JPS61179232A - Actinic energy ray-curable composition - Google Patents

Abstract

PURPOSE:The titled composition which can give a flexible and tough cured product excellent in weather resistance, water resistance, etc., essentially consisting of a polyisocyanate derivative and an ethylenically unsaturated monomer. CONSTITUTION:5-95wt% polyisocyanate derivative (A) having at least two groups of the formula (wherein R1 is a 1-14C alkylene) in the molecule is mixed with 95-5wt% ethylenically unsaturated monomer (B) such as a monomer or oligomer having at least one polymerizable unsaturated double bond in the molecule (e.g., trimethylolpropane triacrylate) and, optionally, 100wt% or below polyurethane resin (C) having an ethylenically unsaturated group or the like and/or 20wt% or below, based on the total of A+B+C+D, compound (D) having at least one SH group in the molecule (e.g., o-mercaptobenzoic acid) and 0.1-10wt%, on the same basis, photopolymerization initiator (E) for ultraviolet curing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition that is cured by irradiation with active energy rays, and more particularly relates to a composition that is cured by irradiation with active energy rays and is useful for paints, printing inks, adhesives, pressure-sensitive adhesives, molding materials, etc. A novel composition of the invention.

Compositions whose main component is a compound having an ethylenically unsaturated bond that undergoes a crosslinking reaction upon irradiation with active energy rays such as electron beams and ultraviolet rays are already known, and are widely used in the fields of paints, printing inks, adhesives, etc. It is used.

However, in the current situation where technological innovation is rapidly progressing, the level of required performance for the above compositions is inevitably high. There is a strong desire to improve corrosion resistance.

Therefore, as a result of extensive research aimed at improving the above-mentioned performance of active energy ray-curable compositions, the present inventors have now developed a product obtained by adding a mercapto group-containing alcohol to a polyisocyanate compound. The present invention was completed by discovering that the object can be achieved by using the present invention.

Thus, according to the invention: (a) at least two →JHCOO-R1 in one molecule;
-SH group [here, R1 represents an alkylene group having 1 to 14 carbon atoms] and (b) an ethylenically unsaturated monomer, as essential components, and optionally Furthermore, it is characterized by containing (c) a resin containing an ethylenically unsaturated group, and/or (d) a compound having one or more mercapto groups in one molecule [however, the above component (a) is excluded]. An active energy ray-curable composition is provided.

The main feature of the present invention is that the above-mentioned components (a) and (b) are used, and in particular, the reaction product of a polyincyanate compound and a mercapto group-containing alcohol is used as the component (a). be. Upon irradiation with active energy rays, this composition essentially forms a mercapto group (-SH) in component (a) and an ethylenically unsaturated group (C) in component (b).
=CH*) crosslinks and cures, resulting in good curability.Moreover, the curing reaction converts the molecules into linear polymers, so shrinkage stress is small, and adhesion and adhesion (especially adhesion to plastics, adhesion) is good. excellent in sex)
It has the advantage of providing an excellent cured product. Also,
The composition of the present invention has a urethane bond (-NH
COO-), the cured film or layer formed from the composition is flexible and tough. Furthermore, the cured film or layer has excellent properties such as weather resistance, water resistance, and corrosion resistance.

Therefore, the composition of the present invention can be used as a coating material, a printing material, an adhesive,
It can be widely used as a molding material, etc.

Each component constituting the composition according to the present invention will be explained below.

(a) Component = at least 2 NHCO in 1 molecule
A polyisocyanate derivative having an OR+ SH group (R1 represents an alkylene group having 1 to 14 carbon atoms, preferably 1 to 6 carbon atoms); This is usually a polyisocyanate having two or more isocyanate groups in one molecule. It can be obtained by reacting a compound with a mercapto group-containing alcohol.

“Polyisocyanate compound J is obtained by reacting a relatively low molecular weight polyisocyanate having two or more isocyanate groups in one molecule and a polyol having two or more hydroxyl groups in one molecule. Urethane prepolymers having two or more isocyanate groups in one molecule are included.

The polyisocyanate having 2 or more, preferably 2 to 3 isocyanate groups in one molecule is any type of polyisocyanate, including aliphatic, cycloaliphatic, aromatic, and aromatic-aliphatic. For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane2.
4 (or 2,6) diisocyanate), 1,3-(isocyanatomethyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate , butylene diisocyanate,
Propylene diisocyanate, octadecylene diisocyanate, 1,5 naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, naphthylene diisocyanate, polymer of tolylene diisocyanate, polymer of diphenylmethane diisocyanate, polymer of hexamethylene diisocyanate. combination, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate,
4-methoxy-1,3-phenylene diisocyanate,
4-ethoxy-1,3-phenylenedi・f-socyanane)
, 2.4'-diisocyanate diphenyl ether, 5
．． 6-dimethyl-1,3-phenylene diisocyanate, 4,4'-cyisocyanate, diphenyl ether, penzidine diisocyanate), 9.10-anthracene diisocyanate, 4,4'-benzyl diisocyanate, 3,3'- Dimethyl-4,4'-diisocyanate diphenylmethane, 2,6-dimethyl-4,4'-diisocyanate diphenyl, 3,3'-dimethoxy-4,
4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenyl diisocyanate ane 6-tolylene triisocyanate, 2,4.4'-)
+7-1 Socyanate diphenyl ether,! .

4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate), 1,10-decamethylene diisocyanate), 1,3-cyclohexyl diisocyanate), 4,4'-methylene-bis(cyclohexyl isocyanate) ), and these can be used alone or in combination of two or more. Among these, particularly preferred are isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate), 1.6-
Includes hexane diisocyanate.

Examples of polyols having two or more hydroxyl groups in one molecule that can be reacted with the polyisocyanate include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and polyethylene glycol (molecular weight 400
0 or less), trimethylene glycol, polypropylene glycol (with a molecular weight of 4000 or less), tetramethylene glycol, polytetramethylene glycol (
molecular weight of 4000 or less), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,
1,3-bentanediol, neopentyl glycol,
1,2-hexylene glycol, 1,6-hexanediol, heptanedio-/I/, 1,1o-tecanediol, cyclohexanediol, 2-butene-1,4-
Diol, 3-cyclohexene-1,1-dimetatool, 4-methyl-3-cyclohexene-1,1-dimetatool, 3-methylene-1,5-bentanediol, (2
-hydroxyethoxy)-1-propatool, 4-(2
-hydroxyethoxy)-1-butanol, 5-(2-
hydroxyethoxy)-pentanol, 3-(2-hydroxypropoxy)-1-propatol, 4-(2-hydroxypropoxy)-1-butanol, 5-(2-hydroxypropoxy)-1-bettanol, 1-( 2-
hydroxyethoxyl)-2-butanol, 1-(2-
Hydroxyethoxy)-2-pentanol, hydrogenated bisphenol A1 glycerin, polycaprolactone, 1,
2.6-hexanediol, trimethylolpropane,
Trimethylolethane, pentanetriol, trishydroxymethylaminomethane, 3-(2-hydroxyethoxy)-1゜2-propanediol, 3-(2-hydroxypropoxy)-1,2-propanediol, 6-
Examples include polyhydric alcohols such as (2-hydroxyethoxy)-1,2-hexanediol, pentaerythritol, dipentaerythritol, mannitol, and glucose.

4fc, the polyhydric alcohol, ethylene oxide,
Polyether polyols obtained by adding alkylene oxides such as propylene oxide and butylene oxide can also be used as polyols. Furthermore, the above-mentioned polyhydric alcohols include, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, methylcyclohexenetricarboxylic acid, adipic acid, cepacic acid, azelaic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hymic acid, succinic acid, etc. acids, saturated polybasic acids or their anhydrides such as dodecynylsuccinic acid, methylglutaric acid, pimelic acid, malonic acid and their anhydrides, and for example maleic acid, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, A polyester obtained by reacting a polybasic acid component selected from unsaturated polybasic acids or anhydrides thereof such as mesaconic acid, itaconic acid, tetrahydrophthalic acid, carpic acid, het acid, aconitic acid, glutaconic acid, and anhydrides thereof. Polyols can also be used as polyols. Furthermore, in addition to those mentioned above, hydroxyl group-containing acrylic resins, hydroxyl group-containing epoxy resins and epoxy-modified resins, hydroxyl group-containing butyral resins, polyvinyl alcohol copolymers, hydroxyl group-containing polybutadiene resins, and the like can also be used as polyols.

Among these polyols, particularly preferred are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol (with a molecular weight of 1000 or less), trimethylene glycol, tetramethylene glycol, polytetramethylene glycol (with a molecular weight of 1000 or less). things), 1,
Polyhydric alcohols selected from 4-butanediol, 1,5-bentanediol, neohentyl glycol, 1,6-hexanediol, chrycerin, polycaprolactone (with a molecular weight of 2000 or less), trimethylolpropane, and these polyhydric alcohols and at least one polybasic acid selected from phthalic acid, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic acid, hexahydrophthalic acid and succinic acid, and the molecular weight is 5.
000 or less, as well as 3-15 mole propylene oxide adducts of glycerin.

Using the urethane prepolymer thus prepared,
In general, a composition that forms a cured film or layer with excellent flexibility and toughness can be obtained.

The reaction between polyisocyanate and polyol is carried out by reacting 2 or more moles of polyisocyanate per mole of polyol according to a conventional method, so that two or more isocyanate groups remain in one molecule of the reaction product. be able to.

The mercapto group-containing alcohol to be reacted with the polyisocyanate compound described above has the general formula H8-R,
-OH [wherein R1 represents a linear or branched alkylene group having 1 to 14 carbon atoms, preferably 1 to 6 carbon atoms] is used, such as mercaptomethanol, mercaptoethanol Preferred examples include mercaptopropertool, mercaptobutanol, and the like. Among these, mercaptoethanol is particularly suitable.

The reaction between the polyisocyanate compound and the mercapto group-containing alcohol is a urethanization reaction between the incyanate group and the hydroxyl group, and the reaction is carried out using 2 or more moles of the latter per 1 mole of the former, and the reaction product 1 2 or more, preferably 2 to 6 free mercapto groups (-8R
) is introduced. Note that unreacted isocyanate groups may remain in the polyisocyanate derivative produced.

(b) Component: Ethylenically unsaturated monomer; Ethylenically unsaturated monomers include monomers and oligomers containing at least one polymerizable unsaturated double bond in one molecule (however, (Excluding diesters of (meth)acrylic acid starting from tricyclodecane dialcohol).

Examples of such monomers include, first, esters of acrylic acid or methacrylic acid and monohydric alcohols having 1 to 25 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
n-butyl acrylate, n-butyl methacrylate, acrylic acid is.

-butyl, 1so-butyl methacrylate, tacrylate
ert-butyl, tert-butyl methacrylate, propyl acrylate, propyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, methacryl These include 2-ethylhexyl acid, cyclohexyl acrylate, cyclohexyl methacrylate, stearyl acrylate, stearyl methacrylate, and the like.

Also, the monomers include styrene, vinyltoluene, methyl? Vinyl aromatic compounds such as tyrene, chlorostyrene, divinylbenzene; other vinyl compounds such as vinyl acetate, vinyl chloride, vinyl isobutyl ether, methyl vinyl ether, acrylonitrile, 2-ethylhexyl vinyl ether, etc. can also be used. Further, as the monomer, carboxyl group-containing monomers such as acrylic acid and methacrylic acid; hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate; butyl isocyanate, Adducts of polyisocyanates such as phenyl isocyanate and the above hydroxyl group-containing monomers; esterification products of phosphoric acid and the above hydroxyl group-containing monomers; unsaturated monomers having nitrogen-containing heterocycles such as vinylpyrrolidone and vinylpyridine can also be used.

Examples of oligomers include diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1.3-butanediol diacrylate, 1.3
-butanediol diacrylate, 1,4-butanediol diacrylate), 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanethiol diacrylate), 1 .6-hexanethiol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
di-, tri- or tetravinyl compounds such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate;
, a product obtained by reacting the adduct of the polyhydric alcohol and ethylene oxide with acrylic acid and/or methacrylic acid; a product obtained by reacting the adduct of the polyhydric alcohol and propylene oxide with acrylic acid and/or methacrylic acid. products obtained by reacting the adduct of polyhydric alfur and ε-caprolactone with acrylic acid and/or methacrylic acid; and polymerizable unsaturated oligomers.

The monomers and oligomers mentioned above may be used alone or in combination.
Can be used in combination with more than 100ml.

As component (b), it is preferable to use an oligomer having 2 or more, preferably 2 to 6, polymerizable unsaturated double bonds in one molecule alone or in a mixture of 2 or more seconds,
When using a monomer having only one double bond in one molecule, the amount used is the same as component (a), regardless of whether or not a monomer having two or more double bonds in one molecule is used together. It is preferably 10% by weight or less based on the total amount with component (b).

Examples of oligomers having two or more polymerizable unsaturated double bonds in one molecule, which are preferably used as component (b), include polyethylene glycol di(meth)acrylate (with a molecular weight of 500 to 1200); Polypropylene glycol di(meth)acrylate (molecular weight 500-1
200), 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. Examples include esters of alcohol and (meth)acrylic acid.

The composition of the present invention contains the above-mentioned components (a) and (b) as essential components, and the composition ratio thereof is as follows:
Based on the total amount of both components, component (a) generally contains 5
95% to 95% by weight, in particular 30 to 70% by weight, and component (b) generally 95 to 5% by weight, particularly preferably 70 to 30% by weight.

The composition of the present invention can be substantially composed of the above-mentioned components (a) and (b), but if necessary, the composition of the present invention may further contain an ethylenically unsaturated group. Improve physical properties and adjust viscosity by blending resin ((cls) and/or compound having one or more mercapto groups in one molecule (excluding component (a)) (component (d)) can be done.

Examples of the ethylenically unsaturated group-containing resin as component (c) include a resin obtained by condensing (meth)acrylic acid with polyester, an ethylenically unsaturated group-containing polyurethane resin,
Ethylenically unsaturated group-containing epoxy resin, ethylenically unsaturated group-containing phosphorus-containing epoxy resin, ethylenically unsaturated group-containing acrylic resin, ethylenically unsaturated group-containing silicone resin,
Examples include melamine resin containing ethylenically unsaturated groups. The blending ratio of component (c) is not strictly limited and can be varied widely depending on the use of the composition of the present invention, but generally it is the sum of component (&) and component (b). Based on the amount, component (c) is not more than 100% by weight, preferably 1
It can be blended in a proportion of ~25% by weight.

Next, compounds having one or more, preferably 1 to 6 mercapto groups in one molecule used as component (d) include, for example, mercaptomethanol, mercaptoethanol, mercaptopropanol, mercaptobutanol,
Mercapto alcohols such as 3-mercapto-1,2-propanediol; mercaptocarboxylic acids such as thioglycolic acid, mercaptosuccinic acid, and 0-mercaptobenzoic acid; mercapto group/containing polyester resins, mercapto group-containing polyether resins, mercapto groups Examples include mercapto group-containing resins such as epoxy resins containing mercapto groups, acrylic resins containing mercapto groups, and polyurethane resins containing mercapto groups. The blending amounts of these compounds are (a) component, (b)
A suitable amount is 20% by weight or less, preferably 10% by weight or less, based on the total amount of components (C) and (d).

The composition of the present invention has the above components (a) and (b) as essential components, and optionally contains the above components (c) and/or (d). Furthermore, the composition may optionally contain a thermal polymerization inhibitor and a curing reaction (which occurs when irradiated with active energy rays).
A coloring agent (pigment or dye) that does not substantially inhibit radical polymerization (radical polymerization) may be added, and a small amount of an organic solvent having a low boiling point (preferably 180° C. or less) may be included.

Thermal polymerization inhibitors that can be incorporated into the composition of the present invention include hydroquinone, hydroquinone monomethyl ether, p
- liL of benzoquinone, N-nitronecyphelamine, N-nitrosophenylhydroxyamine, ammonium salt of N-nitronephenylhydroxyamine, phenothiazine, and other conventional radical polymerization inhibitors.

The composition of the present invention can be cured by irradiation with active energy rays such as electron beams and ultraviolet rays. When curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator to the cough composition in advance. As the photopolymerization initiator, a conventional photopolymerization initiator that generates radicals when excited by ultraviolet irradiation is used, such as EVA, benzoin, benzoin methyl ether, pentuin ethyl ether, and pentuin n-propyl. Ether, pentwinisopropyl ether, benzoin n-butyl ether, α-hydroxy imbutylphenone, benzophenone, p-methylbenzophenone,
Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, 2-methylanthraquinone,
Examples include phenyl disulfide and 2-nitronluolene.

These photopolymerization initiators can be used alone or in combination of two or more. The amount to be blended is 0.0000000000000000000000000 is based on the total amount of component (a), component (b), component (C) and component (d).
A range of 1 to 10% by weight is preferred. Furthermore, in order to promote the photopolymerization reaction by these photopolymerization initiators, a photosensitization accelerator may be used in combination with the photopolymerization initiator. Examples of photosensitizers that can be used in combination include tertiary amines such as triethylamine, triethanolamine, and 2-dimethylaminoethanol; alkylphosphine-based agents such as phenylphosphine; and thioether-based agents such as β-thiodiglycol. Examples include sensitization promoters. These photosensitization accelerators can be used alone or in combination of two or more, and the blending amount is based on the total amount of component (a), component (b), component (C), and component (d). It is preferably in the range of 0.1 to 10% by weight.

On the other hand, when electron beam irradiation is used, it is not necessary to incorporate the photopolymerization initiator and photosensitization accelerator as described above into the composition of the present invention.

Examples of electron beam generation sources for curing the composition of the present invention by irradiation with electron beams include Cockcroft type, Cockcroft-Walton type, Pan de Gras 7 type, resonant transformer type, transformer type, and insulation type. Electron beam generators such as core transformer type, dynamidron type, linear filament type, and high frequency type can be used. The electron beam irradiation conditions at that time vary depending on the shape, thickness, etc. of the composition of the present invention, but generally a dose in the range of 1 to 20 megalashes is suitable.

Further, as the ultraviolet irradiation source, a mercury lamp, a xenon lamp, a carbon arc, a metal height lamp, sunlight, etc. can be used. Although the conditions for irradiation with ultraviolet rays are not particularly limited, it is preferable to irradiate with ultraviolet rays containing ultraviolet rays within a range of 150 to 450 nm for several seconds or more in air or in an inert gas atmosphere. In particular, when irradiating in air, it is preferable to use a high-pressure mercury lamp.

The composition of the present invention has the above-mentioned characteristics and advantages, and is particularly useful in paints, printing inks, adhesives, pressure-sensitive adhesives, molding materials, and the like.

For example, the compositions of the present invention can be applied to metals (e.g., iron, copper,
metal oxides, compounds, and chemical conversion treatments; products, wood (e.g., cedar, cypress, 2-wan, pine, cypress, veneer, plywood, verticle board, hardboard, veneer, etc.), paper (e.g.,
(tissue paper, cardboard paper, plastic-impregnated paper, printing paper, etc.), plastic products (e.g., polyethylene, polypropylene, polycarbonate, polyterephthalate resin, acrylic resin, polybutadiene resin, epoxy resin, melamine resin, silicone resin, polyester resin, Ether resin, polyurethane resin, cellulose ester resin, polyacetal, polyamide resin, novolak resin, phenol resin, vinyl chloride resin, vinyl acetate resin, vinyl alcohol resin, copolymers or mixtures of two or more of these, or metal, wood, paper , mixtures with inorganic materials), inorganic materials (cement products, slate, plaster,
Marble, stone, glass, silicon products, ceramics, new ceramics, etc. can be easily painted, printed, bonded, etc., and the hardened layer has the above characteristics, making it extremely advantageous. It is.

Additionally, the compositions of the present invention can be used as adhesives, for example, to impart tackiness by reducing the amount of active energy irradiated to the compositions of the present invention than is necessary for complete curing. You can get good results.

Next, the content of the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited in any way by this example. Parts and units in Examples are parts by weight and t% by weight.
It is.

■ Production Example 1-1 Example of producing component (a) ■ (a) Component (1) 550 parts of polycaprolactone (average molecular weight 550) and 383 parts of tolylene diisocyanate were placed in four flasks, and stirred continuously until 80 parts were added. After 1 hour at 0.degree. C., it is cooled to a temperature of 70.degree. Next, at the same temperature, 0.5 parts of hydroquinone and 187 parts of 2-mercaptoethanol were added to a fourth flask, and the temperature was raised to 80°C by stirring while blowing nitrogen gas.
After holding the mixture for a certain period of time and confirming by a conventional method that almost no residual free incyanate groups were observed, the mixture was cooled to obtain component (a) (1).

■ Ca) component (2) Compound with propylene oxide added to glycerin [
ADEKA G400 (manufactured by Asahi Denka Co., Ltd., molecular weight 4oo)]
4oo parts and 666 parts of isophorone diisocyanate.
The mixture was placed in a double flask and kept at 100°C for 2 hours with stirring, and then cooled to a temperature of 70°C. Then, at the same temperature, 0.7 parts of hydroquinone and 234 parts of 2-mercaptoethanol were added into the four flasks.
The temperature was raised to 100°C with stirring while blowing gas into it, and held for 5 hours. After confirming by the usual method that almost no free incyanate groups remained, the product was cooled. (a) component (2) was obtained.

1-2 Production example of component (c) ■ 550 parts of ethylenically unsaturated group-containing urethane resin polycaprolactone (average molecular weight 550) and 440 parts of inphoron diisocyanate were placed in a four-piece Lof flask,
After keeping the mixture at 100°C for 1 hour with stirring, the mixture was cooled to a temperature of 70°C, and 232 parts of 2-hydroxyethyl acrylate was added to a fourth flask, and the mixture was stirred and brought to a temperature of 80°C while blowing air. 'cK was raised and maintained for 5 hours, and after confirming by a conventional method that almost no free incyanate groups remained, this product was cooled to obtain component (c) (1).

(2) Examples Examples 1 to 6 The components shown in Table 1 were uniformly mixed to obtain silk W products which are the object of the present invention.

331 Application Example 1 The composition of Example 1 was applied to a printed nine-paper plywood board using a roll coater to a film thickness of about 100μ, and then
When irradiated with an electron beam at a dose of Mrad, a coated surface with excellent adhesion and gloss was obtained.

Application Example 2 The composition of Example 1 was applied to a 50μ thick polyethylene sheet using a bar coater to a film thickness of 10μ, and then a 50μ thick aluminum foil was laminated thereon, and 3Mr.
When irradiated with an electron beam at a dose of ad, a laminated sheet with good adhesiveness was obtained.

Application Example 3 100 parts of the composition of Example 1 50 parts of cyanine blue The above mixture was applied to a phosphate-treated board using a coater to a film thickness of 30μ, and then exposed to an electron beam using 2 MradO radiation. Upon irradiation, a coating film with good adhesion was obtained, and the weather resistance was also good.

Application Example 4 When the same mixture as used in Application Example 3 was printed on high-quality paper using a letterpress printing machine and irradiated with an electron beam at a dose of 2 Mrad, a print with clear characters was obtained.

Application Example 5 Mixture of Application Example 3 150 parts Ethyl acetate 30 parts The above mixture was applied onto a slate board using a spray gun to a film thickness of 30μ, and then irradiated with an electron beam at a dose of 3 Mrad. A good coating film was obtained, and the weather resistance was also good.

Application Example 6 Composition of Example 1 100 parts α-hydroxyisobutylphenone 5 parts The above mixture was mixed with 2I
After coating on a polymethyl methacrylate plate of IJI thickness using a bar coater, a polymethyl methacrylate plate of the same thickness was laminated, and when ultraviolet rays were irradiated for 5 seconds through the plate with a high-pressure mercury lamp of 80 W/cTrL, good adhesion was observed. A laminated board was obtained.

Application Example 7 The composition of Example 2 was applied to a particle board using a roll coater to a film thickness of 10 μm, and a polypropylene sheet with wood prints was laminated thereon. When irradiated with an electron beam, a plastic-covered wood board with good adhesiveness was obtained.

Application Example 8 Composition of Example 2 100 parts Titanium white 80 parts The above mixture was coated on an aluminum plate using a bar coater to a film thickness of 30μ, and then irradiated with a 3M rad electron beam. However, a coating film with good adhesion and water filling was obtained.

Application Example 9 Composition of Example 3 100 parts Red dye 2 parts The above mixture was coated on a glass plate using a bar coater to a film thickness of 20μ, and then irradiated with an electron beam of 3 Mrad.
A coating film with good adhesion and light X resistance was obtained.

Application example 10 Composition of Example 4 100 parts r-iron oxide powder 400 parts The above mixture was coated on a polyester film using a bar coater to a film thickness of 5μ, and irradiated with an electron beam of 8 Mrad, resulting in good quality. A magnetic film was obtained.

Application Example 11 The composition of Example 5 was coated onto coated paper using a roll coater to a film thickness of 50 μm, and then 0.5 Mr.
A sticky sheet was obtained by irradiating it with a low-intensity electron beam.

Claims (1)

[Claims] (a) At least two -NHCOO-R_ in one molecule
Contains a polyisocyanate derivative having a 1-SH group (where R_1 represents an alkylene group having 1 to 14 carbon atoms) and (b) an ethylenically unsaturated monomer as essential components, and optionally Furthermore, it is characterized by containing (c) a resin containing an ethylenically unsaturated group, and/or (d) a compound having one or more mercapto groups in one molecule [however, the above component (a) is excluded]. Active energy ray curable composition.