JP2003147230A - Radiation-curable aqueous composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-curable composition for producing a low-odor food packaging material having a low level of extractable component, and print ink. SOLUTION: A method for producing a low extractable film comprises coating the surface of a film with a chemical ray-curable aqueous composition comprising at least one α,β-ethylenic unsaturated radiation-polymerizable group- containing water-soluble compound and water as essential components and irradiating the film with chemical rays in the presence of water to form a cured film. The content of a water-soluble compound to be extracted by a false body of food or its residual amount is <50 ppb.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation curable composition and a printing ink for producing a packaging material. In particular, the invention relates to radiation curable aqueous compositions and printing inks for the production of low odor food packaging materials having low levels of extractable ingredients.

[0002]

BACKGROUND OF THE INVENTION Energy curable, low viscosity inks generally consist of a mixture of acrylated oligomers and monomers. Monomers are commonly used to control the viscosity of flexographic, gravure, roller and tower print and coating inks or coating compositions. However, the diluted monomer does not react completely during polymerization upon irradiation with ultraviolet (UV) or electron beam (EB). Such unreacted monomer remains as a residual component in the dried printing ink or coating film and is transferred by absorption as well as surface contact. This migration of residual components can occur when printing or coating on "odor" or "off taste" sensitive packaging such as containers for food, beverages, tobacco, perfumes, etc., and on curing such as pharmaceutical or healthcare packaging. It is a problem when the amount of extractables from the applied printing ink or coating needs to be negligible. In addition, solvents are sometimes used to form low viscosity coatings.

Examples of solvent-based coatings are described in US Pat. No. 5,824,717, Merrill et al., With isobutylene copolymers having acrylate functional groups,
Radiation (energy) curable compositions optionally containing fillers are disclosed. The disclosed copolymer is an acrylate modified copolymer of a C4-7 isoolefin and a paraalkylstyrene comonomer. Merrill
Discloses that the proportion of extractables from the cured composition is negligible and that the cured composition is suitable for use in the manufacture of various high purity rubber products used in the pharmaceutical and healthcare industries. There is. Merrill further discloses that the composition can be used as capacitor packaging, food contact material, wire cable insulation material, and for the manufacture of high purity hoses. Merrill discloses making coatings by dissolving this copolymer in toluene as the primary solvent.

Problems arising from the odor, off-taste and residual extract of currently available UV / EB printing inks and coatings are conventional solvent or water based flexographic printing inks which require removal of the solvent or water prior to curing. And the inability to use energy curable products in high volume packaging still widely offered by coatings. Acrylated oligomers are usually too viscous to be used by themselves (ie without monomer diluent) for low viscosity coatings, and especially for the production of printing inks.

The use of water as a diluent for a mixture of UV / EB curable acrylated oligomers for wood and floor coatings is disclosed in US Pat. No. 6,011,078. The composition is a dispersion or emulsion that requires water to evaporate on a non-absorbing substrate before exposure to light.

[0006]

Single liquid, monomer and solvent free, UV / EB curable aqueous printing inks and coatings that form cured films with low levels of extractable components and / or odors. A composition is required.

[0007]

The present invention provides the following step a) an actinic radiation-curable aqueous composition containing water and a water-soluble compound containing at least one α, β-ethylenically unsaturated radiation-polymerizable group. B) applying the aqueous composition to a surface, andc) irradiating the surface with actinic radiation in the presence of water to form a cured film, the cured film 10 ml per square inch
Is a method for producing a low extractable film (that is, a print ink film or coating) in which an uncured residue extracted from the cured film when immersed in a pseudo liquid and heated is less than 50 ppb.

Another aspect of the present invention is an improved actinic radiation curable single liquid aqueous composition comprising a water-soluble compound containing at least one α, β-ethylenically unsaturated radiation-polymerizable group and water. Yes, the surface was coated with this composition and exposed to actinic radiation in the presence of water to form a cured film, which cured when immersed in 10 ml of pseudo liquid per square inch of this cured film and heated. Such a composition has less than 50 ppb of uncured residue extracted from the film. Preferably, this water-soluble compound is a water-soluble oligomer containing two or more acrylic groups.

Yet another aspect of the present invention comprises a substrate and a cured film adhered to the surface of the substrate, wherein the cured film comprises a water-soluble oligomer containing two or more acrylic groups and water. Providing an essentially aqueous composition,
An uncured residue obtained by curing this aqueous composition with actinic radiation in the presence of water, which is extracted from this cured film when immersed in 10 ml of simulated liquid per square inch of cured film and heated. Is less than 50 ppb.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises at least one α,
The present invention relates to a novel aqueous radiation-curable composition containing a water-soluble compound containing a β-ethylenically unsaturated radiation-polymerizable group and water. Preferably, the water soluble compound is a water soluble oligomer containing two or more acrylic groups and the composition comprises a photoinitiator. Here, "low extractable film" means that the cured film is substantially free of solvent extractable oligomers or residual components when exposed to a solvent in the solvent extraction method described below (ie less than 50 ppb. ) Means that. The curable composition of the present invention may contain a colorant such as a dye or a pigment. Such pigmented compositions can be used as printing inks or in the formation of pigmented coatings. Here, "printing ink" has its conventional meaning, i.e., a colored liquid composed of a colored body, usually a solid pigment, dispersed in a liquid vehicle. In particular, the radiation curable printing ink of the present invention comprises a pigment and a liquid vehicle. Although this curable composition can be used in many applications requiring a limited extract, it is used in the packaging industry, in particular in hardened coatings and / or printed objects. And / or is particularly useful in the printing industry where it comes into contact with products that have stringent purity and contamination requirements under processing conditions. The cured compositions of the present invention have low or no odor and provide a product that is substantially non-contaminating when used in packaging foods, beverages, cosmetics, pharmaceuticals and the like.

Aqueous Curable Composition The aqueous radiation curable composition of the present invention contains, as an essential component,
By a water-soluble compound containing at least one α, β-ethylenically unsaturated radiation-polymerizable group (preferably this water-soluble compound is a water-soluble oligomer containing two or more acrylic groups), water, and optionally UV rays. It includes activatable photoinitiators and / or colorants such as dyes and pigments.

Water-Soluble Compound The term "water-soluble compound" as used herein includes a limited number of water-soluble groups, such as carboxyl, hydroxyl, ether, etc., sufficient to provide an aqueous solution of this compound at ambient temperature, and at least A radiation-curable compound containing one α, β-ethylenically unsaturated radiation-polymerizable group. Preferably the water soluble compound is an oligomer. As used herein, the term "oligomer" means two or more terminal or side chain α, β-ethylenically unsaturated groups bonded to a central aliphatic or aromatic main chain through a polymer main chain or a similar bonding group. Compounds containing groups are included. The water-soluble compound used in the present invention is epoxy acrylate,
Epoxy methacrylate, polyether acrylate,
It is polyether methacrylate, polyester acrylate, polyester methacrylate, polyurethane acrylate, polyurethane methacrylate, melamine acrylate, or melamine methacrylate. Usually the acrylate is an aromatic or aliphatic acrylate or methacrylate, preferably the compound is
Diacrylate ester of alkanol glycidyl ether such as 1,4-butanediol diglycidyl ether, ethoxylated aromatic epoxide, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated aliphatic or aromatic epoxy Acrylate, ethoxylated aliphatic or aromatic epoxy methacrylate,
They are polyoxyethylene glycol diacrylate and polyoxyethylene glycol dimethacrylate. Preferably, the ethoxylated aromatic epoxide contains from 6 to 20 ethoxy groups.

Suitable water-soluble compounds are aliphatic and aromatic epoxy acrylates and epoxy methacrylates, preferably aliphatic compounds are used. This includes, for example, the reaction product of acrylic acid or methacrylic acid with an aliphatic glycidyl ether.

Further suitable compounds are polyether acrylates and methacrylates, polyester acrylates and methacrylates, and polyurethane acrylates and methacrylates. Of these, reaction products of acrylic acid or methacrylic acid with polyesterol and polyetherol are preferred. Radiation curable acrylates as described in EP-A-126341 and EP-A-279303 are particularly preferred. The polyetherols used here are preferably alkoxylated, especially ethoxylated and / or propoxylated mono-, di-, tri- or polyfunctional alcohols.

Other suitable compounds are melamine acrylates and methacrylates. This is, for example, by esterifying the free methylol groups of the resin with acrylic acid or methacrylic acid or with etherified melamine compounds by ether exchange with hydroxyalkyl methacrylates such as hydroxyethyl, hydroxypropyl and hydroxybutyl methacrylate, hydroxybutyl acrylate. It is obtained by

Still other suitable compounds are thickeners containing unsaturated groups. It contains, on the one hand, a polyurethane thickener, which contains α, β-ethylenically unsaturated double bonds as a result of the incorporation of the abovementioned hydroxyalkyl methacrylates, hydroxyalkyl acrylates. It also comprises a polyacrylate thickener, for example the reaction of a hydroxy-containing polymer or a polymer containing acid groups with an epoxide-containing methacrylate, an acrylate such as glycidyl methacrylate, glycidyl acrylate,
Or by reaction of hydroxy-containing polymers esterified with methacrylic acid or acrylic acid with methacrylic anhydride, acrylic acid, or with NCO-terminated methacrylates, acrylates such as methacryloyl isocyanate, isocyanatoethyl methacrylate, isocyanato acrylate, etc. By a polymer-analogous reaction according to. It further includes polyvinyl alcohols modified, for example, by reaction with maleic anhydride, acrylic anhydride, or by esterification with methacrylic acid having a double bond, acrylic acid. Finally, it comprises a copolymer containing maleic anhydride as a comonomer, said polymer being derived from the above hydroxyalkyl methacrylates, hydroxyalkyl acrylates or hydroxy vinyl ethers, such as butanediol monovinyl ether with double bonds, cyclohexanedimethanol monovinyl ether, etc. It is modified by ring opening of the anhydride.

Particularly preferred water-soluble compounds are diacrylate esters of alkanol glycidyl ethers (wherein the alkanol contains 2-3 hydroxy groups), for example diacrylates of 1,4-butanediol diglycidyl ether, trimethylolpropane diester. Triacrylates of glycidyl ether, or mixtures thereof, and ethoxylated acrylic oligomers, such as ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane diacrylate, or mixtures thereof (ethoxylated oligomers have 9-12 ethoxy groups. Including). A particularly preferred water-soluble compound is the diacrylate ester of 1,4-butanediol diglycidyl ether, which is available from BASF Corporation as Laromer LR 8
765 Available as aliphatic epoxy acrylate.

The aqueous radiation curable coating composition of the present invention comprises from about 0.1 to about 95 wt% of a water soluble radiation curable compound.
%, Preferably 75 to 95 wt% of a water soluble radiation curable compound formed from at least one α, β-ethylenically unsaturated radiation curable double bond. Preferably, the curable composition comprises about 5 to about 50 wt% water. Usually, this water-soluble compound is added to the coating composition in an amount sufficient to achieve a solids content of 75-95 wt%.

Unless the photoinitiator radiation-curable composition is specifically formulated for use in electron beam curing, the radiation-curable coatings of the present invention optionally release when exposed to UV at a wavelength of 200 to 420 nm. An addition polymerization photoinitiator generating a group may be included. The aqueous radiation curable coating composition of the present invention optionally comprises 0 to 10 wt% photoinitiator. Such photoinitiators include one or more compounds that directly provide free radicals when activated by UV light. The photoinitiator may include a sensitizer that broadens the spectral response in the near UV, visible and / or near infrared region. When cured by UV light, the coating composition typically has a concentration of from about 0.05 to about 20 wt%, preferably
It has 0.05 to 10 wt%, more preferably 0.1 to 5 wt% photoinitiator. Various photoinitiators can be used, so long as the components or residues after polymerization do not migrate or substantially leach from the cured film. An effective photoinitiator of this type is BM Monroe and GC Weed's "Photoinitiator".
s for Free-Radical-Initiated Photoimaging System
s ", Chem. Rev., 1993, 93, 435-448.
Photoinitiators that can be used alone or in combination are benzophenones, alkylbenzophenones such as 4-methylbenzophenone, halomethylated benzophenones, Michler's ketone (4,4'-bisdimethylaminobenzophenone), halogenated benzophenones such as 4-chloro. Benzophenone, 4,4'-dichlorobenzophenone, anthraquinone, anthrone (9,10-dihydro-9-anthracenone), benzoin, isobutyl benzoin ether, benzyl and benzyl derivatives such as benzyl dimethyl ketal, and phosphine oxides or phosphine sulfides such as bis It includes acylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. A preferred photoinitiator that can be used alone or in combination with others is 4- (2-hydroxyethoxy).
Examples include phenyl (2-hydroxy-2-methylpropyl) ketone and isopropylthioxanthone.

If desired, the photoinitiator may further comprise a synergist, preferably a tertiary amine. Suitable synergists include triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, amino acrylates such as amine modified polyether acrylates (eg BASF Laromer grade LR8956, LR8889, LR88.
69, LR8894, PO83F and PO84F), and mixtures thereof. In the case of pure tertiary amines, it is used in amounts of up to 5% by weight, based on the total weight of the coating composition, in the case of aminoacrylates, in amounts corresponding to the number of amino groups.

Colorant The aqueous radiation curable composition of the present invention may further comprise from 0 to about 50 wt% of a colorant such as a dye or pigment. Preferably, such dyes or pigments are soluble or dispersible in the curable composition and form a permanent, non-migratory component in the coated curable composition. When used as a radiation curable ink, the aqueous coating solution typically contains one or more solid pigments dispersed therein. This pigment can be any conventional organic or inorganic pigment such as zinc sulfide, Pigment White 6, Pigment Yellow 1, Pigment Yel.
low 3, Pigment Yellow 12, Pigment Yellow 13, Pigme
ntYellow 14, Pigment Yellow 17, Pigment Yellow 6
3, Pigment Yellow 65, Pigment Yellow 73, Pigment Y
ellow 74, Pigment Yellow 75, Pigment Yellow 83, Pi
gment Yellow 97, Pigment Yellow 98, Pigment Yellow
106, Pigment Yellow 114, Pigment Yellow 121, Pigm
ent Yellow 126, Pigment Yellow 127, Pigment Yellow
136, Pigment Yellow 174, Pigment Yellow 176, Pigm
ent Yellow 188, Pigment Orange 5, Pigment Orange 1
3, Pigment Orange 16, Pigment Orange 34, Pigment R
ed 2, Pigment Red 9, Pigment Red 14, Pigment Red 1
7, Pigment Red 22, Pigment Red 23, Pigment Red 3
7, Pigment Red 38, Pigment Red 41, Pigment Red 42,
Pigment Red 57, Pigment Red 112, Pigment Red 122,
Pigment Red 170, Pigment Red 210, Pigment Red 23
8, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blu
e 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigm
ent Green 7, Pigment Green 36, Pigment Violet 19,
Pigment Violet 23, Pigment Black 7, etc. may be used.
This colorant may be selected from dyes or pigments whose use is guaranteed by the Federal Food Drug and Cosmetics Act.FD & C Red No.3, D & C Red No.6, D & C Red No.7, D & C
Red No.9, D & C Red No.19, D & C Red No.21, D & C Red N
o.22, D & C Red No.27, D & C Red No.28, D & C Red No.3
0, D & C Red No.33, D & C Red No.34, D & C Red No.36, D &
C Red No.40, D & C Orange No.5, FD & CYellow No.5, D & C
Yellow No.6, D & C Yellow No.10, FD & C Blue No.1, Ir
on Oxide Yellow, Iron Oxide Brown, Iron Oxide Re
d, Iron Oxide Black, Ferric Ammonium Ferrocyanid
e, Manganese Violet, Ultramarine Blue, Chrome Oxid
e Green, Hydrated Chrome Oxide Green, Titanium Dio
Including xide. Pigment compositions useful in the energy curable inks of the present invention are described in U.S. Patent No. 4,946,508, 4,9.
46,509, 5,024,894 and 5,062,894. Such a pigment composition is a blend of pigment and poly (alkylene oxide) grafted pigment. Aqueous curable compositions containing colorants are particularly useful in formulating radiation curable printing inks for use in conventional printing such as flexographic, gravure letterpress, dry offset and lithographic printing. Each of these printing operations requires inks with special properties, such as a particular viscosity range, which is achieved by adjusting the solid to water ratio, including pigment and water soluble compounds. To be done.

Other Auxiliaries The aqueous curable composition may include other auxiliaries as long as it does not affect the essential properties of the composition and does not migrate the cured film after polymerization and substantially leach out. Accordingly, the radiation curable compositions and inks of the present invention may include conventional aids to control the fluidity, surface tension and gloss of the cured coating or printed ink. Such auxiliaries included in the ink or coating are usually surfactants, waxes, fillers, matting agents, or combinations thereof. These auxiliaries function as leveling agents, wetting agents, dispersants, antifog agents, or additional auxiliaries may be added to provide specific functions. Preferred auxiliaries are fluorocarbon surfactants such as FC-430, a product of 3M Company, silicones such as Dow Chemical Cor.
Includes poration products DC57, polyethylene wax, polyamide wax, paraffin wax, polytetrafluoroethylene wax, etc.

The coating composition may comprise from about 0 to about 50 wt% filler, preferably from about 1 to 50 wt% filler. Examples of suitable fillers are silicates obtained by hydrolyzing silicon tetrachloride (Aerosil from Degussa), diatomaceous earth, talc, aluminum silicate, sodium aluminum silicate,
Examples include magnesium silicate. Coating composition is 0
20 wt% protective colloids or coresin and / or emulsifiers may also be included. A suitable emulsifier is Houben-W
eyl, Methoden der Prganischen Chemie, VolumeXIV / 1,
Makromoleculare, Stoffe, Georg-Thieme-verlag, Stu
ttgart, 1961, pp. 411-420, as well known to those skilled in the art and commonly used as a dispersant in aqueous emulsion polymerization. Suitable protective materials include polyvinyl alcohol, polyvinylpyrrolidone, cellulose, cellulose derivatives, starch, starch derivatives, gelatin, gelatin derivatives and the like.

Manufacturing Low Extraction Cured Films One aspect of the present invention is a method of forming low extraction films.
In this method, the above aqueous composition is applied to the surface of a substrate, the aqueous composition applied without substantially removing water is irradiated with high-energy electrons or ultraviolet rays in the presence of water to form a cured film. Form. The aqueous composition may be applied to the substrate surface as a uniform coating using conventional coating methods. Therefore, spin coating this composition,
It may be bar-coated, roller-coated, curtain-coated or may be applied by brush, spray or the like. The aqueous composition may also be imaged as a printing ink using conventional printing methods. When this aqueous coating composition is applied to the surface of a substrate, it is cured by either high-energy electrons or UV light immediately before removing the water. Typically, the high energy electrons have about 50 to about 200 kV electrons, preferably 85 to 180 kV electrons and are usually formed by high energy electronic devices. The amount of this high-energy electron is about 2 to about 4 megarads (Mrad),
It is preferably 2.7 to 3.5 Mrad. UV irradiation is about 200
It may be carried out using conventional non-contact irradiators, which emit in the spectral region of about 420 nm. The water in the coated composition does not affect the curing process, even on non-absorbent surfaces, rather it is water soluble in a fully cured film or image with little or no extractable residual compounds left behind. Promotes complete cure of the compound. It is believed that water is removed at the same time as the curing process and / or during treatment of the substrate. As used herein, "cured film" or "cured film" includes continuous cured film compositions as well as discontinuously cured ink image compositions. In either sense, the cured film adheres to the substrate and has an externally cured surface, which defines the surface area used in the extraction method described below.

Substrate The substrate and its surface are made of conventional substrate materials such as plastics (eg polystyrene, polyvinyl chloride, polynaphtherene terephthalate, polyacrylate, polyacrylic), metals, composites, glass, paper and the like. May be configured. The cured coating on the substrate can be used in a variety of applications where low or no contamination from the substrate is required. Preferably, this substrate is a food packaging material formed from sheet material, containers such as bottles or cans. More preferably, this food packaging material is selected from polyolefin, metal-deposited polyethylene terephthalate, polystyrene, polycarbonate, polyurethane, polyester, polyamide, polyimide or metal, and more preferably polyethylene, polypropylene, aluminum foil, or metal container.
Alternatively, the packaging material may be used to house cosmetics, biological materials such as proteins or tissue debris, pharmaceuticals and the like.

Solvent rub test A sample of the cured film is placed on a flat hard surface with the film facing up. The cured film surface is then repeatedly rubbed with an applicator pad saturated with a solvent such as methyl ethyl ketone, isopropyl alcohol and the like. The applicator pad is usually a bunch of cotton, soft cloth or paper product that is rubbed back and forth with normal hand pressure. The number of times the film surface is rubbed until the film surface deteriorates (for example, decomposes, softens, wears, etc.) is taken as the solvent resistance value of the cured film. Generally, the cured film is considered to be solvent resistant when the film is rubbed 10 times or more, preferably 20 to 75 times, or more, with the solvent selected until degradation is observed.

Extractable Ingredients Many of the health-safety applications relate to plastic films in direct contact with food, cosmetics, pharmaceuticals, and children's toys. However, most applications are packaging, where "packaging" is meant to include all situations in contact. Food packaging is the largest use for plastic film packaging. Consumers want plastic suppliers to be responsible for the health and safety of packaged foods. Much of the quality of food is affected by packaging. Therefore, it is necessary to assess all the mutual effects for consumer approval of the food. Processed foods are often formulated with, for example, additives or processed (eg, dehydrated) to enhance shelf life and control spoilage. On the other hand, a mixture of different food products may be more reactive. Thus, food products change almost universally over time and usually deteriorate. Therefore, it is necessary to assess the health risks associated with packaging food products in contact with plastic films.

In order to evaluate the scientific basis of health safety, it is necessary to establish a standardized model system that decomposes every food packaging situation (or every food contact situation) into its components. The usual factor is considered to be a barrier between the risks resulting from the interaction between the food and its environment or ingredients. In fact, packaging is not uniform and includes one or more elements. Also, the effect of scale is considered. Interaction models are used to better understand the effects of the components.

The interacting ingredients include foods, plastic films, residual ingredients, additives, volatile ingredients, non-volatile ingredients and the environment. Plastic films are defined as high molecular weight polymers. Additives are non-polymeric components that are added after the initial production of the polymer and include processing agents such as heat stabilizers and end use modifiers such as UV stabilizers, antistatic agents and the like. Residual components are the few raw materials from the plastic that did not react to form the polymer in the original manufacturing process and were not removed in subsequent purification. It contains unreacted monomers (eg styrene in polystyrene, caprolactane in nylon, VCM in polyvinyl chloride),
Also included is a small amount of solvent and unaltered catalyst. However, in a thermosetting polymer (for example, polyurethane), the basic component from which this thermosetting resin is produced is also included in the residual components.
Degradation products (eg acetaldehyde from PEP) that occur at any stage are classified as volatile components or residual reactants. The environment contains all odorous and non-odorous components that diffuse into the plastic itself. The most important materials are oxygen, water vapor and carbon dioxide, but in some circumstances other materials are also important (eg chlorine constitutes sterilization). Odor components are those that can change the taste and odor of foods or plastics. Some ingredients are purely technically relevant, but not important. However, some are related to health and safety and are shown below.

[0030]

[Table 1]

Radiation Radiation is sometimes applied to foods, films or filled packages for sterilization. Its use for this purpose is limited to the storage and packaging of pharmaceuticals. Two points must be noted in the use of radiation. First, there are legislative constraints on the limits of radiation that can be used with food. Second, the intense radiation causes the decomposition of many plastics, especially polyolefins (due to fission, crosslinking, oxidation, etc.), producing odors. The preferred radiation is sunlight or UV from fluorescent lamps, which has a sufficient effect on foods, for example, exposing milk to sunlight for 3 hours reduces the vitamin C content and destroys riboflavin.
These effects on other foods are related to nutrition, as opposed to toxicity, so their effect on health is of little concern and is not significant. In fact, UV light has been found to be advantageous due to its bactericidal effect on pathogens.

A transparent film is required to make the food product visible at the point of sale. If a maximum barrier to radiation is required, this is not achieved by choosing a particular plastic, but also by coloring the plastic. Over 90 percent of all radiation is rejected by the pigments used to achieve the usual coloring of plastics. With respect to ultraviolet rays, the transmissivity also decreases by incorporating an ultraviolet absorber. Pigments that are transparent to UV radiation but relatively opaque to UV radiation have recently been developed. This solves the problem of reducing UV transparency while maintaining the desired transparency. Of course, exposure to radiation is reduced or eliminated by the use of hot coatings, printing inks, or opaque ingredients such as paper.

Movement Movement is the movement of an object between plastic and food.
It acts in two ways, from plastic to food (which has its usual meaning) or from food to plastic (which has the opposite meaning). The nutritional quality of foods is affected when certain components of the food are lost to a significant extent.
The main effect is the loss of preservatives, but in some cases nutritional or sensory changes occur, for example the fat component of milk is extracted into polyolefins. For example, if a colorant is extracted from a food product, the effect on the food product is usually not a problem, but the large discoloration of the film becomes unattractive.

There has been no proven health hazard resulting from the transfer of plastic film to food. Most regulations cover mobility and sensuality. There are three basic types of movement mechanisms.
That is, non-migrating, spontaneous migration, and leaching. Non-migrated is a high molecular weight polymer component that is inert to most foods and certain inorganics, as well as plastic
For example including contact with dry sugar and salt. Spontaneous transfer occurs when contact with food does not occur, ie the transfer material diffuses into the environment and food. Leaching occurs when plastic comes into contact with food and food mimics (extracts). It is clear that there must be a physical or chemical effect that modifies the locomotive mechanism of the mobile. This can be two paths. (1) In plastics, when the migration has a relatively high diffusion coefficient and comes into direct contact, the surface layer of the mobile body dissolves, the concentration of the extract in the food increases, and the food or one of its components If the plastic penetrates to a certain depth and the plastic matrix changes to such an extent that the mobility of the components therein is greatly enhanced, the components diffuse from this layer into the food product.
The second mechanism is the most difficult to measure by scientific analysis and has only recently been elucidated. But,
Most important for most additives in plastics that come in contact with most foods.

A "pseudo liquid" should ideally be a food product to be packaged and can sometimes be used. However, usually severe problems occur: degradation of foods makes analysis difficult, non-uniform distribution of mobiles makes this film suitable for a wide range of foods. Therefore, "food mimetics" are convenient for analysis and are used instead of liquids that mimic the action of food. The range of mimetics is determined on the basis of the binary mixture. Its components include tetrahydrofuran, methanol, water and chloroform. Commonly used food mimetics include:

[0036]

[Table 2]

The normal movement test is carried out at a normal processing temperature, and the following are general. Sterilization: 115 ° C, boiling in bag: 100 ° C, tropical storage: 38 ° C, and normal refrigeration:
4 or 5 ° C. Often 40 ° C is used to facilitate long-term migration at 23 ° C.

There are further restrictions on migration, which is defined by the concentration in the food, typically 50-60 ppm, or by migration per unit area. Claims to justify the limits are protection against toxic hazards, protection against inferior products, and reduced need for analytical testing.

The means applied to food packaging apply, with some variations, to the packaging of pharmaceuticals, cosmetics and toiletries. The main difference is that toxicity testing is done in contact with skin or other body surfaces and in the case of aerosols by inhalation. There are complex scientific problems in devising a system for controlling plastic films that come into contact with food. Both packaging and the use of plastic films have grown explosively over the last few decades and, as such, relatively regulatory systems have been problematic and continuously changing.
For example, in the United States, packaging materials are Food and Drug Administration (F
DA) range. The FDA regulations include a detailed list of base polymers and additives. The use of plastics and their components is allowed for food, temperature, application type (eg film, molding or polymer composition). In many cases, US regulations are recognized abroad.

In the selection of organoleptic foods, the consumer generally decides on the type, for example meat for protein, potato for rice, rice or bread, vegetables, fruits, etc. However, stable nutritional value or content is affected when choosing which product to actually purchase at the time of sale. In addition, the main factors related to the recognition by the five main sensations of sight, hearing, touch, taste and smell are affected. These are called sensory effects,
Overall, it is a sensory property. In packaging, they are mainly limited to odor and taste.

For example, a plastic film that comes into contact with food is usually not required to contribute to the taste and odor of food. On the other hand, it is usually required that they should not contribute. Changes in the taste or odor of food products are almost always considered unfavorable. If the change is unpleasant, it is called "offensive odor", "off taste" or "rot". This is the basis for the toxicity hazard and is caused by the interaction between food and plastic or the environment.
With exceptions, most high molecular weight polymers are tasteless and odorless, and the major constituents of all commercial plastic films do not produce off-flavors or off-tastes. This is a general principle that does not apply to all packaging materials. Volatiles that diffuse from the plastic into the contents of the package are divided into residues (including residual reactants) from the manufacturing process, degradable products formed during the conversion process, and additives. The decomposition products formed during the conversion process usually result from polymerization. Some plastics decompose slightly when heated. In a few cases, for example polystyrene and nylon, the main reaction is depolymerization and the by-products are monomers or oligomers. In most cases the product is not obvious.

There are still no mechanical devices that can be reliably used for odor or taste. Also, animals can be used in special cases, but they are not suitable for testing plastics. Therefore, humans must be used and human panel members must exhibit off-flavors and off-tastes. Although not a trivial requirement, it is desirable for the panel members' selection to examine their sensation for a particular stimulus.

Low Extractable Film The aqueous radiation-curable composition of the present invention, when cured by ultraviolet rays or high-energy electrons in the presence of water, causes the coating of the composition to undergo an extraction test as described below. It has the unique feature of forming a cured film with less than 50 ppb of water soluble oligomers or residual components extracted by the pseudo liquid in. Here, the “pseudo liquid” means a liquid or a solvent that simulates a substance that is expected to come into contact with the cured film under the use conditions. For example, if the cured film is incorporated into a food packaging material, this pseudo liquid should mimic the packaged food during processing and storage. In this case, the simulated liquid is preferably a “food simulation”.

The extraction method used for the simulated food is Office of
Premarket Approval (OPA), HFS-215, Center for Food
Safety & Applied Nutrition (CFSAN), FDA, 200 CS
"Guidan available from t., SW, Washington DC 20204
ce for Industry Preparationof Premarket Notificati
ons for Food Contact Substrates: Chemistry Recomme
ndations ", September 1999. According to the FDA method, a food mimetic (ie, a solvent or a food mimic) that simulates a food product in which a sample of the cured film is contacted with the cured film during normal processing, storage and use. (Solvent mixture).

The amount of food simulant used for extraction is determined by the exposed surface area of the cured film. For each square inch (6.45 cm ² ) of cured film, 10 ml of food mimic is used for this extraction. Examples of food mimetics suitable for the present invention are 10%
Ethanol / water solution, 50% ethanol / water solution, 95% ethanol / water solution, food oil, boiling point of 240-270 ℃, composed of saturated C ₈ (50-65%) and C ₁₀ (30-45%) triglyceride Fractionated coconut oil, a mixture of synthetic C ₁₀ , C ₁₂ , and C ₁₄ triglycerides. In one extraction test, the soaked sample is heated to at least 40 ° C for 240 hours. In a more stringent extraction test, the soaked sample is first heated to about 121 ° C for 2 hours and then to about 40 ° C for 238 hours.

When the cured film is formed on the inside surface of a container such as a can or a beverage bottle, the appropriate amount of food simulant is placed in the container and tested. Cured films are typically tested using a transfer cell containing a test piece having a known surface area extracted by a known volume of a food mimetic. The usual mobile cells used are Snyder, RC and
Breder, CV J. Assoc. Off. Anal. Chem., 68 (4),
It is a two-sided mobile cell described in 770-777, 1985.
Such a mobile cell should have the following characteristics:
Samples containing cured films of known surface area and thickness are separated by internal spacers, such as glass beads, to allow free flow of mimetics into each sample, minimal headspace, hermeticity and liquidity. Maintaining a hermetic seal (preferably if the mimetic is volatile), the cell should be gently agitated to minimize localized solubility that confers migration resistance to the food mimic. Conventional analytical methods may be used to determine the amount of residual components or extracted oligomers present in the food simulant. The characteristics of the extract are determined by suitable chemical or physical tests such as NMR, UV-visible spectrum, atomic absorption spectrum, FTIR spectrum, mass spectrum, gas or liquid chromatography and the like.

In the present invention, the level of extract is determined using two methods, the sensory odor test and the analyzer method. The residual odor of the cured film corresponds to residual unreacted material in the coating that migrates in the coating. This unreacted material can be extracted and quantified by analytical methods. Odor is a subjective measure, but it is very important for products where odor exhibits physiological reactions such as allergic reactions and dermatitis.

The residual odor test coating composition was applied to a paperboard and aluminum foil with a # 3 Meyer bar and then UV (UV) radiation from UV energy of 120-500 mJ / cm ² depending on the composition.
3M with 165kV electrons or cured with curable composition)
Cured under rad electron beam conditions. Coated and cured paperboard and foil samples of the same dimensions are cut and placed inside a 1 liter glass bottle fitted with a sealed screw lid. Place this bottle containing the sample in an oven at 60 ° C for 30
Put in minutes. Several people (at least 5 people) then open each bottle and rate the odor on a scale of 1-5. Here, 1 means that the odor is weakest, and 5 means that the odor is strongest. Record the average score for each sample. The residual odor corresponds to the amount of unreacted material or extract.

Direct solvent extraction 100 cm ² of hardened film is cut into small squares and 16 ml
Place in a vial. Add 10 ml of solvent, acetonitrile or methylene chloride and leave the sample for 24 hours at room temperature. After 24 hours, remove 3 ml of the solution and
Filter through a polytetrafluoroethylene filter disc of 1. and place in an autosampler vial for analysis. The extracts are then analyzed using high performance liquid chromatography (HPLC). The mobile phase is 50% water / 50% methanol and is run at 0.8 ml / min at ambient temperature. 2 effluents
Photodiode array detector (PDA) monitoring at 05nm
To analyze. The column is a Phenomenex LUNA C18 column, 4.6 mm x 250 mm, 5μ particle size, 3400 psi high pressure limit.

Backside Extraction with Food Mimicry The food mimicry (extraction solution) used is a water / ethanol solution containing 95 vol% ethanol and 5 vol% water. 10 g
Of food is exposed to 1 square inch of packaging film. Therefore, 1 ml of extraction solution is placed in a 20 ml vial. The unprinted side of the UV cured film is placed on the vial mouth and sealed using a Teflon lined cap. Surface area of 3 vials (opening)
Is 1.1 square inches and has 15 ml (3 vials x 5 m
The extraction solution of l) is 11 g. Place inverted vial in oven and heat to 40 ° C for 10 days. To increase the limit of detection, extract solutions from 12 vials are combined, evaporated to less than 1 ml and then diluted with acetonitrile. This method yields a total extraction area of 4.4 square inches. The solution is then analyzed. The concentrated sample is analyzed by the HPLC method described in the direct extraction method.

The aqueous radiation curable composition of the present invention is illustrated by the following examples. Example 1 80 parts of aliphatic epoxy acrylate (Laromar from BASF
LR8765), 19.5 parts of water, and 0.5 parts of acrylated silicone (Rad 2500 from Tego) were mixed to produce a stable coating. This composition is rolled 3 to 6 by a wound wire rod.
It was applied to a thickness of μm and cured by EB irradiation of 165 kV electrons at 3 Mrad. The resulting coating had a gloss of> 70 and was fully cured as shown by the solvent rub test, i.e. 30+ methyl ethyl ketone (MEK) double rubs.

Example 2 77 parts of aliphatic epoxy acrylate (Laromar from BASF
LR8765), 19.5 parts water, and 3 parts photoinitiator (Ciba I
rgacure 2959) (and 0.5 parts of acrylated silicone (Te
Rad 2500) from Go) was mixed to produce a stable coating. The composition was applied with a wound wire rod to a thickness of 3-6 μm and cured by UV light of at least 120 mJ / cm ² . The resulting coating had a gloss of> 70 and was fully cured as indicated by the solvent rub test, ie 20 MEK double rubs.

Example 3 30 parts of highly ethoxylated trimethylolpropane triacrylate (15 mol EO, SR9035 from Sartomer), 47 parts of aliphatic epoxy acrylate (Laromar LR876 from BASF).
5), 19.5 parts water, and 0.5 parts acrylated silicone (T
Rad 2500) from ego was mixed to produce a stable coating. The composition was applied with a wound wire rod to a thickness of 3-6 μm and cured by EB irradiation of 165 kV electrons at 3 Mrad. The resulting coating had a gloss of> 70 and was fully cured as shown by the solvent rub test, ie, 18 MEK double rubs.

Example 4 30 parts ethoxylated bisphenol A (SR from Sartomer
602), 47 parts of aliphatic epoxy acrylate (L made by BASF
aromar LR8765), 19.5 parts water, 3 parts photoinitiator (Irgacure 2959 from Ciba), and 0.5 parts acrylated silicone (Rad 2500 from Tego) were mixed to produce a stable coating. This composition is 3 to 6 μm with a wound wire rod.
It was applied to a thickness of m and cured by UV light of at least 120 mJ / cm ² . The resulting coating had a gloss of> 82 and was fully cured as indicated by the solvent rub test, ie 40 MEK double rubs.

Example 5 70 parts glycerol-based polyether acrylate (Laromar 8982 from BASF), 10 parts epoxy acrylate (91-275 from Reichhold), 15 parts water, 3 parts photoinitiator (from Ciba). Irgacure 2959) and 2 parts of silicone (L-7602 from Witco) were mixed to produce a stable coating. This composition is rolled by a wire rod to 3 ~ 6μm
And was cured by UV light of at least 120 mJ / cm ² . The resulting coating had a gloss of> 90 and was fully cured as indicated by the solvent rub test, ie 15 MEK double rubs.

Example 6 This example illustrates a red printing ink formulated according to the present invention. 40 parts of red colorant aqueous dispersion (Sun Chemical
Pigs Division Sunsperse RHD6012), 50 parts of aliphatic epoxy acrylate (BASF Laromer LR876)
5) 5 parts water, 5 parts photoinitiator (Irgacure 295 from Ciba
9) was mixed, coated with a flexo hand proofer (300 lines per inch anilox) to a thickness of about 1-2 μm and cured by UV light of at least 250 mJ / cm ² . The resulting ink was fully cured as indicated by the solvent rub test, i.e. 10 or more IPA double rubs.

Example 7 This example illustrates a blue printing ink formulated according to the present invention. 30 parts of Pigment Blue 15: 3 (Sun Chemical
Phthalocyanine blue) and 70 parts of highly ethoxylated trimethylolpropane triacrylate (15 mol E)
O, SR9035 made by Sartomer) is crushed by 3 roll mill
An agricultural base containing 2/0 grounds was formed. This base 2
0 parts to 40 parts (400) diacrylate (SR34 from sartomer
4), mixed with 10 parts photoinitiator (Irgacure 2959 from Ciba), 10 parts highly ethoxylated trimethylolpropane triacrylate (15 mol EO, SR9035 from Sartomer) and 40 parts water to form a blue ink. It was applied with a flexo hand proofer (300 lines per inch anilox) to a thickness of about 1-2 μm and cured by UV light of at least 250 mJ / cm ² . The resulting ink was fully cured as indicated by the solvent rub test, i.e. 12 or more IPA double rubs.

Example 8 The residual odor of the electron beam cured aqueous composition of Example 1 was compared to a conventional electron beam cured composition (Composition B) using the "Residual Odor Test" above.

Composition B: 30 parts of ethoxylated trimethylolpropane triacrylate (Photomer 4 from Cognis
149), 30 parts of tripropylene glycol diacrylate
(TRPGDA from UCB Radcure), 30 parts epoxy acrylate
(Epotuf 91-275 from Reichhold), 7.5 parts benzoate plasticizer (Benzoflex 9-88 from Velsicol), 1 part polyoxypropylene stearate (P from Lambent Technologies).
rolam MR-216), 2 parts polydimethyl silicone (Witco
L7602), 1 part silicone (DC-57 from Dow Corning)
And 0.5 part of wax compound (Ba
reco wax compound) was mixed well to obtain a stable coating composition.

As described in the "Residual Odor Test", each coating composition was coated on paperboard and aluminum foil with a wire rod to a thickness of 3-6 μm and cured by EB irradiation at 165 kV 3 Mrad. The odor of the samples was evaluated and the results are shown in the table below.

[0061]                                   Table 1             Composition Odor on paper Odor on aluminum foil             Example 1 1.8 1.3             Conventional (Composition B) 3.4 3.3

Example 9 The residual odor and extract of the electron beam cured aqueous composition of Example 1 was compared to an electron beam cured comparative composition (Composition C) using the residual odor test and direct extraction method described above.

Composition C: 40 parts of ethoxylated trimethylolpropane triacrylate (EOTMPTA, P from Cognis
hotomer 4149), 26 parts tripropylene glycol diacrylate (TRPGDA from UCB Radcure), 25 parts epoxy acrylate (Epotuf 91-275 from Reichhold), 6.3 parts benzoate plasticizer (Benzoflex 9-88 from Velsicol). , 0.
7 parts polyoxypropylene stearate (Lambent Tech
nologies, Prolam MR-216) and 2 parts of polydimethyl silicone (Witco L7602) were mixed well to obtain a stable coating composition.

Each coating composition was coated on an aluminum foil with a wire rod to a thickness of 3 to 6 μm and cured by EB irradiation at 165 kV 3 Mrad as described in "Residual Odor Test". Samples were evaluated for odor as described in the "Residual Odor Test". The residual extract of each coated and cured composition was measured by the "direct solvent extraction" method using methylene chloride. The results of each test are shown in the table below.

[0065]                                   Table 2       Composition Total extract (ppb) Odor on board       Example 1 <50 2.1       Comparison 3000 EOTMPTA 3.0     (Composition C) 1800 TPGDA

Example 10 A UV curable aqueous composition of the present invention (Composition D) was UV cured with a residual extract using the "backside extraction with food mimetic" method using methylene chloride. Compared with product E).

Composition D: 77 parts of aliphatic epoxy acrylate (Laromer LR8765 from BASF), 19.5 parts of water and 3 parts of photoinitiator (KIP 150 from Lamberti) are mixed well and a stable coating composition is obtained. Was manufactured.

Composition E: 30 parts of trimethylolpropane triacrylate (TMPTA, Cognis Photomer 400
6), 25 parts of tripropylene glycol diacrylate (U
TRPGDA from CB Radcure), 24 parts epoxy acrylate
(Epotuf 91-275 from Reichhold), 7.0 parts benzoate plasticizer (from Velsicol), 1.0 part dimethylbenzyl ketal photoinitiator (Irgacure 651 from Ciba), 3.0 parts triethanolamine (from Chem Central), 8.0 parts acrylated amine (Laromer 8956 from BASF) and 2 parts silicone (DC57 from Dow Corning) were mixed well to give a stable coating composition.

Each coating composition was thickened with a wire rod.
Apply to 3 ~ 6μm, 150mJ / cm ²Cured. Ko
The residual extract of each cured and hardened composition is analyzed by "direct solvent extraction".
The "out" method was used. About each coating composition
The results are shown in the table below.

[0070]                                   Table 3                Coating composition backside extract                     Example 10 <50ppb Laromer 8765                                       <50ppb KIP 150                     Conventional 500ppb TPGDA                   (Composition) 400ppb TMPTA                                         1700 ppb benzophenone

Example 11 The residual extract of the EB-cured aqueous composition of Example 1 of the present invention was compared to an EB-cured conventional composition (Composition B) using the "backside extraction with food mimics" method. Each coating has a thickness of 3 ~
It was applied to 6 μm and cured with 165 KeV 3 Mrad. The residual extract of each coated and cured composition was measured using the "backside extraction" method. The results for each coating composition are shown in the table below.

[0072]                                   Table 4             Coating composition Backside extract (ppb)                     Example 1 <50ppb Laromer 8765                     Conventional 125 TMPTA                 (Composition B) 95 TPGDA

Example 12 70 parts of polyethylene glycol 200 diacrylate (Sar
SR259 from tomer), 29.5 parts water and 0.5 parts silicone (DC57 from Dow Corning) were mixed well to produce a stable coating. This composition was applied with a wire rod to a thickness of 3-6 μm and cured with 165 KeV 3 Mrad. The gloss of the resulting coating was 80 and was fully cured (25 rubs back and forth) as shown by the solvent rub test.

Example 13 82 parts of polyethylene glycol 400 diacrylate (Sar
SR344 from Tomer, 14 parts water, 3 parts photoinitiator (Irgacure 2959 from Ciba) and 1.0 part acrylated silicone (UC
B Radcure Ebercyl 350) was mixed well to produce a stable coating. The composition was applied with a wire rod to a thickness of 3-6 μm and cured by UV light of at least 180 mJ / cm ² . The gloss of the resulting coating is 75
And was fully cured (25 or more double rubs) as shown by the solvent rub test.

Those skilled in the art will be able to make many modifications to the invention described above. The improvements are within the scope of the invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Michelle Laxine             United States, New Jersey             07076, Scotch Plains, Red Woo             Dead Road 2278 (72) Inventor Jean-Dominique Targis             United States, New Jersey             07070, Rutherford, North Aveni             74 (72) Inventor David Bairro             United States, New Jersey             08876, Branchburg, Dakota tray             Le 6 F-term (reference) 4J038 CH011 CH081 CH141 CH151                       CH171 CH191 DG321 MA08                       MA10 PA17 PB01 PB02                 4J039 AD10 CA03 CA06 EA06 EA08

Claims (50)

[Claims] 1. A method for producing a low extractable film, comprising: a) (i) a water-soluble compound containing at least one α, β-ethylenically unsaturated radiation-polymerizable group, and (ii) water. Providing a radiation curable aqueous composition, b) applying the aqueous composition to a surface, and c) irradiating the surface with actinic radiation in the presence of water, thereby curing the film. Forming a cured film having less than 50 ppb of uncured residue extracted from the cured film when immersed in 10 ml of pseudo liquid per square inch and heated. 2. The water-soluble compound is an oligomer,
The method of claim 1. 3. The oligomer is an acrylate,
The method of claim 2. 4. The acrylate is epoxy acrylate, epoxy methacrylate, polyether acrylate, polyether methacrylate, polyester acrylate, polyester methacrylate, polyurethane acrylate, polyurethane methacrylate, melamine acrylate, melamine methacrylate, polyethylene glycol diacrylate, or polyethylene glycol dimethacrylate. The method of claim 3 selected from the group consisting of: 5. The method of claim 4, wherein the acrylate is an aromatic or aliphatic acrylate. 6. The method of claim 4, wherein the acrylate is a diacrylate ester of an alkanol glycidyl ether or an ethoxylated aromatic epoxide or a polyethylene glycol diacrylate. 7. The method of claim 6 wherein the diacrylate ester of alkanol glycidyl ether is a diacrylate ester of ethoxylated aromatic epoxide and 1,4-butanediodiglycidyl ether. 8. The ethoxylated aromatic epoxide is 6
7. The method of claim 6, which comprises .about.20 ethoxy groups. 9. Water is present in an amount from about 5 wt% to about 25 wt%,
The method of claim 8. 10. The method of claim 8, wherein the composition has a viscosity of 10 to 100,000 centipoise. 11. The method of claim 1, wherein the composition further comprises a colorant. 12. The method according to claim 11, wherein the colorant is a dye, a pigment or a mixture thereof. 13. The method according to claim 1, wherein the actinic radiation is performed by high energy electrons. 14. The method of claim 1, wherein the composition further comprises a photoinitiator activatable by ultraviolet light. 15. The actinic radiation is irradiated with ultraviolet rays,
The method of claim 1. 16. The base material is selected from polyolefin, polyethylene terephthalate, metal-deposited polyethylene terephthalate, polycarbonate, cellulose material, paper material, cardboard material, metal, glass, polystyrene, polyvinyl chloride, polynaphthalene terephthalate, polyacrylate and polyacryl. The method of claim 1 selected from the group consisting of: 17. The substrate according to claim 1, which is a food packaging material.
6. The method according to 6. 18. The method of claim 17, wherein the food packaging material is a container or sheet material. 19. The food packaging material is polyolefin,
The method according to claim 18, which is metal-deposited polyethylene terephthalate, polyethylene terephthalate, or a metal. 20. The method of claim 19, wherein the polyolefin is polyethylene or polypropylene. 21. The method of claim 19, wherein the metal is aluminum foil or iron. 22. The method of claim 17, wherein the simulated liquid is a food mimic. 23. The food mimetic is 10% ethanol / water solution, 50% ethanol / water solution, 95% ethanol / water solution, food oil, boiling point is 240 to 270 ° C. and saturated C ₈ (50 to 50 ° C.).
65%) and C ₁₀ (30-45%) triglyceride fractionated coconut oil, and synthetic C ₁₀ , C ₁₂ and C
23. The method of claim 22, selected from the group consisting of a mixture of ₁₄ triglycerides. 24. The method of claim 16, wherein the pseudo liquid is methylene chloride. 25. The method of claim 22, wherein the heating is performed at least 40 ° C. for at least 240 hours. 26. The heating first to at least 121 ° C. for 2 hours.
23. The method of claim 22, wherein the method is conducted for an hour and then for about 238 hours at about 240 ° C. 27. A water-soluble compound comprising (a) at least one α, β-ethylenically unsaturated radiation-polymerizable group and (b) water, the surface of which is coated with this composition in the presence of water. When exposed to actinic radiation at, a cured film is formed, and when the cured film is dipped in 10 ml of pseudo liquid per square inch and heated, the uncured residue extracted from the cured film is less than 50 ppb. Actinic radiation curable aqueous single liquid composition. 28. The composition of claim 27, wherein the water soluble compound is an oligomer. 29. The composition of claim 28, wherein the oligomer is an acrylate. 30. The acrylate is epoxy acrylate, epoxy methacrylate, polyether acrylate, polyether methacrylate, polyester acrylate, polyester methacrylate, polyurethane acrylate, polyurethane methacrylate, melamine acrylate, melamine methacrylate, polyethylene glycol diacrylate, or polyethylene glycol dimethacrylate. 3. A composition selected from the group consisting of
9. The composition according to 9. 31. The composition of claim 30, wherein the acrylate is an aromatic or aliphatic acrylate. 32. The composition of claim 31, wherein the acrylate is a diacrylate ester of an alkanol glycidyl ether or an ethoxylated aromatic epoxide or a polyethylene glycol diacrylate. 33. The diacrylate ester of alkanol glycidyl ether is 1,4-butanediodiglycidyl ether and the diacrylate ester of ethoxylated aromatic epoxide is ethoxylated trimethylolpropane triacrylate. Composition. 34. The composition of claim 33, wherein the ethoxylated aromatic epoxide contains 6 to 20 ethoxy groups. 35. The composition of claim 27, wherein water is present in an amount of about 5 wt% to about 25 wt%. 36. The composition of claim 27, wherein the composition further comprises a colorant. 37. The composition of claim 27, wherein the colorant is a dye, pigment or mixture thereof. 38. The composition of claim 27, wherein the actinic radiation is a high energy electron. 39. The composition of claim 27, wherein the composition further comprises a photoactivator activatable by ultraviolet light. 40. The actinic radiation is ultraviolet light.
9. The composition according to 9. 41. The surface is made of polyolefin, polyethylene terephthalate, metal-deposited polyethylene terephthalate, polycarbonate, cellulose material, paper material, cardboard material, metal, glass, polystyrene, polyvinyl chloride, polynaphthalene terephthalate, polyacrylate and polyacryl. 5. The group selected from the group consisting of
The composition of 0. 42. The composition according to claim 41, wherein the surface is a polyolefin or a metal. 43. The composition of claim 42, wherein the polyolefin is polyethylene or polypropylene. 44. The composition of claim 41, wherein the metal is aluminum foil or iron. 45. The composition of claim 42, wherein the simulated liquid is a food simulant. 46. The food mimetic is 10% ethanol / water solution, 50% ethanol / water solution, 95% ethanol / water solution, food oil, boiling point is 240 to 270 ° C. and saturated C ₈ (50 to 50).
65%) and C ₁₀ (30-45%) triglyceride fractionated coconut oil, and synthetic C ₁₀ , C ₁₂ and C
46. The composition of claim 45, selected from the group consisting of a mixture of ₁₄ triglycerides. 47. The composition of claim 45, wherein the pseudo liquid is methylene chloride. 48. An aqueous composition essentially consisting of a substrate, (a) a water-soluble oligomer containing two or more acrylic groups, and (b) water is provided, and the aqueous composition is coated on the substrate. And cured by actinic radiation in the presence of water,
A cured film adhered to the surface of a substrate such that less than 50 ppb of uncured residue is extracted from the cured film when immersed in 10 ml of pseudo liquid per square inch of the cured film and heated. Packaging material. 49. The packaging material is a food packaging material,
49. The packaging material according to claim 48, wherein the simulated liquid is a simulated food product. 50. A method of packaging a food or a drug with a film which directly contacts the food or the drug and which conforms to governmental standards, wherein at least one α, β-ethylenically unsaturated radiation 10 is used as the film. A method comprising using an actinic radiation-cured composition comprising a water-soluble compound containing a water-soluble double bond group and water.