viscosity modifier, a surface tension reducing agent, a slip aid, a photocatalytic system or a pigment, or a mixture thereof in the remaining weight percent. A highly radiation-sensitive radiation-polymerizable composition that can be cured to form a film. 2 The alkyl acrylate is an esterification or partial esterification reaction product of a lower alkyl polyhydric alcohol and acrylic acid or methacrylic acid, and the epoxy acrylate is an ester of an alkyl or aryl polyfunctional epoxide and acrylic acid or methacrylic acid. Claim 1 which is a reaction product of esterification or partial esterification
Compositions as described in Section. 3 The lower alkyl polyhydric alcohol is diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexanediol, glycerin, neopentyl glycol, pentaerythritol,
trimethylolethanetrimethylolpropane and 2
- 2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate. 4. Claim 2, wherein the alkyl or aryl polyfunctional epoxy is selected from the group consisting of butanediol diglycidyl ether, neopentyl glycol glycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and bisphenol A diglycidyl ether. Compositions as described in Section. 5. The reactive compound that can be copolymerized with the amide acrylate compound is selected from the group consisting of styrene, vinylamide, esters of vinyl alcohol, acrylic esters, maleic esters, and fumaric esters. Composition of. 6 The substantially non-reactive solvent is xylene, toluene,
A composition according to claim 1 selected from the group consisting of 2-methoxyethanol, methyl isobutyl ketone and isopropyl alcohol. 7. The viscosity modifier consists of cellulose acetate butyrate, carboxymethylcellulose, microcrystalline cellulose, fumed silica, a composition based on castor oil, 12-hydroxystearic acid, alkyd polymers, acrylic polymers and modified clays. A composition according to claim 1 selected from the group. 8. A patent in which the surface tension reducing agent is selected from the group consisting of branched lower alkyl acrylate polymers, fluorocarbon polymers, nonionic alkyl ester surfactants, ethoxylated alkyl ester surfactants, and ethoxylated phenolic surfactants. A composition according to claim 1. 9 Branched lower alkyl acrylate polymer is poly(2
-ethylhexyl acrylate). 10. The composition of claim 1, wherein the slip aid is selected from the group consisting of polysiloxanes, fatty acids, fatty acid esters, and waxes of esters of long chain monohydric alcohols and long chain fatty acids. 11. The composition of claim 10, wherein the wax comprises a mixture of cetyl palmitate and similar fatty acid esters. 12. The composition according to claim 11, wherein the wax is spermaceti. 13. The photocatalytic system comprises one or more photosensitizers, photoaccelerators, or photoinitiators and about 0.1% of the polymerizable compounds in the composition.
The composition of claim 1, wherein the composition is present in an amount ranging from 0.01 to about 20% by weight. 14. The composition of claim 13, wherein the photosensitizer is selected from the group consisting of benzyl, anthraquinone, penzophenone, 3-methoxybenzophenone, anthrone, thioxanthone, and chlorothioxanthone. 15. The composition of claim 13, wherein the photoenhancer is selected from the group consisting of tertiary alkylamines, tertiary alkanolamines, and diamines. 16 The photoinitiator is benzoin, methyl benzoin ether, butyl benzoin ether, inbutyl benzoin ether, α・α-diethoxyacetophenone, α・α
14. The composition of claim 13, wherein the composition is selected from the group consisting of -dimethoxy-α-phenylacetophenone, α-chloroacetophenone and methyl phenylglyoxylate. 17 The urethane acrylate co-curing agent is (a) a prepolymer component having a molecular weight of 300 to 3000 and having a plurality of hydroxyl functional groups, and (b) a compound having a plurality of isocyanato groups, wherein a portion of the incyanato groups are the above-mentioned incyanato groups. (c) a polyfunctional compound containing at least one functional group reactive with isocyanato groups, the polyfunctional compound being reactive with the hydroxyl functional groups of the prepolymer component; A composition according to claim 1, wherein the functional compound provides at least one ethylene functionality in the reactive product. 18 (a) the prepolymer component is selected from the group consisting of polyester polyols, polyether polyols, and poly(hydrocarbylsiloxanes) containing hydroxyl functional groups pendant to the siloxane backbone, and (b) the isocyanate-containing compound is an aliphatic polyincia. 18. The composition of claim 17, wherein the composition is selected from the group consisting of polyisocyanates and aromatic polyisocyanates, and wherein (c) the polyfunctional compound is acrylic acid or a hydroxyl-containing acrylic ester. 19. The composition according to claim 1, wherein the pigment is an extender pigment, a hiding pigment, or a colored pigment.