JP2001079481A - Production of cured matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily cure a layer comprising a compsn. cured by the radical reaction of a lower layer by providing a layer of the compsn. cured by radical reaction and a layer of a compsn. cured without receiving obstruction due to oxygen on a base material in this order to irradiate them with electron beam. SOLUTION: A layer of a compsn. cured by radical reaction containing a compd. having an ethylenic unsaturated double bond, a pigment and, if necessary, an inert resin and a layer of a compsn. cured by cation reaction containing an alicyclic epoxy group, a cation polymn. initiator and, if necessary, additives such as a leveling agent, a stabilizer, or the like, are provided to be irradiated with active energy rays such as ultraviolet rays or electron beam. By this constitution, even if the irradiation with electron beam is performed in air without carrying out nitrogen substitution, the layer comprising the compsn. cured by radical reaction as the lower layer can be easily cured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a cured product which can be cured well even when irradiated with an electron beam in air without purging with nitrogen to obtain a cured product having excellent coating film properties. About.

[0002]

2. Description of the Related Art Active energy ray curing techniques such as electron beam and ultraviolet ray (1) are quick-curing and have high productivity.
It has the advantages of (2) low energy cost and (3) reduction of the emission of volatile components to the environment by eliminating the use of solvents, and is widely used in applications such as paints, inks and adhesives. Among them, the advantages of electron beam curing include: ・ High curing speed (high productivity). -No heat is applied to the base material (applicable to heat-sensitive materials). -Since there is no need for an initiator and a sensitizer, a product having less impurities can be obtained. Curing is not affected by hue, and can be applied to the curing of films with high pigment concentration. And the like.

However, active energy ray curing, which is generally used industrially, is a radical polymerization system, in which a polymer is formed by a polymerization reaction caused by radicals generated by irradiation of an electron beam or ultraviolet rays, and curing proceeds. In this case, if oxygen is present in the irradiation atmosphere, radical polymerization is inhibited by a reaction between the growing radical in the cured product and the oxygen radical generated by the active energy ray.
In particular, in the case of electron beam curing, which has a great effect, in order to prevent this, an inert gas such as nitrogen is used to reduce the oxygen concentration to 50%.
At present, irradiation is performed at 0 ppm or less, which greatly affects running costs. In addition, when high-speed processing is performed, since the irradiated object has air attached thereto, the oxygen concentration of the curing atmosphere cannot be maintained in the surface layer, and sufficient curability may not be obtained in some cases. .

[0004] In radical polymerization systems, attempts to increase curability even in an atmosphere having a high oxygen concentration have been known, and the addition of a tertiary amine or a phosphite compound is necessary. However, there was a drawback that odor, hygiene, and physical properties of the coating film were deteriorated. On the other hand, the cationic curing system is known as a system that is less susceptible to polymerization inhibition by oxygen with respect to the radical curing system, and there is no restriction that curing must be performed under an inert atmosphere such as nitrogen, and in the air. It has the advantage that rapid and complete polymerization can be performed. However, in the cationic polymerization using active energy rays, an onium salt such as an iodonium salt or a sulfonium salt is cleaved by irradiation of the active energy rays to generate an acid, which acid protonates the monomer, and the monomer molecule grows by addition polymerization. Therefore, if a basic substance is present in the composition, the growth stops and the hardening is inhibited.

[0005] This adverse effect is particularly observed when a composition containing a pigment such as a printing ink or a paint and cured by a cationic reaction is hardened, and the basic structure contained in the pigment structure or the surface treatment substance is contained. Substances are the cause. Therefore, in cationically curable printing inks, a phenomenon in which curing is inhibited by a pigment selected according to the hue has been observed, and there has been a problem that sufficient curability cannot be obtained with printing inks of all hues. Was.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a cured product which does not require nitrogen substitution, which is a drawback of electron beam curing, and has excellent productivity.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition which cures without being inhibited by oxygen on a layer made of a composition which cures by a radical reaction. The present invention has found that a laminated body provided with a layer made of a product can easily cure a layer made of a composition that is cured by a radical reaction of a lower layer even when irradiated with an electron beam in the air without replacing with nitrogen. It was completed.

That is, the present invention provides a layer (1) composed of a composition which is cured by a radical reaction on a substrate,
A method for producing a cured product, comprising: providing a layer (2) made of a composition that cures without being inhibited by oxygen on the layer (1), and then irradiating with an electron beam. .

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The layer (1) is a layer which is cured by a radical reaction when irradiated with an electron beam, and is provided on a substrate to color, protect and pattern printed information by the substrate. Serves purposes such as granting. Layer (1)
The composition which cures by a radical reaction constituting the above contains a compound having an ethylenically unsaturated double bond, a pigment, and if necessary, an inert resin. The compound having an ethylenically unsaturated double bond is a compound whose polymerization is induced by a radical reaction, and specific examples thereof include various (meth) acrylate oligomers and monomers.

Oligomers are those having a weight average molecular weight of 200
It refers to a low polymer of about 5000 or less, and is generally a liquid or a solid having a very high viscosity. As the oligomer,
For example, epoxy acrylate, urethane acrylate, polyester acrylate and the like can be mentioned. Monofunctional or polyfunctional (meth) acrylates can be used as the monomer.

The monofunctional (meth) acrylates include:
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth)
Acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate methyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Methoxytripropylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate,
(Meth) acryloylmorpholine, isobornyl (meth) acrylate, (meth) acrylamide and the like can be mentioned.

The polyfunctional (meth) acrylates include:
Butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, trisacryloyloxyethyl isocyanurate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epoxy adipate (meth) acrylate, hydrogenated bisphenol Ethylene oxide di (meth) acrylate, glycerin ethylene oxide added tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate, triethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide-added pentaerythritol tri ( (Meth) acrylate, propylene oxide-added pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and the like.

The pigment can be freely selected according to the requirements such as the hue and resistance of the obtained cured product. Compositions that cure by a radical reaction include pigments that cure poorly in cationic curing systems and are difficult to use, such as quinacridone pigments having an amino group in the structure (CI Pigme).
nt Violet 19), and pigments surface-treated with basic substances (amines, pigment derivatives, etc.) to improve dispersibility can also be used.

The following are examples of pigments that can be used in compositions that cure by a radical reaction. As an indigo pigment,
C. I. Pigment Blue 15: 1, 15:
3, 23 are red pigments such as C.I. I. Pigment
Red3, 5, 9, 22, 38, 48: 1, 48:
2, 48: 4, 49: 1, 53: 1, 57: 1, 10
1, 122 and 177 are C.I. I. Pigment Vi
olet19 is C.I. I. Pigme
nt Yellow 1, 3, 12, 13, 14, 17,
83, 139 are C.I. I. Pigme
nt Black7. In addition, C.I. I. P
Pigment Green 7, 36, C.I. I. Pigm
ent White 4, 6, 18 and the like can also be used.

The composition of the present invention, which is cured by a radical reaction, can contain an inert resin having no radical reactivity as appropriate according to the physical properties of the film. Examples of the inert resin include, for example, diallyl phthalate resin (for example, Daiso Dap A manufactured by Osaka Soda Co., Ltd.), petroleum resin (for example, Mitsui Petrochemical Co., Ltd .: Hiretz, Arakawa Chemical Co., Ltd .: Alcon), and cyclic ketone resin (for example, Honshu Chemical Co., Ltd .: Halon 80); formaldehyde resin (for example, Mitsubishi Gas Chemical Co., Ltd .: Nicanol); acrylic resin (for example, Arakawa Chemical Co., Ltd .: Beam Set 255). Various pigment dispersants, additives, stabilizers, and the like can be added to the composition of the present invention that cures by a radical reaction, if necessary.

The layer (2) is a layer which is cured without being inhibited by oxygen, and needs to have good adhesion to the substrate and the lower layer (1) and to have excellent flexibility. There are various types of compositions that cure without being inhibited by oxygen constituting the layer (2). Examples of the type of paint include a solvent type, an aqueous type, and a non-solvent type, and are each classified into an unreacted type, a cross-linking agent or a reactive type using active energy rays. In particular, a solvent-free composition which is cured by an active energy ray such as an ultraviolet ray or an electron beam is classified into a radical reaction system and a cation reaction system depending on the form of polymerization.

Among them, the composition of the type that undergoes a radical reaction by ultraviolet rays is slightly affected by the inhibition by oxygen. At present, however, the wavelength of 200 nm or less is cut by adjusting the light emitting source and installing a filter in the ultraviolet ray generating lamp. By doing so, it is possible to improve the degree of inhibition by oxygen to a level at which there is no practical problem. As the composition of the type that undergoes a radical reaction by ultraviolet rays, the same composition as the composition that cures by the radical reaction constituting the layer (1) is used. On the other hand, in the case of a composition of the type that undergoes a radical reaction by an electron beam, it is practically necessary to replace the curing atmosphere with an inert gas such as nitrogen. Is inappropriate.

The aqueous type composition which reacts with the crosslinking agent is obtained by dissolving or dispersing the resin and the crosslinking agent in an aqueous medium. For example, a water-soluble acrylic resin (for example, a copolymer of styrene / (meth) acrylic acid) ), A leveling agent, a pH adjuster, and other additives, and a cross-linking agent such as a polyaziridine compound or an epoxy compound. In addition, the solvent-type composition that reacts with the cross-linking agent is obtained by dissolving or dispersing a petroleum-based, polyester-based, urethane-based, polyvinyl chloride-based, nitrified cotton-based, acrylic-based resin and a cross-linking agent in an organic solvent. There are, for example, those obtained by adding an alkyd resin and a polyester resin, an additive such as a leveling agent, and a diisocyanate compound to an organic solvent.

When the layer (2) is composed of an aqueous or solvent-based composition which is cured by a crosslinking agent, a step of drying and curing after coating is required. It requires a step of irradiating ultraviolet rays after the application, and further requires a step of electron beam curing to cure the lower layer. However, when the layer (2) is composed of a composition that cures by a cationic reaction, the layer (2) can be cured by irradiating an electron beam, and both layers are cured in a single electron beam irradiation step. It is preferable because it can be performed.

The composition of the layer (2), which is cured by a cationic reaction, contains an alicyclic epoxy group, a cationic polymerization initiator and, if necessary, various leveling agents and additives such as a stabilizer. Is preferred. The compound having an alicyclic epoxy group is a compound in which epoxy groups are polymerized by an addition reaction with an acid generated by a cationic polymerization initiator, and specific examples include the following compounds.

[0021]

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[0022]

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[0023]

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[0024]

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Examples of the cationic polymerization initiator used in the present invention include arylsulfonium salt derivatives (for example, UVI-6990, UVI-69 manufactured by Union Carbide).
74, Adeka Optomer SP-15 manufactured by Asahi Denka Kogyo Co., Ltd.
0, ADEKA OPTOMER SP-170), an allyl iodonium salt derivative (for example, RP-207 manufactured by Rhodia)
4), an allene-ion complex derivative (eg, Irgacure 261 manufactured by Ciba Geigy), a diazonium salt derivative,
Acid generators such as triazine initiators and other halides are included. The cationic polymerization initiator is used in an amount of 0.2 to 100 parts by weight of the compound having an alicyclic epoxy group.
It is preferable to contain it at a ratio of 20 parts by weight. If the content of the polymerization initiator is less than 0.2 part by weight, it is difficult to obtain a cured product, and if the content exceeds 20 parts by weight, there is no further effect of improving the curability.

The composition which cures by a cationic reaction includes:
A resin that is solid at normal temperature can be contained for improving the curability and for imparting the adhesion, flexibility and gloss of the cured product. Specific examples of the resin that is solid at room temperature include diallyl phthalate resin, petroleum resin, terpene resin, rosin resin, and epoxy resin. The normal temperature indicates the temperature at the site where the normal printing operation is performed, and 10 to 4
It is about 0 ° C. In addition, it is preferable that a hydroxyl group is introduced into a resin that is solid at room temperature, since curability can be improved.

The use of a diallyl phthalate resin as a solid resin at room temperature is preferred because the curability of the layer (2), the adhesion to the base and the flexibility are improved. The diallyl phthalate resin is a polymer of a diallyl phthalate represented by the following structural formula, such as diallyl orthophthalate or diallyl isophthalate, and has a weight average molecular weight of 1,000.
Those having a size of from 20,000 to 20,000 are preferably used. Examples of commercially available diallyl phthalate resins include Daisodap A manufactured by Osaka Soda Co., Ltd., and DT150 manufactured by Toto Kasei Co., Ltd.

[0028]

Embedded image (Where a represents 0 to 2, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms, an amino group or a silane group.)

Petroleum resin is a general term for resins obtained by directly heating a petroleum unsaturated hydrocarbon as a raw material, heating it using a catalyst, or chemically reacting it with other raw materials. Any of these can be used in the present invention.
As the petroleum resin, use of a ketone-formaldehyde resin obtained by addition condensation of an aromatic and / or aliphatic ketone with formaldehyde and a derivative thereof such as a hydrogenated product thereof and a modified isocyanate product are preferable. Further, a xylene formaldehyde resin obtained by addition condensation of meta-xylene and formaldehyde and a derivative thereof are also used. Examples of these petroleum resins include, for example, Heylets manufactured by Mitsui Petrochemical, Alcon manufactured by Arakawa Chemical Co., and Nicanol manufactured by Mitsubishi Gas Chemical Company.

The terpene resin is a general term for resins obtained from turpentine, kraft pulp, and pine chips obtained from turpentine chips, and includes derivatives thereof. As the terpene-based resin, a terpene polymer, an aromatic modified terpene polymer, a terpene-based water-added resin, a terpene-phenol copolymer, or the like can be used. Examples of terpene-based resins include YS resin, Clearon, Y
S polystar.

The rosin-based resin is a general term for resins obtained from the raw materials obtained by steam distillation and solvent extraction of raw pine tar and pine chips, and also includes derivatives thereof. As the rosin resin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, phenol-modified rosin ester, and the like can be used. Examples of the rosin-based resin include ester gum, stevelite, pentaline, and stevelite ester manufactured by Rika Hercules.

The epoxy resin is a general term for a compound having two or more epoxy groups and a molecular weight of about 350 to 8000, and a resin formed by a ring-opening reaction of the epoxy group. A typical epoxy resin is a bisphenol A type epoxy resin produced by a reaction between bisphenol A and epichlorohydrin. Examples of the epoxy resin include novolak type epoxy resin, brominated epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, and triglycidyl isocyanurate.

The resin which is solid at room temperature is used in an amount of 3 parts by weight per 100 parts by weight of the compound having an alicyclic epoxy group in order to improve the curability and to provide the cured product with adhesion, flexibility and gloss.
It is preferable to contain it in a ratio of 30 parts by weight. If the content of the solid resin at room temperature is less than 3 parts by weight, the above effect is not sufficiently exerted. If the content exceeds 30 parts by weight, the viscosity of the composition may increase and the coating properties such as abrasion resistance may decrease. There is.

The composition which cures by a cationic reaction includes:
Further, a compound having an oxetane ring can be contained. Compounds having an oxetane ring are those that are cured by a cationic reaction, and alone have poor curing properties,
When used in combination with a compound having an alicyclic epoxy group, curability can be improved and the viscosity of the composition can be reduced. Specific examples include the following compounds.

[0035]

Embedded image (Here, R3 represents a hydroxyl group, a (meth) acryloyloxy group, a phenoxy group, an alkyl ether such as hexyl ether, benzyl ether, or allyl ether, or an alkoxy group.)

[0036]

Embedded image (Where R4 is an oxygen atom, p-xylylene diol,
It represents an alkylene chain such as adipate, terephthalate, or cyclohexanedicarboxylate. ) The compound having an oxetane ring is the compound 1 having an alicyclic epoxy group.
It is preferable that the content is 3 to 1000 parts by weight with respect to 00 parts by weight. When the content of the compound having an oxetane ring is less than 3 parts by weight, the effect of improving curability is low, and
Even if it is added in excess of 00 parts by weight, no further effect of improving curability is observed.

The composition which cures by a cationic reaction includes:
Further, a liquid resin having an alcohol or a hydroxyl group can be contained. The liquid resin having an alcohol and a hydroxyl group is not cured alone, but by using it in combination with an alicyclic epoxy group, it is possible to improve curability, impart flexibility to a cured product, and improve adhesion with a base. it can. The liquid resin is a resin that is liquid at normal temperature, and the normal temperature indicates a temperature at a site where a normal printing operation is performed, and is about 10 to 40 ° C.

Specific examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, dodecyl alcohol, cyclohexyl alcohol and benzyl alcohol, and ethylene glycol, propylene glycol, butanediol, butene Diol,
Examples include polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol.

Specific examples of the liquid resin having a hydroxyl group include polycaprolactone diol, polycaprolactone triol, and polyester polyol. Examples of the liquid resin having a hydroxyl group include multimers of polyhydric alcohols such as polyethylene glycol, polypropylene glycol, and polyglycerin. The liquid resin having an alcohol or a hydroxyl group and the alicyclic epoxy have a ratio of hydroxyl group / alicyclic epoxy group of 0.02 to 0.02.
It is preferable to mix them so as to be 0.5, particularly 0.05 to 0.25. The ratio of hydroxyl groups / alicyclic epoxy groups is 0.
If it is less than 02, the effect of improving the curability is low, and if it exceeds 0.5, the curability is rather reduced.

The substrate used in the present invention includes paper, plastic, metal and the like. Examples of paper include coated cardboard, art paper, and polyethylene coated paper, examples of plastic include polyethylene terephthalate, polypropylene, polystyrene, and vinyl chloride; examples of metal include iron, aluminum, and stainless steel. The layer (1) can be formed by applying an offset printing method, a silk screen printing method, a letterpress printing method, or the like. The layer (2) can be formed by applying a gravure printing method, a roll coating method, a gravure offset coating method, a flexographic printing method, a curtain flow coating method, a reverse coating method, a spray method, a dipping method, or the like. Each layer can also be formed by a transfer method.

When each layer is formed on a substrate, it is particularly effective to overlap the layer (2) on the uncured layer (1) in terms of running cost. To form the layer (2) without trapping on the uncured layer (1), the viscosity is 20 ° C.
A composition that cures by a radical reaction of about 10,000 to 100,000 mPa · s (composition constituting the layer (1)) and a composition that cures without being inhibited by oxygen having a viscosity of about 10 to 1000 mPa · s ( It is preferable to use a composition that constitutes the layer (2). When the viscosity of the composition constituting the layer (1) is less than 10,000 mPa · s, trapping or mixing of the layers occurs at the time of coating the layer (2). When the viscosity exceeds 100,000 mPa · s, the ink is fed or transferred. The printing aptitude is hindered. When the viscosity of the composition constituting the layer (2) is less than 10 mPa · s, it is difficult to obtain a sufficient film thickness, and
When it exceeds Pa · s, it becomes difficult to obtain a smooth coated surface.

Although the thickness of each layer varies depending on the application, the layer (1) is about 0.1 to 10 μm, and the layer (2) is 0.5 to 5 μm.
A range of about 0 μm is appropriate. The layer (1) has a thickness of 0.
In the case of 1 μm, the function development such as coloring as the layer (1) is insufficient, and a film thickness exceeding 10 μm is excessive in function development. When the film thickness of the layer (2) is 0.5 μm, gloss and the like are not sufficiently imparted. When the film thickness exceeds 50 μm, curling of the substrate may occur due to the influence of curing shrinkage.

As a specific example of the layer structure of the cured product produced by the method of the present invention, a layer (1) is provided by printing a multicolor printing ink on a base material made of cardboard, and then forming a layer thereon. For example, a layer provided with a layer (2) by applying an overcoat varnish for the purpose of imparting a glossiness.

Examples of the electron beam irradiation device include a curtain beam type, an area beam type, a broad beam type, a scanning beam type, and a vacuum tube type. The electron beam is preferably a low energy beam type having an acceleration voltage of 30 to 300 KV, and it is particularly preferable to irradiate an electron beam of 30 to 100 KV in consideration of the influence of deterioration of the substrate due to the electron beam. The irradiation dose of the electron beam is 5 to 20.
About 0 KGy is preferable, and 3 to 20 KGy is particularly preferable.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described based on embodiments. In the example,
“Parts” and “%” are “parts by weight” and “% by weight”, respectively. The viscosity of the ink and overcoat varnish is 20
It measured using the E-type viscometer at ° C. [Preparation of varnish] In 59.9 parts of trimethylolpropane triacrylate, 0.1 part of hydroquinone and epoxy acrylate ("Lipoxy SP-1" manufactured by Showa Polymer Co., Ltd.)
509 ") and dissolved at 100 ° C. or lower to obtain a varnish.

[Preparation of Radical-Curable Offset Ink Constituting Layer (1)] The pigment, the varnish and the monomer were mixed according to the following formulation, dispersed with a three-roll mill, and had a viscosity of 53000 mPa · s. The ink was adjusted. Indigo pigment (“LIONOL BLUEFG7330” manufactured by Toyo Ink Mfg. Co., Ltd.) 15 parts Varnish 50 parts Dipentaerythritol hexaacrylate 25 parts Pentaerythritol tetraacrylate 10 parts

Example 1 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts Cationic polymerization initiator (“UVI” manufactured by Union Carbide) 0.5 parts of a leveling agent (“BYK-307” manufactured by BYK-Chemie) 0.2 parts were mixed and stirred to prepare an overcoat varnish 1 having a viscosity of 200 mPa · s. The offset ink obtained in (1) was printed by an RI tester (a simple printing machine generally used in the printing ink industry) so that the film thickness became about 1 μm. Coating so that the thickness is 3 μm,
The cured product was manufactured by irradiating an electron beam using an electron beam irradiation apparatus. Irradiation conditions were as follows: acceleration voltage 50 KV, power consumption 20
W, the conveyor speed for transfer was 50 m / min. At the time of irradiation, no replacement with nitrogen was performed.

Example 2 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 80 parts 4-functional alicyclic epoxy monomer (Daicel Chemical Industries, Ltd.) 20 parts Cationic polymerization initiator (“UVR-6974” manufactured by Union Carbide) 0.5 part 0.2 parts of a leveling agent (“BYK-307” manufactured by BYK-Chemie) are mixed and stirred. And an overcoat varnish 2 having a viscosity of 410 mPa · s. Using the offset ink and overcoat varnish 2 obtained above, a cured product was produced in the same manner as in Example 1.

Example 3 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts Diallyl phthalate resin (“Daptote DT- manufactured by Toto Kasei”) 170 ") 25 parts Cationic polymerization initiator (" UVI-6974 "manufactured by Union Carbide) 0.5 part 0.2 parts of a leveling agent (" BYK-307 "manufactured by BYK-Chemie) are mixed and stirred to obtain a viscosity of 320 mPa. s overcoat varnish 3. A cured product was produced in the same manner as in Example 1 using the offset ink and the overcoat varnish 3 obtained above.

Example 4 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 70 parts Bifunctional alicyclic epoxy monomer (Daicel Chemical Industries, Ltd.) "Celoxide 3000") 30 parts Xylene formaldehyde resin derivative ("Nicanol HP-120" manufactured by Mitsubishi Gas Chemical Company) 30 parts Cationic polymerization initiator ("UVI-6974" manufactured by Union Carbide) 0.5 part Leveling agent ( 0.2 parts of “BYK-307” manufactured by BYK-Chemie) were mixed and stirred to prepare an overcoat varnish 4 having a viscosity of 260 mPa · s. Using the offset ink and overcoat varnish 4 obtained above, a cured product was produced in the same manner as in Example 1.

Example 5 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 70 parts Bifunctional alicyclic epoxy monomer (Daicel Chemical Industries, Ltd.) 30 parts Novolak type epoxy resin ("Epicoat 180S80" manufactured by Yuka Shell Epoxy) 30 parts Cationic polymerization initiator ("UVI-6974" manufactured by Union Carbide) 0.5 part Leveling agent (BYK) 0.2 parts of “BYK-307” manufactured by Chemie Co.) was mixed and stirred to prepare an overcoat varnish 5 having a viscosity of 300 mPa · s. Using the offset ink and the overcoat varnish 5 obtained above, a cured product was produced in the same manner as in Example 1.

Example 6 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts Cationic polymerization initiator (“UVI” manufactured by Union Carbide) −6990 ”) 10 parts 0.2 part of a leveling agent (“ BYK-307 ”manufactured by BYK-Chemie) was mixed and stirred to prepare an overcoat varnish 6 having a viscosity of 205 mPa · s. Using the offset ink and the overcoat varnish 6 obtained above, a cured product was produced in the same manner as in Example 1.

Example 7 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 70 parts Trifunctional alicyclic epoxy monomer (Union Carbide) 30 parts diallyl phthalate resin ("Duptote DT-170" manufactured by Toto Kasei) 3 parts Cationic polymerization initiator ("UVI-6974" manufactured by Union Carbide) 0.5 part Leveling agent (BYK-) 0.2 parts of “BYK-307” manufactured by Chemie Co., Ltd.) were mixed and stirred to prepare an overcoat varnish 7 having a viscosity of 90 mPa · s. Using the previously obtained offset ink and overcoat varnish 7, a cured product was produced in the same manner as in Example 1.

Example 8 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts Diallyl phthalate resin (“Daptote DT- manufactured by Toto Kasei Co., Ltd.”) 170 ") 20 parts Cationic polymerization initiator (" UVI-6990 "manufactured by Union Carbide) 10 parts Leveling agent (" BYK-307 "manufactured by BYK-Chemie) 0.2 part is mixed and stirred, and the viscosity is 290 mPa · s. Was prepared. Using the previously obtained offset ink and overcoat varnish 8, a cured product was produced in the same manner as in Example 1.

Example 9 An acrylic resin used as a binder for an overcoat varnish was synthesized by the following method. That is, styrene 5 parts, methyl methacrylate 5 parts, methyl acrylate 50 parts, 2-hydroxyethyl acrylate 1
0 parts, acrylic acid 10 parts, water 30 parts, ethanol 12
0 parts were mixed, half of the mixture was charged into a flask, heated to 80 ° C., and 2 parts of 2,2′-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added as an initiator, and the reaction was performed. Started. After the reaction has started, the remaining half is dropped over 3 hours. After the dropping, the mixture is aged at 80 ° C. for 4 hours, cooled, adjusted to pH with ammonia water and the like, taken out of the flask, and an acrylic resin aqueous solution having a solid content of 35% is added. Obtained. The resulting acrylic resin aqueous solution and other raw materials were mixed according to the following formulation to prepare an overcoat varnish 9 having a viscosity of 240 mPa · s. Pure water 20 parts Acrylic resin aqueous solution 70 parts PH adjuster (25% ammonia water) 1 part Leveling agent ("TSF4440" manufactured by Toshiba Silicone Co., Ltd.) 1 part Aziridine-based cross-linking agent (Meisei Chemical "SU-125F") 2 parts Polyethylene The offset ink obtained by the above procedure was printed on a coated paper by an RI tester (a simple printing machine generally used in the printing ink industry) so that the film thickness became about 1 μm. On the printed material, an overcoat varnish 9 was applied so as to have a thickness of 3 μm, dried at 80 ° C. for 1 minute, and irradiated with an electron beam under the same conditions as in Example 1 to produce a cured product.

Example 10 An overcoat varnish 10 having a viscosity of 240 mPa · s was prepared by mixing the following raw materials. Alkyd resin (Hitachi Kasei Co., Ltd. "phthalic 926-70") 70 parts Ethyl acetate 49.6 parts Antifoaming agent (BYK-077 "BYK-Chemie") 0.2 parts Leveling agent (BYK-Chemie " BYK-307 ") 0.2 part Diisocyanate crosslinking agent (" Takenate D-110N "manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts Using the offset ink and the overcoat varnish 10 obtained earlier, in the same manner as in Example 9. A cured product was produced.

Example 11 The following materials were mixed to prepare an overcoat varnish 11 having a viscosity of 340 mPa · s. Acrylic resin (Arakawa Chemical “Beamset 243”) 20 parts Pentaerythritol polyacrylate (Arakawa Chemical “Beamset 710”) 20 parts Tripropylene glycol diacrylate 55 parts Photopolymerization initiator (Ciba Geigy “Irgacure 184”) )) 5 parts Leveling agent ("BYK-307" manufactured by BYK-Chemie) 0.2 parts The offset ink obtained by the above procedure is applied to a polyethylene coated paper using an RI tester (commonly used in the printing ink industry). Printing was performed by a simple printing machine so that the film thickness became about 1 μm. On printed matter, overcoat varnish 11
Was coated so as to have a thickness of 3 μm, and irradiated with ultraviolet rays using an ultraviolet irradiation apparatus (“Unicure” manufactured by Ushio Electric Co., Ltd.) to form a cured film. Irradiation condition is lamp output 1
20 W / cm and the conveyor speed were 30 m / min. Thereafter, an electron beam was irradiated under the same conditions as in Example 1 to produce a cured product.

Example 12 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts 1,2-bis} [(3-ethyl- 3-Oxetanyl) methoxy] methyl @ benzene (Toa Gosei Co., Ltd. “Aron Oxetane OXT-121”) 100 parts Cationic polymerization initiator (Union Carbide Co., Ltd. “UVR-6974”) 1 part Leveling agent (BYK-Chemie) And 0.4 parts of “BYK-307” manufactured by Toshiba Corporation were mixed and stirred to prepare an overcoat varnish 12 having a viscosity of 250 mPa · s. Using the offset ink and the overcoat varnish 12 obtained above, a cured product was produced in the same manner as in Example 1.

Example 13 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts n-hexyl alcohol 15 parts Cationic polymerization initiator (Union -0.5 part of "UVR-6974" manufactured by Carbide Co., Ltd. 0.2 part of a leveling agent ("BYK-307" manufactured by BYK-Chemie) was mixed and stirred to prepare an overcoat varnish 13 having a viscosity of 300 mPas. Using the offset ink and the overcoat varnish 13 obtained above, a cured product was produced in the same manner as in Example 1.

Example 14 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide) 100 parts Butane-1,4-diol (ISP Japan) 5 parts Cationic polymerization initiator ("UVR-6974" manufactured by Union Carbide) 0.5 part Leveling agent ("BYK-307" manufactured by BYK-Chemie) 0.2 The parts were mixed and stirred to prepare an overcoat varnish 14 having a viscosity of 400 mPa · s. Using the previously obtained offset ink and overcoat varnish 14, a cured product was produced in the same manner as in Example 1.

Example 15 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate (“UVR-6110” manufactured by Union Carbide Co.) 100 parts Caprolactone triol (a liquid resin having a hydroxyl group, Union Carbide) 10 parts Cationic polymerization initiator (“UVR-6974” manufactured by Union Carbide) 0.5 part Leveling agent (“BYK-307” manufactured by BYK-Chemie) 0.2 The parts were mixed and stirred to form an overcoat varnish 15 having a viscosity of 400 mPa · s. Using the offset ink and the overcoat varnish 15 obtained above, a cured product was produced in the same manner as in Example 1.

[Comparative Example 1] 30 parts of an epoxy acrylate oligomer (“Epoxy Ester 200PA” manufactured by Kyoeisha Chemical Co., Ltd.) 40 parts of ethylene oxide-added trimethylolpropane triacrylate 30 parts of tripropylene glycol diacrylate were mixed and stirred to obtain a viscosity of 110 mPa · s. Of overcoat varnish 16 was prepared. Using the offset ink and the overcoat varnish 16 obtained above, a cured product was produced in the same manner as in Example 1.

[Comparative Example 2] At the time of electron beam curing of a coating material prepared in the same manner as in Comparative Example 1, the irradiation atmosphere was replaced with nitrogen and cured at an oxygen concentration of 200 ppm. The oxygen concentration was measured using an oxygen concentration meter (Zirconia LC-7 manufactured by Toray Engineering).
50H).

Comparative Example 3 A cationically curable offset ink was prepared in the following procedure. [Preparation of Varnish] 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (“UVR-6110” manufactured by Union Carbide) 8
In 0 parts, 20 parts of diallyl phthalate resin ("Duptote DT-170" manufactured by Toto Kasei Co., Ltd.) was dissolved at 60 ° C or lower to obtain a varnish.

[Preparation of Cationic Curable Offset Ink Constituting Layer (1)] The pigment, the varnish and the monomer were mixed according to the following formulation, dispersed with a three-roll mill, and dispersed in a cationic curable offset ink having a viscosity of 71,000 mPa · s. The ink was adjusted. Red pigment (Shinkasha Red B-RT-796D manufactured by Ciba Geigy) 15 parts Solspers 24000 (manufactured by Zeneca) 1 part Varnish 73.5 parts 4-functional alicyclic epoxy monomer (Eporide GT401 manufactured by Daicel Chemical Industries, Ltd.) )) 10 parts Cationic polymerization initiator ("UVI-6974" manufactured by Union Carbide Co.) 0.5 part Cured product in the same manner as in Example 1 using the obtained cation-curable offset ink and overcoat varnish 1. Was manufactured.

The cured products obtained in Examples 1 to 15 and Comparative Examples 1 to 3 were evaluated for curability, flexibility and adhesion to the base ink. Table 1 shows the results. The evaluation was performed by the following method. (1) Curability of the cured product: The dryness was evaluated by a finger, and was indicated in five stages, from fully cured to uncured 1. (2) Scratch resistance: The surface of the cured product was rubbed with nails, and the degree of scratching was visually evaluated. (3) Flexibility of the cured product: The cured product was bent, and the degree of cracking of the coating film was visually evaluated. (4) Adhesion to base ink: Evaluated by a cellophane tape peeling test, and expressed in five levels of good to bad 1.

[0067]

[Table 1]

[0068]

According to the present invention, a cured product having good film properties can be produced by electron beam irradiation without replacing with nitrogen.

Claims (11)

[Claims] 1. A layer (1) composed of a composition which is cured by a radical reaction on a substrate, and a composition which is cured on the layer (1) without being inhibited by oxygen. A method for producing a cured product, comprising providing a layer (2) and then irradiating an electron beam. 2. The method for producing a cured product according to claim 1, wherein the layer (2) is composed of a composition that is cured by a cationic reaction. 3. The method according to claim 1, wherein the acceleration voltage of the electron beam is 30 to 100 KV. 4. The method for producing a cured product according to claim 2, wherein the composition which is cured by a cationic reaction contains a compound having an alicyclic epoxy group and a cationic polymerization initiator. 5. A composition which is cured by a cationic reaction, further comprising a resin which is solid at room temperature.
A method for producing the cured product according to the above. 6. A composition which is cured by a cationic reaction, based on 100 parts by weight of a compound having an alicyclic epoxy group.
6. The method for producing a cured product according to claim 5, comprising 3 to 30 parts by weight of a resin which is solid at room temperature. 7. The method for producing a cured product according to claim 5, wherein the resin solid at room temperature is a diallyl phthalate resin. 8. The method for producing a cured product according to claim 4, wherein the composition which is cured by a cationic reaction further contains a compound having an oxetane ring. 9. A composition which is cured by a cationic reaction, based on 100 parts by weight of a compound having an alicyclic epoxy group.
9. The method for producing a cured product according to claim 8, comprising 3 to 1000 parts by weight of a compound having an oxetane ring. 10. A composition which is cured by a cationic reaction,
The method for producing a cured product according to any one of claims 4 to 9, further comprising a liquid resin having an alcohol or a hydroxyl group. 11. A composition which is cured by a cationic reaction,
The method for producing a cured product according to claim 10, comprising a compound having a hydroxyl group such that the ratio of hydroxyl group / alicyclic epoxy group becomes 0.02 to 0.5.