JP4865483B2 - Method for producing molded printed matter, and molded printed matter - Google Patents

Description

  The present invention relates to a method for producing a molded printed material and a molded printed material.

  Today, vending machines for beverage products such as drinking water, tea and juice are widely used, and dummy displays showing products to be sold are displayed on these vending machines. As these dummy exhibits, a flat decorative sheet with decorative printing on a transparent thermoplastic resin sheet is deep-drawn into a half size of a full-size beverage product container, There are some which are made so as to appeal the product image strongly by making a molded product having a high drawing depth of 25 mm or more and giving illumination from the back side.

  As a processing method for producing such a deep-drawn molded product of a decorated thermoplastic resin sheet, vacuum forming, pressure forming, or vacuum / pressure forming is most preferable. In vacuum forming, in principle, a flat decorative sheet is preheated to a temperature at which it can be thermally deformed in advance, and this is sucked into a mold by decompression and stretched by pressure and cooled to the mold. Pressurization is performed from the opposite side of the mold, and it is cooled by pressure bonding to the mold. In vacuum / pressure forming, the pressure reduction and pressurization are performed simultaneously.

  Therefore, in vacuum forming, pressure forming, and vacuum forming (hereinafter referred to as vacuum forming), the thermoplastic resin sheet used as a base material requires a high degree of stretchability in a heated state. Resin sheets, cured vinyl chloride resin sheets, polystyrene resin sheets, etc. are generally used. Polycarbonate resin sheets are easy to use for decorative printing and have excellent resistance to molded products produced by vacuum forming. And polyester resin sheets are most preferably used.

  As the thermoplastic resin sheet to be used, a sheet having a thickness of about 0.1 to 0.8 mm, preferably about 0.3 to 0.6 mm is generally used. In addition, the ink for decorating the sheet as described above includes a colorant such as a pigment, and the solvent-based ink using a vinyl chloride copolymer, a solvent-soluble polyester resin, an acrylic resin, or the like as a binder. Is commonly used. A decorative print layer printed with such an ink has been used very well in vacuum forming and the like because it exhibits good stretchability following a substrate sheet in a heated state.

  However, in the conventional method as described above, there is an environmental problem that the solvent has to be removed by evaporation in order to use the solvent type ink, and heating energy and drying time are required to evaporate and remove the solvent. There was a difficulty.

  On the other hand, the ink jet method is an inexpensive device and does not require a plate at the time of printing, and ink is ejected only to the required image area to form an image directly on the recording medium, so that ink is used efficiently. The running cost is low, especially for small lot production. Furthermore, it has low noise and is excellent as an image recording method, and has attracted attention in recent years.

  In particular, inkjet recording inks that can be cured by irradiation with radiation such as ultraviolet rays (radiation curable inkjet recording inks) are harder than most ink components by irradiation with radiation such as ultraviolet rays. This is an excellent method in that it can be printed on various substrates because it has excellent drying properties and images do not easily bleed. There is a need for radiation-curable inks that cure with high sensitivity and form high-quality images. By achieving high sensitivity, high curability is imparted by irradiation with actinic radiation, so that sufficient curing is achieved in addition to reducing power consumption and extending life by reducing the load on the actinic radiation generator. As a result, there are various advantages such as suppression of volatilization of uncured low molecular weight substances and reduction in the strength of the formed image. In addition, there is a need for an ink composition in which the obtained image (printed material) is unlikely to crack or peel off, and has excellent impact resistance, flexibility, and substrate adhesion of a cured film. Since the cured film has high flexibility, impact resistance, and substrate adhesion, it can be displayed and stored for a long period of time in various environments while maintaining high image quality, and handling of the printed material becomes easy. There are benefits.

  The ink composition applied to the printing sheet (decoration sheet) that has been subjected to molding processing requires a high degree of flexibility of the cured film because the ink film is stretched during processing. Further, a cured film strength that can withstand the molding process is also required. Conventionally, ink compositions having high flexibility have been disclosed (see Patent Document 1 and Patent Document 2), but the film strength is insufficient, and scratches and white spots occur in the image during molding. There was a problem that it could not withstand stretching and would cause cracks.

  Further, Patent Document 3 discloses an ink that can be cured by irradiation with radiation such as ultraviolet rays used for vacuum forming and pressure forming, but has a high viscosity and cannot be applied to an ink jet system.

International Publication No. 02/038688 Pamphlet International Publication No. 05/026270 Pamphlet JP 2003-326591 A

  An object of the present invention is to provide a method for producing a high-quality molded printed material in a method for producing a molded printed material. It is another object of the present invention to provide a molded printed material obtained by the manufacturing method.

The above object has been achieved by the means described in <1> and <6> below. It is shown below with <2>-<5> which are preferable embodiments.
<1> (A) a step of forming an image on a support by an inkjet method using an actinic radiation curable ink composition, (B) a step of irradiating the image with actinic radiation to cure the image, (C Including a step of obtaining a printed matter having an image and a protective layer on a support by coating and / or laminating on the cured image, and (D) a step of vacuum forming or pressure forming the printed matter. A method for producing a molded printed matter characterized by
<2> The actinic radiation curable ink composition has one ethylenically unsaturated double bond group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, and an N-vinyl group. And a method for producing a molded printed matter according to <1>, wherein the composition contains a radically polymerizable monomer having a cyclic structure in an amount of 60% by weight or more,
<3> The method for producing a molded printed material according to <1> or <2>, wherein the actinic radiation curable ink composition contains N-vinyl lactams,
<4> The actinic radiation curable ink composition contains at least one cation polymerizable monomer selected from the group consisting of an oxetane compound, an oxirane compound and a vinyl ether compound, and a monofunctional cation polymerizable monomer. <30> a method for producing a molded printed material according to <1>, wherein 30% by weight or more is contained therein;
<5> The method for producing a molded printed material according to any one of <1> to <4>, wherein the coating material used for the coating process is an ultraviolet curable composition,
<6><1> to <5> A molded printed material obtained by the method for producing a molded printed material according to any one of the above.

  ADVANTAGE OF THE INVENTION According to this invention, in the manufacturing method of the printed matter by which the shaping | molding process was carried out, the manufacturing method of the printed matter by which the high quality image was processed can be provided. Furthermore, it is possible to provide a molded printed matter obtained by the manufacturing method.

The method for producing a molded printed material according to the present invention includes (A) a step of forming an image on a support by an inkjet method using an actinic radiation curable ink composition, and (B) irradiating the image with actinic radiation. Curing the image, (C) obtaining a printed material having an image and a protective layer on a support by coating and / or laminating the cured image, and (D) vacuum forming the printed material. It includes a step of processing or pressure forming.
Hereinafter, after describing in detail the actinic radiation curable ink composition, the coating material, the laminate film and the support used in the present invention, a method for producing a molded printed material will be described.

In the present invention, when a specific portion is referred to as a “group”, it may be substituted with one or more (up to the maximum possible number) substituents unless otherwise specified. For example, “alkyl group” means a substituted or unsubstituted alkyl group.
In the present invention, when a specific moiety is referred to as “ring”, or when “ring” is included in “group”, it may be monocyclic or polycyclic, and may be substituted, unless otherwise specified. Substitution is also possible. For example, the “aryl group” may be a phenyl group, a naphthyl group, or a substituted phenyl group.
In the present invention, oxetane compounds and oxirane compounds are also collectively referred to as “cyclic ether compounds”.

(Actinic radiation curable ink composition)
The method for producing a molded printed material of the present invention uses an actinic radiation curable ink composition (hereinafter also simply referred to as “radiation curable ink composition”, “ink composition” or “ink”).
As the ink composition that can be used in the present invention, a radical polymerizable composition or a cationic polymerizable composition is preferably used.

The ink composition that can be used in the present invention is an ink composition that can be cured by irradiation with actinic radiation.
The “active radiation” as used in the present invention is not particularly limited as long as it can impart energy capable of generating an initial species in the composition by the irradiation, and is broadly α-ray, γ-ray, X-ray. , Ultraviolet rays (UV), visible rays, electron beams, and the like. Among them, ultraviolet rays and electron beams are preferable from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are particularly preferable. Accordingly, the ink composition in the present invention is preferably one that can be cured by irradiation with ultraviolet rays as radiation.

  The ink composition that can be used in the present invention preferably contains a polymerizable monomer, and contains a colorant and a polymerization initiator. Moreover, you may contain another component as needed. Hereinafter, the properties of each component and the ink composition will be described.

(1) Polymerizable monomer The ink composition that can be used in the present invention contains at least a polymerizable monomer.
The polymerizable monomer that can be used in the present invention is preferably an addition polymerizable compound, and more preferably a radical polymerizable compound or a cationic polymerizable compound.
Moreover, the polymeric compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types, for example, may use together a radically polymerizable compound and a cationically polymerizable compound. Good.

<Radically polymerizable compound>
There is no restriction | limiting in particular as long as it does not deviate from the meaning of this invention as a radically polymerizable compound which can be used for this invention, A well-known radically polymerizable compound can be used.
Examples of the radical polymerizable compound are described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-80675, and the like. A photocurable material using a photopolymerizable composition is known.

The radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and may be any compound as long as it has at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. , Oligomers, polymers and the like having a chemical form. The radical polymerizable compound may contain one kind at an arbitrary ratio in order to improve the desired properties, and may contain two or more kinds.
Radical polymerization having an ethylenically unsaturated double bond group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, and an N-vinyl group as the radical polymerizable compound that can be used in the present invention. Preferred examples of the monomer are as follows.

Further, as the radical polymerizable compound, monofunctional radical polymerizable having only one ethylenically unsaturated double bond group selected from the group consisting of acrylate group, methacrylate group, acrylamide group, methacrylamide group and N-vinyl group. A monomer is preferably used, and the monofunctional radically polymerizable monomer preferably has a cyclic structure.
In the present invention, there is only one ethylenically unsaturated double bond group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group and an N-vinyl group, and a cyclic structure. It is preferable that the functional radical polymerizable monomer is contained in the ink composition in an amount of 60% by weight or more. The content is more preferably 65% by weight or more, and still more preferably 70% by weight or more. Further, the radical polymerizable monomer is preferably 95% by weight or less, more preferably 90% by weight or less in the ink composition. It is preferable that the content of the radical polymerizable monomer is in the above range since the flexibility of the obtained image is good and the curability is good.

As the radical polymerizable compound that can be used in the present invention, it is more preferable to use a cyclic monomer having an N-vinyl group, and N-vinylcarbazole, 1-vinylimidazole, and N-vinyllactams are used. It is more preferable to use N-vinyl lactams.
Preferable examples of N-vinyl lactams that can be used in the present invention include compounds represented by the following formula (I).

In the formula (I), n represents an integer of 1 to 5, and n is 2 to 4 from the viewpoint of flexibility after the composition is cured, adhesion to a recording medium, and availability of raw materials. It is preferably an integer, more preferably n is 2 or 4, and particularly preferably n is 4, that is, N-vinylcaprolactam. N-vinylcaprolactam is preferable because it is excellent in safety, is generally available and can be obtained at a relatively low price, and provides particularly good curability and adhesion of a cured film to a recording medium.
The N-vinyl lactams may have a substituent such as an alkyl group or an aryl group on the lactam ring, and may be linked with a saturated or unsaturated ring structure.
Since N-vinyl lactams are compounds having a relatively high melting point, when N-vinyl lactams are used, the content is preferably 40% by weight or less, more preferably 30% by weight in the ink composition. In addition, good solubility is exhibited even at a low temperature of 0 ° C. or lower, and the temperature range in which the ink composition or the surface coating composition can be handled is widened.

Moreover, as a radically polymerizable compound that can be used in the present invention, a monomer having an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, and / or an N-vinyl group and having a cyclic structure is preferably exemplified. it can. More preferable examples include cyclic monomers having an acrylate group, a methacrylate group, an acrylamide group, and / or a methacrylamide group.
Cyclic monomers include phenyl groups, naphthyl groups, anthracenyl groups, pyridinyl groups and other aromatic groups, tetrahydrofurfuryl groups, piperidinyl groups and other heterocyclic groups, cyclohexyl groups, cyclopentyl groups, cycloheptyl groups, isobornyl groups, And monomers having a hydrocarbon cyclic group such as a cyclodecanyl group.

  The cyclic monomer having a (meth) acrylate group and / or a (meth) acrylamide group is preferably norbornyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl. (Meth) acrylate, cyclooctyl (meth) acrylate, cyclodecyl (meth) acrylate, dicyclodecyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-benzyl ( (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meta) Acrylate, EO modified cresol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene Glycol (meth) acrylate, N-phthalimidoethyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, N-cyclohexyl (meth) acrylamide, N- (1,1-dimethyl-2-phenyl) Phenyl) ethyl (meth) acrylamide, N-diphenylmethyl (meth) acrylamide, N-phthalimidomethyl (meth) acrylami N- (1,1′-dimethyl-3- (1,2,4-triazol-1-yl)) propyl (meth) acrylamide, 5- (meth) acryloyloxymethyl-5-ethyl-1,3- An example is dioxacyclohexane.

Moreover, (M-1)-(M-29) shown below as a cyclic monomer which has an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, and / or a vinyl ether group can also be illustrated preferably.
In some of the chemical formulas described later, the hydrocarbon chain is described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted.

  Moreover, (N-1)-(N-28) shown below as a cyclic monomer which has an acrylate group, a methacrylate group, an acrylamide group, and / or a methacrylamide group can also be illustrated preferably.

If necessary, the following acyclic monofunctional monomer can also be used as the radical polymerizable monomer. The acyclic monofunctional monomer has a relatively low viscosity and can be preferably used for the purpose of reducing the viscosity of the composition. However, the proportion of the following acyclic monofunctional monomer in the entire composition is 20% by weight or less from the viewpoint of suppressing the stickiness of the cured film and giving a high film strength that does not cause scratches during molding. Is preferable, more preferably 15% by weight or less, and particularly preferably 10% by weight or less.
Specifically, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, 2 -Hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, 2-ethylhexyl-diglycol acrylate, polyethylene glycol (meth) acrylate monomethyl ether, polypropylene glycol (meth) acrylate monomethyl ether, polytetraethylene glycol (meth) acrylate monomethyl ether, etc. Can be illustrated.

If necessary, the following polyfunctional monomers can also be used as the radical polymerizable monomer. By containing a polyfunctional monomer, a composition having excellent curability and high cured film strength can be obtained. However, from the viewpoint of maintaining cured film stretchability suitable for molding, the proportion of the following polyfunctional monomer in the entire composition is preferably 15% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
Specifically, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylol propane triacrylate, tetramethylol methetate Acrylate, tetramethylol methane triacrylate, dimethylol tricyclodecane diacrylate, modified glycerin triacrylate, modified bisphenol A diacrylate, bisphenol A PO adduct diacrylate, bisphenol A EO adduct diacrylate, dipentaerythritol hexaacrylate And caprolactone-modified dipentaerythritol hexaacrylate.

  The total amount of radically polymerizable monomers in the ink composition that can be used in the present invention is preferably 60 to 95 parts by weight, more preferably 65 to 90 parts by weight, based on the total amount of the composition. More preferably, it is 70-90 weight part. It is preferable for it to be in the above range since the curability is excellent and the viscosity is moderate.

  Of the radical polymerizable monomers of the ink composition that can be used in the present invention, at least one is preferably a monofunctional monomer, and at least one is more preferably a monofunctional acrylate. It is preferable to use a monofunctional monomer because sufficient cured film flexibility can be obtained in addition to sufficient curability.

  When a monofunctional radical polymerizable monomer is used as the polymerizable monomer, the proportion of the monofunctional radical polymerizable monomer in the ink composition is preferably 1 to 95 parts by weight, and preferably 50 to 90 parts by weight. Is more preferable, and it is still more preferable that it is 65-90 weight part. Within the above range, the curability and flexibility are excellent, and the viscosity is appropriate, which is preferable.

  When the polymerizable monomer has a bifunctional or higher monomer (polyfunctional monomer), the proportion of the bifunctional or higher monomer in the ink composition is preferably 0.5 to 50 parts by weight, More preferably, it is -30 weight part, It is still more preferable that it is 0.5-20 weight part. Within the above range, the curability and flexibility are excellent, and the viscosity is appropriate, which is preferable.

<Cationically polymerizable compound>
The cationic polymerizable compound that can be used in the present invention is not particularly limited as long as it is a compound that initiates a polymerization reaction by a cationic polymerization initiating species generated from a cationic polymerization initiator described later, and cures. Various known cationically polymerizable monomers known as can be used. Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and 2001-2001. Preferred examples include oxirane compounds (hereinafter also referred to as “epoxy compounds”), vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526. In addition, as the cationic polymerizable compound, for example, a cationic polymerization-based photocurable resin is known, and recently, a photocationic polymerization-based photocurable resin sensitized to a visible light wavelength region of 400 nm or more, For example, they are disclosed in JP-A-6-43633 and JP-A-8-324137.

An epoxy compound is a compound having at least one oxirane group in the molecule. Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts and epichlorohydrin, such as bisphenol A or its alkylene oxides. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably.
Examples of the aliphatic epoxide include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, or 1 Of diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its adduct of alkylene oxide Dialkylidyl ether, polypropylene glycol, or polyalkylene glycol jig represented by diglycidyl ether of its alkylene oxide adduct Glycidyl ether and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The monofunctional and polyfunctional epoxy compounds that can be used in the present invention are exemplified in detail.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, and 1,3-butadiene monooxide. 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. It is done.

  Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S di Glycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, Bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4- Poxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene Diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1 , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,13-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, etc. Is mentioned.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, Di- or trivinyl ether compounds such as methylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl Pills vinyl ether, isopropyl vinyl ether, isopropenyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

Below, monofunctional vinyl ether and polyfunctional vinyl ether are illustrated in detail.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and the like.

Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide. Divinyl ethers such as divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Savinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound that can be used in the present invention refers to a compound having at least one oxetane ring in the molecule, and is described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. Such known oxetane compounds can be arbitrarily selected and used.
The compound having an oxetane ring that can be used in the present invention is preferably a compound having 1 to 4 oxetane rings in its structure. By using such a compound, it becomes easy to maintain the viscosity of the composition in a favorable range of handling properties, and when used as an ink composition or a composition for surface coating, a recording medium after curing High adhesion can be obtained.

  Examples of the compound having 1 to 2 oxetane rings in the molecule include compounds represented by the following formulas (1) to (3).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.
R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, an alkylcarbonyl group having 2 to 6 carbon atoms, or 2 to 6 carbon atoms. Represents an alkoxycarbonyl group, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkenyl group include a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, and 2-methyl-2. -Propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and the like. Examples of the group having an aromatic ring include phenyl group, benzyl group, fluorobenzyl group, methoxybenzyl group, phenoxyethyl group and the like. Can be mentioned. As the alkylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, a butylcarbonyl group, etc., as an alkoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, etc., as an N-alkylcarbamoyl group, Examples thereof include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group. R ^a2 may have a substituent, and examples of the substituent include an alkyl group of 1 to 6 and a fluorine atom.

R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group Represents an alkylene group containing, an alkylene group containing a carbamoyl group, or a group shown below. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

When R ^a3 is the above polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, Represents a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure. In the following formula, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  Examples of the compound represented by the formula (1) include 3-ethyl-3-hydroxymethyloxetane (OXT-101: manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane. (OXT-212: manufactured by Toagosei Co., Ltd.) and 3-ethyl-3-phenoxymethyloxetane (OXT-211: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (2) include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: manufactured by Toagosei Co., Ltd.). Examples of the compound represented by the formula (3) include bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd.).

  As a compound which has 3-4 oxetane rings, the compound shown by following formula (4) is mentioned, for example.

In the formula (4), R ^a1 has the same ^{meaning as} in the formula (1). In addition, as R ^a9 which is a polyvalent linking group, for example, a branched polyalkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly ( An alkyleneoxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Another embodiment of the oxetane compound that can be suitably used in the present invention includes a compound represented by the following formula (5) having an oxetane ring in the side chain.

In the formula (5), R ^a1 and R ^a8 have the same ^{meaning as} in the above formula. R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

Such a compound having an oxetane ring is described in detail in JP-A No. 2003-341217, paragraphs 0021 to 0084, and the compound described herein can be suitably used in the present invention. Further, oxetane compounds described in JP-A-2004-91556 can also be used in the present invention. This is described in detail in paragraphs 0022 to 0058.
Among the oxetane compounds used in the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of the viscosity and tackiness of the composition.

  The cationically polymerizable compound that can be used in the present invention may be used alone or in combination of two or more, but from the viewpoint of effectively suppressing shrinkage during curing, an oxetane compound and It is preferable to use a vinyl ether compound in combination with at least one compound selected from epoxy compounds.

In the present invention, the cation polymerizable monomer preferably contains at least one cation polymerizable monomer selected from the group consisting of an oxetane compound, an oxirane compound, and a vinyl ether compound. The total content of the compound, monofunctional oxirane compound and monofunctional vinyl ether compound) is preferably 30% by weight or more in the ink composition. It is more preferably 35% by weight or more, and further preferably 40% by weight or more. Moreover, it is preferable that it is 95 weight% or less, and it is more preferable that it is 90 weight% or less.
When the content of the monofunctional cation polymerizable monomer is within the above range, the curability is excellent, the flexibility of the resulting image is good, and the stretchability is excellent, so that it can be suitably used for molding processing. Therefore, it is preferable.
Among these, it is preferable to use a monofunctional oxetane compound and / or a monofunctional oxirane compound, and it is more preferable to use a monofunctional oxetane compound. Of the monofunctional monomers, monomers having a cyclic group such as an aromatic group, an alicyclic cyclic group, and a heterocyclic group-containing are more preferable.

In the present invention, when a polyfunctional oxetane compound and / or a polyfunctional oxirane compound is used, the total amount of the polyfunctional oxetane compound and the polyfunctional oxirane compound is preferably less than 25% by weight based on the entire ink composition. An ink composition excellent in stretchability of the cured film can be provided at a ratio of less than 25% by weight.
In the present invention, when a cationically polymerizable compound is used, it preferably contains an oxetane compound and an oxirane compound, and more preferably contains a polyfunctional oxirane compound and a polyfunctional oxetane compound. By allowing the oxetane compound and the oxirane compound to coexist in the composition, a composition can be provided that provides a cured film having excellent curability and high scratch resistance that hardly causes scratches. More preferably, the polyfunctional oxetane compound and the polyfunctional oxirane compound coexist.

  Preferred examples of the cationically polymerizable compound that can be used in the present invention include monomers (C-1) to (C-24) having a cyclic structure shown below.

  The total amount of the cationic polymerizable monomer in the ink composition that can be used in the present invention is preferably 60 to 95 parts by weight, more preferably 65 to 90 parts by weight, based on the total amount of the composition. More preferably, it is 70-90 weight part. It is preferable for it to be in the above range since the curability is excellent and the viscosity is moderate.

  Of the polymerizable monomers of the ink composition that can be used in the present invention, at least one is preferably a monofunctional monomer, and more preferably a monofunctional oxetane compound or a monofunctional oxirane compound. It is preferable to use a monofunctional monomer because sufficient cured film flexibility can be obtained in addition to sufficient curability.

  When a monofunctional cation polymerizable monomer is used as the polymerizable monomer, the proportion of the monofunctional cation polymerizable monomer in the ink composition is preferably 1 to 90 parts by weight, and 20 to 90 parts by weight. Is more preferable, and it is still more preferable that it is 30-90 weight part. Within the above range, the curability and flexibility are excellent, and the viscosity is appropriate, which is preferable.

  When the polymerizable monomer has a bifunctional or higher monomer (polyfunctional monomer), the proportion of the bifunctional or higher monomer in the ink composition is preferably 0.5 to 50 parts by weight, More preferably, it is -30 weight part, It is still more preferable that it is 0.5-20 weight part. Within the above range, the curability and flexibility are excellent, and the viscosity is appropriate, which is preferable.

(2) Polymerization initiator As a polymerization initiator that can be used in the present invention, a known polymerization initiator can be used. The polymerization initiator that can be used in the present invention may be used alone or in combination of two or more. Moreover, you may use together a radical polymerization initiator and a cationic polymerization initiator.
The polymerization initiator that can be used in the present invention is a compound that absorbs external energy and generates a polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays. Among these, visible light, ultraviolet rays and electron beams are preferable, ultraviolet rays and electron beams are more preferable, and ultraviolet rays are more preferable.

<Radical polymerization initiator>
The radical polymerization initiator that can be used in the present invention includes (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, and (e) thio compounds. (F) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) carbon halogen bond And (m) an alkylamine compound. These radical polymerization initiators may use the above compounds (a) to (m) alone or in combination. The radical polymerization initiator in the present invention is preferably used alone or in combination of two or more.

  Preferable examples of (a) aromatic ketones and (e) thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. FOUASSIER J.M. F. RABEK (1993), pp. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77-117. Preferred examples of (a) aromatic ketones, (b) acylphosphine compounds, and (e) thio compounds include α-thiobenzophenone compounds described in JP-B-47-6416, JP-B-47-3981. Benzoin ether compounds described in Japanese Patent Publication No. 47-22326, α-substituted benzoin compounds described in Japanese Patent Publication No. 47-22326, benzoin derivatives described in Japanese Patent Publication No. 47-23664, and aroylphosphonic acid esters described in Japanese Patent Publication No. 57-30704. Dialkoxybenzophenone described in JP-B-60-26483, benzoin ethers described in JP-B-60-26403, JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318 791, α-aminobenzopheno described in European Patent No. 0284561A1 P-di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, Examples thereof include acylphosphine described in JP-B-2-9596, thioxanthones described in JP-B-63-61950, and coumarins described in JP-B-59-42864.

  Examples of the benzophenone compound include benzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4'-methylphenyl sulfide and the like. Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like.

In addition, (a) the aromatic ketone is preferably α-hydroxyketone, such as 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one. 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
Among these, as the (a) aromatic ketone, a 1-hydroxycyclohexyl phenyl ketone compound is particularly preferable. In the present invention, the 1-hydroxycyclohexyl phenyl ketone compound means a compound in which 1-hydroxycyclohexyl phenyl ketone and 1-hydroxycyclohexyl phenyl ketone are substituted with an arbitrary substituent. The substituent can be arbitrarily selected as long as it can exhibit the ability as a radical polymerization initiator, and specific examples thereof include alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group). it can.

Further, as the (b) acylphosphine compound, an acylphosphine oxide compound is preferable.
Examples of the acylphosphine oxide compound include those having the structural formula of formula (7) or formula (8) in the structure of the compound.

  In particular, as the acylphosphine oxide compound, those having a chemical structure of the formula (9) or the formula (10) are particularly preferable.

（式中、Ｒ₆、Ｒ₇、Ｒ₈はメチル基又はエチル基を置換基として有していてもよい芳香族炭化水素基を表す。）

(In the formula, R ₆ , R ₇ and R ₈ represent an aromatic hydrocarbon group which may have a methyl group or an ethyl group as a substituent.)

（式中、Ｒ₉、Ｒ₁₀、Ｒ₁₁はメチル基又はエチル基を置換基として有していてもよい芳香族炭化水素基を表す。）

(In formula, R < ₉ >, R < ₁₀ >, R < ₁₁ > represents the aromatic hydrocarbon group which may have a methyl group or an ethyl group as a substituent.)

  As the acylphosphine oxide compound, a monoacylphosphine oxide compound, a bisacylphosphine oxide compound, or the like can be used. As the monoacylphosphine oxide compound, a known monoacylphosphine oxide compound can be used. Examples thereof include monoacylphosphine oxide compounds described in JP-B-60-8047 and JP-B-63-40799. Specific examples include isobutyrylmethylphosphinic acid methyl ester, isobutyrylphenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid methyl ester, 2-ethylhexanoylphenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid isopropyl Ester, p-toluylphenylphosphinic acid methyl ester, o-toluylphenylphosphinic acid methyl ester, 2,4-dimethylbenzoylphenylphosphinic acid methyl ester, p-tert-butylbenzoylphenylphosphinic acid isopropyl ester, acryloylphenylphosphinic acid methyl ester , Isobutyryl diphenyl phosphine oxide, 2-ethylhexanoyl diphenyl phosphine oxide, o-toluyl diphenyl phosphite Oxide, p-tert-butylbenzoyldiphenylphosphine oxide, 3-pyridylcarbonyldiphenylphosphine oxide, acryloyl-diphenylphosphine oxide, benzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid vinyl ester, adipoylbisdiphenylphosphine oxide, pivaloyl Diphenylphosphine oxide, p-toluyldiphenylphosphine oxide, 4- (tertiarybutyl) benzoyldiphenylphosphine oxide, terephthaloylbisdiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, versatoyldiphenylphosphine oxide, 2-methyl-2 -Ethylhexanoyldiphenylphosphine oxide, 1- Chill - cyclohexanoyl diphenylphosphine oxide, pivaloyl phenyl phosphinic acid methyl ester and pivaloyl phenyl phosphinic acid isopropyl ester.

  A known bisacylphosphine oxide compound can be used as the bisacylphosphine oxide compound. Examples thereof include bisacylphosphine oxide compounds described in JP-A-3-101686, JP-A-5-345790, and JP-A-6-298818. Specific examples include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxy. Phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthyl Phosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) decylphosphite Oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,5- Dimethylphenylphosphine oxide, bis (2,6-dichloro3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2- Methyl-1-naphthoyl) -2-naphthy Phosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methoxy-1-naphthoyl) ) -4-engineered phenylphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Etc.

  Among these, in the present invention, as the acylphosphine oxide compound, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819: manufactured by Ciba Specialty Chemicals), bis (2,6-dimethoxybenzoyl) -2,4,4-Trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO: manufactured by Ciba Specialty Chemicals, Lucirin TPO: manufactured by BASF) and the like are preferable.

  (C) As aromatic onium salt compounds, elements of Groups 15, 16 and 17 of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se, Te, or I fragrances Group onium salts are included. For example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, and 297443 are disclosed. The diazonium salts described in the specifications of U.S. Pat. Nos. 2,974,279, 279210, and 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,444, and 2,833,827. Benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, US Pat. No. 4,743,528, JP-A-63) -138345, JP-A-63 142345, JP-A-63-142346, and JP-B-46-42363, specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc.) The compounds described in JP-A 52-147277, 52-14278, and 52-14279 are preferably used. Generates radicals and acids as active species.

  (D) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 3,3 ′, 4,4′-tetra- ( t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-hexylperoxycarbonyl) ) Benzophenone, 3,3 ′, 4,4′-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (cumylperoxycarbonyl) benzophenone, 3,3 ′, Perester ester compounds such as 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di-t-butyldiperoxyisophthalate Thing is preferable.

  (F) Examples of hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2 , 2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5 ' Tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 Examples include ', 5,5'-tetraphenylbiimidazole.

  (G) Examples of the ketoxime ester compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane-3. -One, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  (H) Examples of the borate compound include compounds described in US Pat. Nos. 3,567,453, 4,343,891, European Patents 109,772, and 109,773. Can be mentioned.

  (I) Examples of azinium salt compounds include JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, JP-A-63-143537, and JP-B-46-42363. The compound group which has NO bond of each gazette description can be mentioned.

  (J) Examples of metallocene compounds include titanocenes described in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2-4705. Examples thereof include iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  (K) Examples of the active ester compound include the specifications of European Patent Nos. 0290750, 046083, 156153, 271851, and 0388343, U.S. Pat. Nos. 3,901,710, and 4,181,531. Nitrobenzol ester compounds described in JP-A-60-198538 and JP-A-53-133022, European Patents 0199672, 84515, 199672, 0441115, and 0101122. No. 4,618,564, U.S. Pat. No. 4,371,605, and U.S. Pat. No. 4,431,774, and JP-A 64-18143, JP-A-2-245756, and JP-A-4-365048. Iminosulfonate compound, Japanese Examined Patent Publication No. 62-6223, Japanese Examined Publication No. 63 No. 14340, and compounds, and the like described in the JP-A No. 59-174831.

  (L) Preferable examples of the compound having a carbon halogen bond include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, Examples thereof include compounds described in Japanese Utility Model Publication No. 53-133428, compounds described in German Patent No. 3337024, and the like.

  Further, compounds described in J. Org. Chem., 29, 1527 (1964) by FC Schaefer et al., Compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and the like can be mentioned. it can. A compound as described in German Patent No. 2641100, a compound described in German Patent No. 3333450, a compound group described in German Patent No. 3021590, or a compound group described in German Patent No. 3021599, etc. Can be mentioned.

<Cationic polymerization initiator>
When a cationically polymerizable compound is used in the present invention, it is preferable to use a cationic polymerization initiator. As the cationic polymerization initiator (photoacid generator) that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization is used (Organic Electronics Materials Research Group, “For Imaging”). “Organic materials”, Bunshin Publishing (1993), pages 187-192). Examples of the cationic polymerization initiator suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, phosphonium, etc. be able to. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, an iron allene complex can be mentioned.

  Examples of cationic polymerization initiators [(b-1) to (b-96)] suitably used in the present invention are listed below, but the present invention is not limited thereto.

In the ink composition that can be used in the present invention, the total use amount of the polymerization initiator is preferably 0.01 to 35% by weight, more preferably 0.5%, based on the total use amount of the polymerizable monomer. It is -20 weight%, More preferably, it is the range of 1.0-15 weight%. When it is 0.01% by weight or more, the ink composition can be sufficiently cured, and when it is 35% by weight or less, a cured film having a uniform degree of curing can be obtained.
Moreover, when using the sensitizer mentioned later for the ink composition which can be used for this invention, the total usage-amount of a polymerization initiator is a weight ratio of a polymerization initiator: sensitizer to a sensitizer, respectively. And preferably in the range of 200: 1 to 1: 200, more preferably 50: 1 to 1:50, and even more preferably 20: 1 to 1: 5.

(3) Colorant The ink composition that can be used in the present invention preferably contains a colorant.
The colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used. As the colorant that can be used in the present invention, it is preferable to select a compound that does not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction, from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation.

<Pigment>
Although it does not necessarily limit as a pigment which can be used for this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used.
Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36,
Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22,27,28,29,36,60 as a blue or cyan pigment ,
As a green pigment, Pigment Green 7, 26, 36, 50,
As yellow pigments, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137 , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193,
As the black pigment, Pigment Black 7, 28, 26,
As a white pigment, Pigment White 6, 18, 21
Etc. can be used according to the purpose.

<Oil-soluble dye>
Below, the oil-soluble dye which can be used by this invention is demonstrated.
The oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the weight of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.

  Among the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Examples include methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye species such as quinophthalone dyes, nitro / nitroso dyes, and acridines. And dyes and acridinone dyes.

  Of the oil-soluble dyes usable in the present invention, any magenta dye can be used. For example, aryl or hetaryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Among the oil-soluble dyes applicable to the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes;

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated. In this case, the counter cation may be an alkali metal or ammonium. Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.

Although not limited to the following, preferred specific examples include C.I. I. Solvent Black 3, 7, 27, 29 and 34; C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2,11,25,35,38,67 and 70; I. Solvent Green 3 and 7; I. Solvent orange 2; and the like.
Among these, particularly preferred are the Black Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue chemistry 2606e Bile 2OSe 2B eO (Manufactured by Co., Ltd.), Aizen Spillon Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, and Neo42 Cy FF4012.
In the present invention, the oil-soluble dye may be used alone or in combination of several kinds.

Moreover, when using an oil-soluble dye as a colorant, other water-soluble dyes, disperse dyes, pigments, and other colorants can be used in combination as long as the effects of the present invention are not impaired.
In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent. Preferable specific examples of the disperse dye include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1,177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse Violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 , 257, 266, 267, 287, 354, 358, 365 and 368; I. Disperse Green 6: 1 and 9;

  The colorant that can be used in the present invention is preferably appropriately dispersed in the ink after being added to the ink composition. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.

In preparing the ink composition, the colorant may be blended with each component by direct addition, but in order to improve dispersibility, it is added in advance to a dispersion medium such as a solvent or a polymerizable monomer used in the present invention, It can also be blended after being uniformly dispersed or dissolved.
In the present invention, in order to avoid the problem of deterioration of solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the colorant contains a polymerizable monomer. It is preferable to add and mix in advance in such a dispersion medium. In consideration of only dispersibility, it is preferable to select a monomer having the lowest viscosity as the polymerizable monomer used for adding the colorant.

  These colorants may be used by appropriately selecting one type or two or more types according to the purpose of use of the ink composition.

When using a colorant such as a pigment that remains solid in the ink composition, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0.01 to It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so as to be 0.45 μm, more preferably 0.015 to 0.4 μm. This particle size control is preferable because clogging of the head nozzle can be suppressed and the storage stability, transparency, and curing sensitivity of the ink composition can be maintained.
The content of the colorant in the ink composition is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by weight with respect to the weight of the entire ink composition.

(4) Dispersant It is preferable to add a dispersant when dispersing the colorant. The type of the dispersant is not particularly limited, but a polymer dispersant is preferably used.
Dispersor BYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-164D, DisperBYK-164D, , DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA5080, EFKA5504, EFKA5504, EFKA5504, 62, EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco); Solsperse) 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. (Avicia); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ( Manufactured by Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.) “Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polyvalent carboxylic acid)” manufactured by Enomoto Kasei Co., Ltd. # 7004 (polyether ester type) ”.
In addition, pigment derivatives such as a phthalocyanine derivative (trade name: EFKA-745 (manufactured by Efka)), Solsperse 5000, 12000, Solsperse 22000 (manufactured by Avicia) can also be used.
The content of the dispersant in the composition is appropriately selected depending on the purpose of use, but is preferably 0.01 to 5% by weight with respect to the total weight of the ink composition or the surface coating composition.

(5) Surfactant It is preferable to add a surfactant to the ink composition that can be used in the present invention in order to impart stable ejection properties for a long time.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts.
An organic silicon compound or an organic fluoro compound may be used in place of the surfactant. The organic silicon compound and the organic fluoro compound are preferably hydrophobic. Examples of the organosilicon compound include silicone surfactants and silicone oils. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.
The content of the surfactant in the composition is appropriately selected depending on the purpose of use, but is preferably 0.0001 to 1% by weight based on the total weight of the ink composition.

(6) Other components In addition, other components can be added to the ink composition as necessary. Examples of other components include sensitizers, co-sensitizers, ultraviolet absorbers, antioxidants, antifading agents, conductive salts, solvents, polymer compounds, basic compounds, and the like.

<Sensitizer>
A sensitizer may be added to the ink composition that can be used in the present invention in order to absorb specific actinic radiation and promote the decomposition of the polymerization initiator. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
As a sensitizer that can be used in the present invention, a sensitizing dye is preferably used.
Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
Polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squalium (for example, squalium) ), Coumarins (eg 7-diethylamino-4-methylcoumarin).

  More preferable examples of the sensitizing dye include compounds represented by the following formulas (IX) to (XIII).

In the formula (IX), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

In formula (X), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in Formula (IX).

In the formula (XI), A ₂ represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with adjacent A ₂ and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (XII), A ³ and A ⁴ each independently represent —S—, —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ each independently represents a hydrogen atom or a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

In the formula (XIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or ═NR ⁶⁷ . R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

  Preferable specific examples of the compounds represented by formulas (IX) to (XIII) include (E-1) to (E-20) shown below.

  The content of the sensitizer in the ink composition is appropriately selected depending on the purpose of use, but is preferably 0.05 to 4% by weight with respect to the total weight of the ink composition.

<Co-sensitizer>
The ink composition that can be used in the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye to actinic radiation or suppressing polymerization inhibition of the polymerizable compound by oxygen.
Examples of such co-sensitizers include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in Japanese Patent Application No. 6-191605 H, Ge-H compound, etc. are mentioned.
The content of the co-sensitizer in the ink composition is appropriately selected depending on the purpose of use, but is preferably 0.05 to 4% by weight with respect to the total weight of the ink composition.

<Ultraviolet absorber>
In the present invention, an ultraviolet absorber can be added to the ink composition from the viewpoint of improving the weather resistance of the resulting image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194843, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492 and 56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in US Pat. No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, and so-called fluorescent brighteners.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.5 to 15% by weight in terms of solid content.

<Antioxidant>
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European published patents, 223739, 309401, 309402, 310551, 310552, 359416, and 3435443. JP, 54-85535, 62-262417, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, Examples thereof include those described in Kaihei 3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

<Anti-fading agent>
In the ink composition that can be used in the present invention, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, Nos. VII to I, J. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
Although the addition amount is appropriately selected according to the purpose, it is preferably 0.1 to 8% by weight in terms of solid content.

<Conductive salts>
Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition that can be used in the present invention for the purpose of controlling ejection properties.

<Solvent>
It is also effective to add an extremely small amount of an organic solvent to the ink composition that can be used in the present invention in order to improve the adhesion to the recording medium.
As the solvent that can be used in the present invention, when a resin is used for the internal structure of the polymerizable particles, the difference between the solubility parameter value (SP value) of the resin and the solubility parameter value of the solvent used is 2 It is preferable that it is above, and it is more preferable that it is 3 or more.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether Examples include ether solvents.
In this case, it is effective to add the solvent within a range that does not cause the problem of solvent resistance and VOC, and the amount thereof is preferably 0.1 to 5% by weight, more preferably 0.1 to 5% by weight based on the whole ink composition. It is in the range of 3% by weight.

<Polymer compound>
Various polymer compounds can be added to the ink composition that can be used in the present invention in order to adjust film properties.
High molecular compounds include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellacs, vinyl resins, acrylic resins. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester” or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer compound.

In addition to this, if necessary, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to inhibit the adhesion to recording media such as polyolefin and PET, and the like, The tackifier which does not do can be contained.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifier resin having a polymerizable unsaturated bond.

(Physical properties of ink composition)
In the present invention, it is preferable to use an ink composition having a viscosity at 25 ° C. of 40 mPa · s or less in consideration of ejection properties. More preferably, it is 5-40 mPa * s, More preferably, it is 7-30 mPa * s. Moreover, it is preferable that the viscosity in discharge temperature (Preferably 25-80 degreeC, More preferably, 25-50 degreeC) is 3-15 mPa * s, More preferably, it is 3-13 mPa * s. It is preferable that the composition ratio of the ink composition that can be used in the present invention is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous support (recording medium) is used, penetration of the composition into the recording medium can be avoided, and uncured monomers can be reduced. Further, it is preferable because bleeding at the time of landing of the droplet can be suppressed, and as a result, the image quality is improved.

  The surface tension at 25 ° C. of the ink composition that can be used in the present invention is preferably 20 to 35 mN / m. More preferably, it is 23-33 mN / m. In the case of recording on various supports (recording medium) such as polyethylene terephthalate and polycarbonate, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 35 mN / m or less.

(Coating material and laminate film)
Since the coating material and the laminate film are heated to 80 to 200 ° C. during vacuum forming, it is preferable to use a coating material or laminate film having plasticity at that temperature. In addition, it is preferable to use a material having a stretchability equal to or higher than the stretchability of the support, and more specifically, it is more preferable to use a material having a stretchability of 100% or more at the temperature during molding.

(Coating material)
In the present invention, both a solvent-type coating material and an ultraviolet curable coating material can be used as a coating material used in the coating process. Among these, the coating material is preferably an ultraviolet curable coating material, that is, an ultraviolet curable composition. Each will be described below.

(1) Solvent type coating material As a solvent type coating material, what diluted and / or melt | dissolved resin in the solvent can be used.
<Resin>
The thermoplastic resin used for the solvent-type coating material is not particularly limited and can be appropriately selected depending on the purpose. For example, ethylene and vinyl acetate, acrylic acid, acrylic acid ester, maleic acid, etc. Polymers: various synthetic rubbers such as amorphous polyester, natural rubber, isoprene rubber, nitrile rubber, ethylene propylene rubber; alkyl acrylate polymer, polyethylene (high density, medium density, low density), polypropylene, biaxially oriented polypropylene, Polyolefin resins such as crystalline copolymerized polyolefins; Aliphatic polyesters such as polylactic acid, polybutyric acid, polybutylene succinate or copolymers thereof; atactic polymethyl methacrylate, atactic polystyrene, acetate, polyvinyl chloride, ABS Resin, and the like.
Among these, low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), biaxially oriented polypropylene [PP (OPP)], a polyethylene copolymer obtained by copolymerizing ethylene and other monomers, and Any of the polypropylene resins is preferred. As said other monomer, vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, etc. are preferable, for example.

  Examples of the polyethylene copolymer obtained by copolymerizing ethylene and other monomers include linear low density polyethylene (LLDPE), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), ethylene / meta. Examples include acrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / ethyl acrylate copolymer (EEA), ethylene / methyl methacrylate copolymer (EMMA), ionomer, and the like.

  The number average molecular weight of the resin is preferably 10,000 to 300,000, more preferably 40,000 to 200,000. The number average molecular weight is preferably 10,000 or more because the strength of the coating layer (protective layer) is good. Further, it is preferable that the number average molecular weight is 30,000 or less because good processability can be obtained.

Moreover, the following thermosetting resins can also be used suitably. Thermosetting resins are resins that cure by heat, and are available in one-part and two-part types, such as alkyd resins, amino resins, epoxy resins, and urethane resins.
Specifically, a urethane-based (or polyamine-based or polycarboxylic acid-based) used by mixing a polyol-based resin (or polyamine-based resin or polycarboxylic acid-based resin) and a polyisocyanate resin immediately before coating. The two-component curable thermosetting resin solution can be used.

The urethane-based two-part curable resin liquid is a polyol resin such as an alkyd resin having a hydroxyl group (—OH), an acrylic resin, a cellulose derivative resin, or a polyvinyl alcohol resin, or a polyamine having an amino group (—NH ₂ ), Resin having active hydrogen such as polycarboxylic acid having a carboxyl group (—COOH) and polyisocyanate resin having an isocyanate group (—NCO) are mixed before use (for example, immediately before) for coating to form one liquid. After coating, the two-component curable thermosetting resin solution is polymerized and cured at room temperature by a cross-linking polymerization reaction between a hydroxyl group (—OH) and an isocyanate group (—NCO) and dried. Is.

  In addition, as other two-component thermosetting resin solutions, alkyd resins having a hydroxyl group (—OH), resins such as acrylic resins, nitrocellulose, and polyvinyl alcohol are mixed with a polyvinyl chloride-polyvinyl acetate copolymer. And then use a clear resin mixed with a polyisocyanate resin (tolylene diisocyanate resin, methylene diisocyanate resin, hexamethylene diisocyanate resin, or other polyisocyanate) having an isocyanate group (—NCO). Is appropriate.

In the two-component curable thermosetting resin solution, an alkyd resin having a hydroxyl group (—OH), a polyol resin such as an acrylic resin, a cellulose derivative resin, a polyvinyl alcohol resin, or an amino group (—NH ₂ ) is used. In order to give flexibility, the blending ratio of the resin having active hydrogen such as polyamine and polycarboxylic acid having a carboxyl group (—COOH) and the resin mainly composed of polyisocyanate resin or polyisocyanate resin is, for example, polyol. It is preferable that the resin is blended in an amount of about 5 to 20 parts by weight (preferably 10 to 14 parts by weight) based on a polyisocyanate resin or a polyisocyanate resin with respect to 95 to 80 parts by weight of the resin. Alternatively, polyol resin: polyisocyanate resin or resin mainly composed of polyisocyanate resin = 3: 2, 1: 1, or 1: 2 is suitably blended, but in the present invention, it is flexible. If it is the range which can be obtained, it will not specifically limit.

As the resin for the solvent-type coating material, it is preferable to use a thermoplastic resin. Since it heats at 80-200 degreeC at the time of vacuum forming, since ductility can be ensured in heating temperature by making the glass transition temperature of resin below heating temperature, it is preferable.
The glass transition temperature referred to in the present invention is a general polymer as described in, for example, Eizo Omori, “Acrylic acid ester and its polymer (II)”, pages 110-115 issued by Shojido Co., Ltd. In the case of a copolymer, it is the calculated glass transition temperature described on page 120 of the same document. That is, the glass transition temperature of the copolymer is calculated by the following formula.

In the above formula, Tg is the glass transition temperature of the copolymer and is calculated in terms of absolute temperature. _{Tg 1, Tg 2, ···,} Tg n are the components 1, 2, respectively pure homopolymers 1 and 2 n, ..., the glass transition temperature of the n, the absolute temperature Calculated by conversion. W ₁ , W ₂ ,..., W _n are specific monomer weight fractions in the copolymer component.

  Moreover, in this invention, it is also preferable to use a urethane-type resin as resin of a solvent type coating material. A urethane-based resin is preferable because the stretchability is easily controlled.

<Solvent>
The solvent for dissolving and / or diluting the resin is not particularly limited, but amide solvents, esters, ketones, ethers, hydrocarbon solvents generally used as ink solvents can be used, and mixtures thereof are also included. Can be used. Typical solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N, N-dimethyl. Amide solvents such as imidazolidinone, ether solvents such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, γ-butyrolactone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, isopropanol, Alcohol solvents, aromatic solvents such as toluene, xylene, phenol, xylenol, chlorophenol, acetone, methyl ethyl ketone Diethyl ketone, cyclohexanone, isophorone, isopropanol, methyl acetate, ethyl acetate, ketone solvents such as butyl acetate, may be mentioned ester solvents, these may be used alone or as a mixed solvent of two or more components.

  The ratio of the resin to the solvent is preferably in the range of 10:90 to 90:10, and is preferably adjusted as appropriate so that the viscosity becomes appropriate for the following coating process. The coating material can be applied by an industrial method such as spraying, roll coating, spin coating, screen printing or flexographic printing. Furthermore, the coating film thickness after drying is usually in the range of 5 to 50 μm from the viewpoints of image protection and processability.

<Release agent>
Moreover, it is desirable to contain various mold release agents in order to give mold releasability.
The release agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silicone oil, polyethylene wax, carnauba wax, silicone particles, polyethylene wax particles, and the like. These can be added singly or in combination of two or more.
The content of the release agent in the protective layer is preferably 0.05 to 20% by weight, and more preferably 0.5 to 5% by weight. It is preferable that the content of the release agent is within the above range because good release properties can be obtained.

(2) Ultraviolet curable coating material In the present invention, the coating material is preferably an ultraviolet curable coating material (also referred to as an ultraviolet curable composition or a coating composition).
As the ultraviolet curable coating material, known radically polymerizable and cationically polymerizable coating materials can be used.
Examples of the ultraviolet curable coating material include an ultraviolet curable composition containing a polymerizable monomer and / or a polymerizable oligomer and a photopolymerization initiator.

<Polymerizable monomer>
[Radically polymerizable monomer]
As the ultraviolet curable coating material, a radically polymerizable monomer can be suitably used, and an ethylenically unsaturated double bond selected from the group consisting of acrylate group, methacrylate group, acrylamide group, methacrylamide group and N-vinyl group A monofunctional radically polymerizable monomer having only one group and having at least one group having a cyclic structure can be used more suitably.

  Examples of the radical polymerizable monomer that can be used in the present invention include an ethylenically unsaturated compound represented by the following formula (R-1).

上記式（Ｒ−１）において、Ｒ¹は水素原子、又は、メチル基を表す。
Ｘ¹は、式（Ｒ−１）に示すエチレン性不飽和二重結合に（−Ｃ（Ｏ）Ｏ−）又は（−Ｃ（Ｏ）ＮＨ−）が結合した第１の二価の連結基を示し、この第１の二価の連結基に単結合、エーテル結合（−Ｏ−）、エステル結合（−Ｃ（Ｏ）Ｏ−若しくは−ＯＣ（Ｏ）−）、アミド結合（−Ｃ（Ｏ）ＮＨ−若しくは−ＮＨＣ（Ｏ）−）、カルボニル結合（−Ｃ（Ｏ）−）、分岐を有していてもよい炭素数２０以下のアルキレン基、又は、これらを組み合わせた第２の二価の連結基が結合してもよく、第１の二価の連結基のみ又は第２の二価の連結基を有する場合はエーテル結合、エステル結合及び炭素数２０以下のアルキレン基を有するものが好ましい。
Ｒ²は少なくとも１つ以上の環状構造を有する基であり、単環芳香族基及び多環芳香族基を含む芳香族基、並びに、シクロアルカン骨格、アダマンタン骨格及びノルボルネン骨格を有する脂環式炭化水素基を表す。上記の芳香族基及び脂環炭化水素基の環状構造には、Ｏ、Ｎ、Ｓ等のヘテロ原子を含んでいてもよい。

In the above formula (R-1), R ¹ represents a hydrogen atom or a methyl group.
X ¹ is a first divalent linking group in which (—C (O) O—) or (—C (O) NH—) is bonded to the ethylenically unsaturated double bond represented by the formula (R-1). This first divalent linking group has a single bond, an ether bond (—O—), an ester bond (—C (O) O— or —OC (O) —), an amide bond (—C (O ) NH- or -NHC (O)-), a carbonyl bond (-C (O)-), an optionally substituted alkylene group having 20 or less carbon atoms, or a second divalent combination thereof In the case of having only the first divalent linking group or the second divalent linking group, those having an ether bond, an ester bond and an alkylene group having 20 or less carbon atoms are preferable. .
R ² is a group having at least one cyclic structure, an alicyclic carbon group having a monocyclic aromatic group and an aromatic group containing a polycyclic aromatic group, and a cycloalkane skeleton, an adamantane skeleton and a norbornene skeleton. Represents a hydrogen group. The cyclic structure of the above aromatic group and alicyclic hydrocarbon group may contain heteroatoms such as O, N, and S.

In the formula (R-1), the aromatic group represented by R ² is preferably a monocyclic aromatic phenyl group or phenylene group, or a polycyclic aromatic group having 2 to 4 rings. Specific examples include, but are not limited to, naphthyl group, naphthidiyl group, naphthytriyl group, anthryl group, anthridyl group, anthritriyl group, 1H-indenyl group, 1H-indendiyl group, 1H-indenetriyl group, 9H. -Fluorenyl group, 9H-fluorenediyl group, 9H-fluorenetriyl group, 1H-phenalenyl group, 1H-phenalenediyl group, 1H-phenalenediyl group, phenanthrenyl group, phenanthrenediyl group, phenanthrenetriyl group, triphenylenyl Group, triphenylenediyl group, triphenylenetriyl group, pyrenyl group, pyrenedi Group, pyrenetriyl group, naphthacenyl group, naphthacenediyl group, naphthacentriyl group, tetraphenyl group, tetraphendiyl group, tetraphentriyl group, biphenylenyl group, biphenylenediyl group, biphenylenetriyl group, as-indacenyl group, as- Indacenediyl group, as-indacentriyl group, s-indacenyl group, s-indacenediyl group, s-indacentriyl group, acenaphthylenyl group, acenaphthylenediyl group, acenaphthylenetriyl group, fluoranthenyl group, fluoranthendyl group Yl group, fluoranthene triyl group, acephenanthryleneyl group, acephenanthrylene diyl group, acephenanthrylene triyl group, aceanthryllenyl group, aceanthrylene diyl group, aceanthrylene triyl group, chryseni Group, chrysenediyl group, chrysantylyl group, preadenyl group, preadendiyl group, preadentriyl group and the like.

These aromatic groups may be aromatic heterocyclic groups containing heteroatoms such as O, N, and S. Specifically, Friyl group, Flangyl group, Furantriyl group, Thiophenyl group, Thiophenediyl group, Thiophenetriyl group, 1H-Pyrroylyl group, 1H-Pyrroldiyl group, 1H-Pyrroltriyl group, 2H-Pyrroylyl group, 2H -Pyrroldiyl group, 2H-pyrroletriyl group, 1H-pyrazolyl group, 1H-pyrazolediyl group, 1H-pyrazoletriyl group, 1H-imidazoliyl group, 1H-imidazolediyl group, 1H-imidazoletriyl group, isoxazolyl Yl group, isoxazolediyl group, isoxazoletriyl group, isothiazolylyl group, isothiazolediyl group, isothiazoletriyl group, 2H-pyraniyl group, 2H-pyrandiyl group, 2H-pyrantriyl group, 2H-thiopyraniyl group 2 -Thiopyrandiyl group, 2H-thiopyrantriyl group, pyridiyl group, pyridinediyl group, pyridinetriyl group, pyridazinyl group, pyridazinediyl group, pyridazinetriyl group, pyrimidinyl group, pyrimidinediyl group, pyrimidinetriyl group, pyrazinyl group , Pyrazinediyl group, pyrazinetriyl group, 1,2,3-triazolyl group, 1,2,3-triazolediyl group, 1,2,3-triazoletriyl group, 1,2,4-triazolylyl And monocyclic aromatic heterocyclic groups such as 1,2,4-triazolediyl group and 1,2,4-triazoletriyl group.
In addition, thiantreniyl group, thianthrene diyl group, thianthrene triyl group, isobenzofuraniyl group, isobenzofuranyl group, isobenzofurantriyl group, isochromeniyl group, isochromendiyl group, isochromementriyl group, 4H -Chromeniyl group, 4H-chromendiyl group, 4H-chromentolyl group, xanthenyl group, xanthenediyl group, xanthenetriyl group, phenoxathiniyl group, phenoxathiindiyl group, phenoxathiintriyl group, indolizinyl Group, indolizinediyl group, indolizinetriyl group, isoindoletriyl group, isoindolediyl group, isoindoletriyl group, indoliyl group, indolediyl group, indoletriyl group, indazoliyl group, indazolediyl group, Danazol triyl group, purinyl group, purine diyl group, print triyl group, 4H-quinolizinyl group, 4H-quinolizine diyl group, 4H-quinolidine triyl group, isoquinolyl group, isoquinolidiyl group, isoquinolitriyl group, quinolyl group, quinolidiyl Group, quinolitriyl group, phthalazinyl group, phthalazinine diyl group, phthalazine triyl group, naphthyridinyl group, naphthyridine diyl group, naphthyridine triyl group, quinoxalinini group, quinoxaline diyl group, quinoxaline triyl group, quinazoline diyl group, Quinozoline triyl group, cinnolinyl group, cinnoline diyl group, cinnoline triyl group, pteridinyl group, pteridine diyl group, pteridine triyl group, carbazolyl group, carbazole di Group, carbazoletriyl group, β-carbolinyl group, β-carbolinediyl group, β-carbolinetriyl group, phenanthridinyl group, phenanthridinediyl group, phenanthridinetriyl group, acridinyl group, acridinediyl group Group, acridinetriyl group, perimidinyl group, perimidinediyl group, perimidinetriyl group, phenanthrolinyl group, phenanthrolinediyl group, phenanthrolinetriyl group, phenazinyl group, phenazinediyl group, phenazinetriyl group, phenothiazinyl group Group, phenothiazinediyl group, phenothiazinetriyl group, phenoxazinyl group, phenoxazindiyl group, phenoxazinetriyl group, pyrrolidinyl group (pyrrolizinyl group), pyrrolidinediyl group (pyrrololizi) ndiyl group) and pyrrolidinetriyl group, and the like.
The aromatic group may have one or more halogen atoms, hydroxyl groups, amino groups, thiol groups, siloxane groups, and substituents having 30 or less carbon atoms. For example, you may form the cyclic structure containing hetero atoms, such as O, N, and S, by two or more substituents which an aromatic group has like phthalic anhydride and phthalimide anhydride.

R ² in formula (R-1) may be an alicyclic hydrocarbon group. Further, it may be a group having an alicyclic hydrocarbon group containing a hetero atom such as O, N, or S.
The alicyclic hydrocarbon group may be a group having a cycloalkane having 3 to 12 carbon atoms.
Specific examples of the alicyclic hydrocarbon group containing a heteroatom such as O, N, and S include a pyrrolidinyl group, a pyrrolidindiyl group, a pyrrolidintriyl group, a pyrazolidinyl group, a pyrazolidinyl group, and a pyrazolidinyl group. Zolidinediyl group, pyrazolidinetriyl group, imidazolidinyl group, imidazolidinediyl group, imidazolidinetriyl group, isoxazolidinyl group, isoxazolidinediyl group, isoxazolidinediyl group, isothiazolidinyl group Group, isothiazolidinediyl group, isothiazolidinetriyl group, piperidinyl group, piperidinediyl group, piperidinetriyl group, piperazinyl group, piperazinediyl group, piperazinetriyl group, morpholiniyl group, mol Olindiyl group, morpholine triyl group, thiomorpholiniyl group, thiomorpholine diyl group, thiomorpholine triyl group, diazolyl group, diazolediyl group, diazoletriyl group, triazolyl group, triazolediyl group, triazoletriyl Group, tetrazolyl group, tetrazolediyl group, tetrazoletriyl group and the like.
These alicyclic hydrocarbon groups and alicyclic hydrocarbon groups having a heteromonocycle are a halogen atom, a hydroxyl group, an amino group, a thiol group, a siloxane group, and a total carbon number that may further have a substituent. It is preferably a hydrocarbon group of 30 or less, a heterocyclic group containing a heteroatom such as O, N, or S, or an oxy group (═O) as a divalent substituent.

R ² in the formula (R-1) may be a group having an adamantane skeleton represented by the following formula (RI) or an alicyclic hydrocarbon group having a norbornene skeleton represented by (R-II).

R ³ and R ⁴ in the formula (RI) or the formula (R-II) each independently represent a substituent, and can be bonded at any position on each alicyclic hydrocarbon structure. Further, q R ³ and r R ⁴ may be the same or different.
R ³ present in q and R ⁴ present in r may each independently be a monovalent or polyvalent substituent, and as a monovalent substituent, a hydrogen atom, a hydroxyl group, substituted or unsubstituted An amino group, a thiol group, a siloxane group, a hydrocarbon group or heterocyclic group having a total carbon number of 30 or less which may further have a substituent, or an oxy group (= O) as a divalent substituent. It is preferable.
The substitution number q of R ³ represents an integer of 0 to 5, and the substitution number r of R ⁴ represents an integer of 0 to 5.
In addition, one carbon atom in the adamantane skeleton in the formula (RI) may be substituted with a carbonyl bond (—C (O) —) and / or an ester bond (—C (O) O—). One carbon atom in the norbornene skeleton in R-II)) may be substituted with an ether bond (—O—) and / or an ester bond (—C (O) O—).

  The norbornene skeleton represented by the formula (R-II) may have a cyclic hydrocarbon structure as represented by the formula (R-III). N in the formula (R-III) represents a cyclic hydrocarbon structure, and both ends thereof may be substituted at any position of the norbornene skeleton, and may be a monocyclic structure or a polycyclic structure. In addition to the hydrocarbon bond, the cyclic hydrocarbon structure may contain a carbonyl bond (—C (O) —) and / or an ester bond (—C (O) O—).

  The cyclic structure represented by the formula (R-III) is preferably a structure represented by the formula (R-IV), the formula (R-V), or the formula (R-VI).

In formula (R-IV), formula (R-V) and formula (R-VI), R ⁵ , R ⁶ and R ⁷ each independently represent a substituent, k represents an integer of 1 to 6, , T and u each independently represent an integer of 0 to 5, and s R ⁵ , t R ⁶ and u R ⁷ are the same or different. May be.
X ^{1 in} formula (R-1) binds at any position on each alicyclic hydrocarbon structure shown below in formula (R-IV), formula (R-V) or formula (R-VI). be able to.
R ⁵ , R ⁶ and R ⁷ in formula (R-IV), formula (R-V) or formula (R-VI) each independently represent a substituent, and formula (R-IV), formula (R-V) Or an arbitrary position on each alicyclic hydrocarbon structure below in formula (R-VI). The substituents in R ⁵ , R ⁶ and R ⁷ are the same as the substituents in R ³ and R ⁴ in formula (RI) to formula (R-III), and the preferred ranges are also the same.

  Further, as the radical polymerizable monomer that can be used for the ultraviolet curable coating material, the radical polymerizable monomer that can be used for the ink composition described above can also be suitably used, and the preferable range is also the same.

  It has only one ethylenically unsaturated double bond group selected from the group consisting of acrylate group, methacrylate group, acrylamide group, methacrylamide group and N-vinyl group as an ultraviolet curable coating material, and has a cyclic structure When a monofunctional radical polymerizable monomer having at least one group is used, the monofunctional radical polymerizable monomer is preferably contained in an amount of 60% by weight or more, more preferably 60 to 90% by weight, and more preferably 60 to 85%. More preferably, it is contained by weight%. Within the above numerical value range, it has high stretchability that can follow deformation, has excellent curability, has no scratches during molding, and has a highly scratched cured film that does not cause cracks or image loss Is possible.

  When N-vinyl lactams are used as the ultraviolet curable coating material, the N-vinyl lactams are preferably contained in an amount of 10% by weight or more of the entire ultraviolet curable coating material, more preferably 10 to 40% by weight, It is more preferable to contain 10 to 35% by weight. When the amount of N-vinyl lactam used is within the above range, the curability, the flexibility of the cured film, and the adhesion of the cured film to the support are excellent. N-vinyl lactams are compounds having a relatively high melting point. When the content of N-vinyl lactam is 40% by weight or less, favorable solubility is exhibited even at a low temperature of 0 ° C. or less, and the temperature range in which the ultraviolet curable coating material can be handled is widened.

[Cationically polymerizable monomer]
(A) Monofunctional oxetane compound and monofunctional oxirane compound In the present invention, a monofunctional cation polymerizable monomer having only one oxetane group is a monofunctional oxetane compound, and a monofunctional cation polymerizable monomer having only one oxirane group is a single monomer. Also called a functional oxirane compound.
For the cationically polymerizable coating composition used in the present invention, a highly polar monofunctional oxetane compound and / or a highly polar monofunctional oxirane compound (hereinafter, also simply referred to as “a highly polar cyclic ether compound”) can be used. .
A highly polar cyclic ether compound is a highly polar cyclic ether compound having a high polarity, and a highly polar cyclic ether compound having a highly polar group in the molecule. In the present invention, it is preferable that the coating composition contains a highly polar monofunctional cyclic ether compound because good dispersibility can be obtained.
A high polar cyclic ether compound can be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, only a highly polar monofunctional oxetane compound can be used, only a highly polar monofunctional oxirane compound can be used, and both compounds can also be used together.

  The highly polar monofunctional compound used in the present invention is preferably a compound having a molecule log P value (octanol / water partition coefficient) of less than 1.0. Compounds having a log P value of 1.0 or more.

In the present invention, the high polar group may be an ester bond, carbonate bond, hydroxyl group, substituent, amino group, urethane bond, amide bond, urea bond, bisphenoxy bond, nitrogen-containing cyclic compound group, A functional group containing a highly polar group such as an oxygen-containing cyclic compound group and an alkylene glycol structure is shown.
Examples of the alkylene glycol structure include alkylene glycol chains such as ethylene glycol chain, propylene glycol chain, and tetraethylene glycol chain, and polyalkylene glycol chains such as polyethylene glycol chain, polypropylene glycol chain, and polytetraethylene glycol chain.

  The highly polar monofunctional oxetane compound and the highly polar monofunctional oxirane compound have one cyclic ether structure. Specifically, from the viewpoint of reactivity and availability, the following structures can be preferably exemplified. In addition, a wavy line part is a coupling | bond part with another structure.

The cyclic ether structure in the highly polar cyclic ether compound may further have a substituent on the ether ring if it can be introduced.
Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a nitro group, and an amino group. In these substituents, if possible, the substituent may be further substituted with the substituent. Further, two substituents may be connected to form a ring structure, or may be connected to other structural parts other than the cyclic ether structure to form a ring structure.

  The highly polar cyclic ether compound that can be used in the present invention may have one partial structure containing the cyclic ether and one partial structure represented by the following formula (I) in its molecular structure. .

In formula (I), X ¹ is a single bond, an alkylene group having 5 or less carbon atoms which may have a branch, an ether bond, an ester bond, a carbonate bond, a urethane bond, an amide bond, a urea bond, a bisphenoxy bond, A divalent linking group containing a group having an alkylene glycol structure or a highly polar group in which two or more of these groups are combined is shown.
The structure represented by the formula (I) is preferably linked to any carbon atom in the cyclic ether (oxetane ring or oxirane ring) via a linking group such as an alkylene group.

In the partial structure represented by the formula (I), R ¹ is composed of an alkyl group, an aromatic group containing a monocyclic aromatic group and a polycyclic aromatic group, and a cycloalkane skeleton, an adamantane skeleton and a norbornane skeleton. An alicyclic hydrocarbon group having a structure selected from the group, or a group in which two or more of these groups are combined is represented. The cyclic structure of the above aromatic group and alicyclic hydrocarbon group may contain heteroatoms such as O, N, and S.

The alkyl group represented by R ¹ is preferably an alkyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 2 to 6 carbon atoms. Specifically, an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group and the like are preferable.

The group having a cycloalkane skeleton represented by R ¹ is preferably a cycloalkane having 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and more preferably 5 to 7 carbon atoms. Is more preferable. Specifically, a group in which one hydrogen atom is removed from a cycloheptyl group, a cyclohexyl group, a cyclopentyl group, a bicyclo ring group, an adamantyl group, a norbornyl group, or the like is preferable.

The aromatic group represented by R ¹ is preferably an aromatic group having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and 6 to 8 carbon atoms. Further preferred. Specifically, a group obtained by removing one hydrogen atom from a group such as a phenyl group, a biphenyl group, or a naphthyl group is preferred, and a group obtained by removing one hydrogen atom from a phenyl group is more preferred. R ¹ may be a group obtained by combining two or more of these groups, and more preferably a group obtained by removing one hydrogen atom from a benzyl group.

R ¹ may have a substituent.
Examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, a nitro group, and an amino group.
R ¹ is particularly preferably an alkylene group having no substituent, a cycloalkylene group having no substituent, or an arylene group having no substituent.

  The total number of oxygen atoms in the highly polar cyclic ether compound is preferably 3 or more, more preferably 3 to 7. When the total number of oxygen atoms is 3 or more, good dispersion stability can be provided.

  Specific examples that can be preferably used in the present invention [Exemplary compounds (1) to (60)] are listed below, but the present invention is not limited to these specific examples. In some of the following exemplary compounds, the hydrocarbon chain is described by a simplified structural formula in which the symbols of carbon (C) and hydrogen (H) are omitted. Moreover, it may describe with a simple structural formula also in the compound mentioned later.

In the present invention, a low-polar monofunctional oxetane compound and / or a low-polar monofunctional oxirane compound (hereinafter also simply referred to as “low-polar cyclic ether compound”) can be used for the cationic polymerizable coating composition. .
The low polar cyclic ether compound is an oxetane or oxirane compound having a low polarity, and more specifically, an oxetane or oxirane compound having no highly polar group in the molecule.
In the low-polar monofunctional cyclic ether compound that can be used in the present invention, the total number of oxygen atoms in the molecule is one or two, and the molecular structure other than the oxetane ring or oxirane ring is a hydrocarbon chain only, or A compound composed of a hydrocarbon chain and one ether bond is preferred.

  The low-polar cyclic ether compound has one cyclic ether structure, and the following structures can be preferably exemplified from the viewpoints of reactivity and availability.

The cyclic ether structure may have a substituent if it can be introduced.
Examples of the substituent include an alkyl group, a cycloalkyl group, and an aryl group, and specific examples include a methyl group, an ethyl group, and a phenyl group.
In these substituents, if possible, the substituent may be further substituted with the substituent. Two or more substituents may be linked to form a ring structure, or may be linked to other structural parts other than the cyclic ether structure to form a ring structure. For example, an adamantane skeleton or a norbornane skeleton The structure which has the said cyclic ether structure may be sufficient. However, a total of two or more oxetane structures and oxirane structures are not formed in one molecule.

  The low-polar cyclic ether compound that can be used in the present invention may have one partial structure represented by the following formula (II) in its molecular structure, in addition to the partial structure containing the cyclic ether. . The structure represented by the formula (II) is preferably linked to any carbon atom in the cyclic ether via a linking group such as an alkylene group. Moreover, the partial structure shown to Formula (II) may be contained in the low polar monofunctional oxetane compound or in the low polar monofunctional oxirane compound, and may be contained two or more.

In Formula (II), X ² represents a single bond, an ether bond, an alkylene group having 20 or less carbon atoms which may have a branch, or a divalent linking group in combination of these. When X ² contains an ether bond, the formula (II) contains only one ether bond.

In the formula (II), R ² represents an alicyclic hydrocarbon group containing a structure selected from the group consisting of an alkyl group, a cycloalkane skeleton, an adamantane skeleton, and a norbornane skeleton, or a monocyclic aromatic group and a polycyclic aromatic group. Represents an aromatic group containing a structure selected from the group consisting of group groups, and in the present invention, an alkyl group having 1 or more carbon atoms which may have a substituent, and a carbon number which may have a substituent. It is preferable that it is an aromatic group which may have 4 or more alicyclic hydrocarbon groups, or a substituent.

Examples of the alkyl group represented by R ² include an alkyl group having 1 or more carbon atoms which may have a substituent. Moreover, it is preferable that it is 30 or less carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group , 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-stearyl group and the like.

Examples of the alicyclic hydrocarbon group represented by R ² include an alicyclic hydrocarbon group having 4 or more carbon atoms which may have a substituent. Moreover, it is preferable that it is 30 or less carbon atoms. Specific examples include a cycloheptyl group, a cyclohexyl group, a cyclopentyl group, a bicyclo ring group, an adamantyl group, and a norbornyl group.

The aromatic group represented by R ² is preferably an aromatic group having 6 to 18 carbon atoms which may have a substituent, more preferably 6 to 12 carbon atoms, More preferably, it has 6 to 8 atoms. Specific examples include a phenyl group, a biphenyl group, a naphthyl group, and a p-nonylphenyl group.

  Hereinafter, preferred specific examples [Exemplary compounds (1) to (63)] of low-polar monofunctional oxetane compounds or low-polar monofunctional oxirane compounds that can be used in the present invention will be given, but the present invention is not limited to these specific examples. It is not limited.

  In the present invention, the use ratio of the high-polar cyclic ether compound and the low-polar cyclic ether compound is arbitrary, and can be selected as necessary in consideration of the dispersibility of the coating composition. In the present invention, a low polar cyclic ether compound can be preferably used.

(B) Polyfunctional oxetane compound and polyfunctional oxirane compound The coating composition that can be used in the present invention is a polyfunctional oxetane compound or a polyfunctional oxirane compound (hereinafter, these are also simply referred to as “polyfunctional cyclic ether compound”). Can be contained.

A polyfunctional oxetane compound is a compound having two or more oxetane rings in the same molecule. In this invention, a polyfunctional oxetane compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.
The polyfunctional oxetane compound has two or more oxetane rings in the molecule, preferably 2 to 6 and more preferably 2 to 4. When the number of oxetane rings in the molecule is within the above range, good curability and flexibility of the cured film can be obtained.

  Examples of the compound having two oxetane rings in the molecule include compounds represented by the following formulas (1) and (2).

R ^a1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. When two R ^a1 are present in the molecule, they may be the same or different.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.

R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or an alkylene group containing a carbonyl group, a carboxyl group Represents an alkylene group containing, an alkylene group containing a carbamoyl group, or a group shown below. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

When R ^a3 is the above polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, Represents a lower alkyl carboxyl group, a carboxyl group, or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
R ^a6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2,000. R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure. In the following formula, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  Preferred examples of the compound represented by the formula (1) include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: manufactured by Toagosei Co., Ltd.). A preferred example of the compound represented by the formula (2) is bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd.).

  Examples of the compound having 3 to 4 oxetane rings in the molecule include compounds represented by the following formula (3).

In the formula (3), R ^a1 has the same ^{meaning as} in the formula (1). In addition, as R ^a9 which is a polyvalent linking group, for example, a branched polyalkylene group having 1 to 12 carbon atoms such as groups represented by the following A to C, a branched poly ( An alkyleneoxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Further, as another embodiment of the oxetane compound that can be suitably used in the present invention, a compound represented by the following formula (4) having an oxetane ring in the side chain can be exemplified.

In the formula (4), R ^a1 and R ^a8 have the same ^{meaning as} in the above formula. R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

  The compound having such an oxetane ring is described in detail in JP-A No. 2003-341217, paragraph numbers 0021 to 0084, and the compound described here can be suitably used in the present invention. In addition, oxetane compounds described in JP-A-2004-91556 can also be used in the present invention. This is described in detail in paragraphs 0022 to 0058.

A polyfunctional oxirane compound is a compound having two or more oxirane rings in the same molecule. In this invention, a polyfunctional oxirane compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.
In the present invention, the polyfunctional oxirane compound has two or more oxirane rings in the molecule, preferably 2 to 6, and more preferably 2 to 4. It is preferable for the number of oxirane rings in the molecule to be in the above range because good curability and good flexibility of the cured film can be obtained.

  Examples of the polyfunctional oxirane compound include a polyfunctional aromatic oxirane compound, a polyfunctional alicyclic oxirane compound, a polyfunctional aliphatic oxirane compound, and the aromatic oxirane compound includes a polyfunctional oxirane compound having at least one aromatic nucleus. Examples include di- or polyglycidyl ethers produced by the reaction of a monohydric phenol or its alkylene oxide adduct and epichlorohydrin, such as di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, hydrogenated bisphenol A or its alkylene. Examples thereof include di- or polyglycidyl ethers of oxide adducts and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  The polyfunctional alicyclic oxirane compound is obtained by epoxidizing a compound having at least two cycloalkane rings such as cyclohexene ring or cyclopentene ring with an appropriate oxidizing agent such as hydrogen peroxide or peracid. Preferred are cyclohexene oxide or cyclopentene oxide-containing compounds. Moreover, the cyclohexene dioxide and cyclopentene dioxide containing compound obtained by epoxidizing the compound which has cycloalkadiene rings, such as a cyclohexadiene ring or a cyclopentadiene ring, can also be illustrated.

  Examples of the polyfunctional aliphatic oxirane compound include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol and diglycidyl of propylene glycol. Polyglycidyl ethers of polyhydric alcohols such as diglycol or diglycidyl ether of alkylene glycol such as ether or 1,6-hexanediol, diglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or alkylene oxide thereof Polyalkylene glycols typified by diglycidyl ethers of adducts, polypropylene glycol or diglycidyl ethers of adducts thereof with alkylene oxide. Diglycidyl ethers of Lumpur thereof. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The polyfunctional oxirane compound which can be used for this invention is illustrated in detail.
For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated Bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4 Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene Diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1 , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol di Glycidyl ether, polypropylene glycol diglycidyl ether, 1,13-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, etc. Can be mentioned.

  Among these polyfunctional oxirane compounds, polyfunctional aromatic oxirane compounds and polyfunctional alicyclic oxirane compounds are preferable from the viewpoint of excellent curing speed, and polyfunctional alicyclic oxirane compounds are particularly preferable.

  In the present invention, the coating composition preferably contains an oxetane compound and an oxirane compound, and more preferably contains a polyfunctional oxirane compound and a polyfunctional oxetane compound. Coexistence of an oxetane compound and an oxirane compound in the coating composition provides a cured film having excellent curability, high peelability to the mold during the molding process, and high scratch resistance that is unlikely to cause scratches. A coating composition can be provided. More preferably, the polyfunctional oxetane compound and the polyfunctional oxirane compound coexist.

  In the present invention, the ratio of the total amount of the polyfunctional oxetane compound and the polyfunctional oxirane compound to the entire coating composition is preferably less than 25% by weight. A coating composition excellent in stretchability of the cured film can be provided at a ratio of less than 25% by weight.

(C) Monofunctional vinyl ether compound A monofunctional vinyl ether compound can be used for the coating composition used for this invention. Examples of monofunctional vinyl ether compounds that can be used in the present invention include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, Examples thereof include monovinyl ether compounds such as isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, dodecyl vinyl ether, and diethylene glycol monovinyl ether.

Hereinafter, monofunctional vinyl ether compounds will be exemplified in detail.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples thereof include ethyl vinyl ether, phenyl ethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, and among them, cyclohexane dimethanol monovinyl ether can be preferably used.

(D) Polyfunctional vinyl ether compound A polyfunctional vinyl ether compound can be used for the ink composition used for this invention. As the polyfunctional vinyl ether compound that can be used in the present invention, examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and butanediol divinyl ether. Hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane trivinyl ether, and the like.

Below, monofunctional vinyl ether and polyfunctional vinyl ether are illustrated in detail.
Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexabi Ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added penta Examples include polyfunctional vinyl ethers such as erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether, and among them, triethylene glycol divinyl ether can be preferably used.

  As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

  In the present invention, the content of the monofunctional monomer is preferably 30% by weight or more based on the total amount of the cationic polymerizable coating composition, more preferably 40 to 80% by weight, and particularly preferably 50 to 70% by weight. It is. A coating composition having excellent curability and excellent stretchability of a cured film at the time of molding can be provided within the above numerical range.

  Among monofunctional monomers, it is more preferable to contain at least one monofunctional oxirane compound or monofunctional oxetane compound, and a monofunctional oxetane compound is particularly preferable. Among the monofunctional monomers, monomers having a cyclic structure containing a hetero atom such as an aromatic group, an alicyclic hydrocarbon group, N, S, and O are more preferable.

The cationically polymerizable coating composition that can be used in the present invention contains a polyfunctional oxetane compound and / or a polyfunctional oxirane compound, and the total amount of the polyfunctional oxetane compound and / or the polyfunctional oxirane compound is the ink composition. It is preferably less than 25% by weight of the whole product. Furthermore, it is more preferable that the coating composition contains a polyfunctional oxetane compound, and the total amount of the oxetane compound is less than 15% by weight of the entire coating composition.
It is preferable for it to be in the above numerical value range since a coating composition having excellent curability and stretchability of the cured film can be provided.

  Among these, the ultraviolet curable coating material is preferably a colorless ink obtained by removing the colorant from the ink composition. That is, it is preferable to use a monomer having a cyclic structure.

<Oligomer and polymer>
In the present invention, oligomers and polymers can be used together. Here, an oligomer means a compound having a molecular weight (weight average molecular weight for those having a molecular weight distribution) of 2,000 or more, and a polymer has a molecular weight (weight average molecular weight for those having a molecular weight distribution) of 10. Means more than 1,000 compounds. The oligomer or polymer may or may not have a radical polymerizable group. It is preferable that a radically polymerizable group in one molecule of the oligomer or polymer is 4 or less (in terms of a compound having a molecular weight distribution, an average of 4 or less in the whole molecule included), because a coating film having excellent flexibility can be obtained. . It can also be suitably used in the sense that the viscosity is adjusted to an optimum level for coating.

[Radically polymerizable oligomer and / or polymer]
An ultraviolet curable oligomer having a (meth) acryloyl group can be added to the radical polymerization type coating material. As said compound, it is an oligomer which has an acryloyl group or a methacryloyl group in the terminal or side chain of a molecule | numerator. Examples of the oligomer include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate (bisphenol A type, novolak type, alicyclic system, etc.), polybutadiene (meth) acrylate, and the like, and mixtures thereof. Can be mentioned.
In consideration of stretchability adapted to the molding process, preferably bisphenol A type epoxy (meth) acrylate and / or urethane (meth) acrylate can be exemplified.

[Cationically polymerizable oligomer and / or polymer]
An oligomer and / or a polymer having a cationic polymerizable group can be added to the cationic polymerization type coating material. Examples of the oligomer and polymer include an epoxy resin, a styrene compound, a vinyl ether compound, a spiro ortho ester, a bicyclo ortho ester, and a spiro ortho carbonate.
Epoxy resins are roughly classified into aromatic epoxy resins and aliphatic epoxy resins. Aliphatic epoxy resins can be further classified into alicyclic epoxy resins and alicyclic epoxy resins.
The aromatic epoxy resin is a polyglycidyl ether of a polyhydric phenol having at least one aromatic ring or an alkylene oxide adduct thereof. Specific examples thereof include glycidyl ethers synthesized by reaction of bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S or alkylene oxide (for example, ethylene oxide) adducts of bisphenol compounds with epichlorohydrin, novolak-type epoxy resins, and the like. Is mentioned.
An alicyclic epoxy resin is an epoxy compound having an alicyclic structure. Specific examples thereof include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis- (2,3-epoxycyclopentyl) ether, and the like.
The alicyclic epoxy resin is a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. Specific examples thereof include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Polyglycidyl ethers of polyether polyols synthesized by adding one or more alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin.

[Other resins]
Moreover, you may contain resin used as the said solvent-type coating material. By containing said resin, since the coating-film intensity | strength after ultraviolet curing can be improved and stretchability can be improved, it is preferable. As the resin compound, a resin compound that can be dissolved in an ultraviolet curable coating material can be preferably used. The resin compound is preferably contained in an amount of 1 to 20% by weight.

[Preferred embodiment]
In the present invention, it is preferable to use a combination of a urethane oligomer excellent in stretchability and a monofunctional monomer as the ultraviolet curable coating material. It is preferable to combine a urethane-based oligomer and a monofunctional monomer because the stretchability of the cured film can be secured. In order to control the glass transition point, it is preferable to add an acrylic resin.

<Polymerization initiator>
[Radical polymerization initiator]
When the ultraviolet curable coating material uses a radical polymerizable monomer as the polymerizable monomer, it preferably contains a radical polymerization initiator.
As the polymerization initiator that can be used for the ultraviolet curable coating material, a known radical polymerization initiator can be used, and the radical polymerization initiator in the ink composition described above can be exemplified, and the preferred range is also the same. The radical polymerization initiator that can be used for the ultraviolet curable coating material may be used alone or in combination of two or more.

  In the ultraviolet curable coating material, the total use amount of the radical polymerization initiator is preferably 0.01 to 35% by weight, more preferably 0.5 to 20% by weight, based on the total use amount of the radical polymerizable monomer. More preferably, it is in the range of 1.0 to 15% by weight.

(Cationic polymerization initiator)
As the polymerization initiator that can be used for the ultraviolet curable coating material, a known cationic polymerization initiator can be used, and the cationic polymerization initiator in the ink composition described above can be exemplified, and the preferable range is also the same. The cationic polymerization initiator that can be used for the ultraviolet curable coating material may be used alone or in combination of two or more.

  In the ultraviolet curable coating material, the cationic polymerization initiator is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the cationic polymerizable compound. it can.

The ultraviolet curable coating material can be applied by a known industrial method such as spraying, roll coating, spin coating, screen printing, flexographic printing or the like.
When using an ultraviolet curable coating material, ultraviolet irradiation is performed after coating. Although the irradiation method is not particularly limited, a low-pressure or high-pressure mercury lamp, metal halide lamp, xenon lamp, electrodeless discharge lamp, carbon arc lamp, or the like can be used as the ultraviolet light source.
The irradiation peak wavelength of ultraviolet rays is preferably 200 to 600 nm, and more preferably 300 to 450 nm.
Further, the amount of ultraviolet rays irradiated is not particularly limited, but is preferably be cured in 10~4,000mW / cm ^2, and more preferably cured at 20 to 2,500 mW / cm ^2.

  As the ultraviolet irradiation condition and irradiation method, a known method can be used. It can be performed by scanning a light source, or can be cured by a light source without driving.

(Laminated film)
In this invention, there is no restriction | limiting in particular as a laminated film used for a lamination process, According to the objective, it can select suitably, The laminated film described in Unexamined-Japanese-Patent No. 2005-234021 can be illustrated.
Specifically, (1) a resin film having an adhesive layer on the surface on the image layer side, (2) a transfer type resin film, and the like are preferably used.
In addition, since the peeling at the time of a process can be suppressed as a laminate film by making stretchability the same as a support body, it is preferable to use the same raw material as a support body.

(1) Resin film having an adhesive layer on the surface on the image layer side As the film of the aspect (1), the surface of the resin film can be used if the laminated film itself is melted by heat and pressure treatment and can be bonded. Although it can be used by superimposing the surface of the image layer without distinction between the back surface and the back surface, for example, a film having an adhesive layer on the surface on the image layer side of the laminated film is preferable.
The surface of the adhesive layer and the surface of the image layer in the laminated film are superposed and subjected to heat and pressure treatment (laminate).
By providing the adhesive layer as described above, the laminating temperature can be lowered or the speed can be increased. It is also possible to increase the adhesive force between the image layer and the protective layer.

The laminated film is not particularly limited and can be appropriately selected according to the purpose. For example, a stretched thermoplastic resin is preferable, and particularly, a polyolefin resin, a polyester resin, an acrylic resin, and the like are used. Can be mentioned. By making the stretchability the same as that of the support, it is possible to suppress peeling during processing, and therefore it is preferable to use the same material as the support.
In addition, the said base film can contain various stabilizers, various fillers, and other mixable components in arbitrary ratios as components other than resin.

(2) Transfer Type Resin Film The transfer type resin film of the aspect (2) preferably has at least a transfer protective layer formed between the resin film and the adhesive layer. There is no restriction | limiting in particular as a layer structure of the said transfer type resin film, Although it can select suitably according to the objective, For example, resin film / transfer protective layer / adhesion layer, resin film / peeling layer / transfer protective layer / Adhesive layer, etc. are preferred. In this case, it is preferable that the layer on the opposite side to the image adhesion surface in the laminate film is a base film.

  The thickness of the transfer type resin film is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 5 to 40 μm. When the thickness is 50 μm or less, the processability is excellent, the heat capacity is appropriate, the temperature is likely to rise, the flexibility of the resin film is good, and defects such as air voids and steps are not preferable. .

  The transfer-type resin film is formed by superposing the surface on the image layer side and the surface of the adhesive layer in the laminate film, and then subjecting the transfer protective layer to the surface on the image layer side by performing heat and pressure treatment. Is transcribed through. Next, the transfer protective layer appears on the outermost surface by peeling the resin film from the interface between the resin film and the transfer protective layer, or the resin film and the release layer from the interface between the release layer and the transfer protective layer. . By providing the transfer protective layer as described above, the transfer protective layer can contain various compounding agents (for example, UV inhibitors, colorants, matting agents, etc.), and functions according to the purpose can be easily performed. Can be granted.

The transfer protective layer is not particularly limited and may be appropriately selected according to the purpose.For example, a polyolefin resin such as polyethylene or polypropylene, a polyester resin such as polyethylene terephthalate resin, an acrylic resin, nylon, or polycarbonate may be used. It is preferable to contain.
There is no restriction | limiting in particular in the thickness of the said transfer protective layer, According to the objective, it can select suitably, Usually, 40 micrometers or less are preferable.

The adhesive layer preferably contains a hot melt polymer.
The hot-melt polymer is not particularly limited as long as it can be melted by heating and can be adhered to the surface on the image layer side, and can be appropriately selected according to the purpose. For example, polyester resin; ethylene copolymer (For example, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / acrylic acid copolymers such as methylmaleic anhydride terpolymers, ethylene / vinyl acetate copolymers, ethylene / Propylene copolymer, ethylene / butene copolymer, etc.); propylene / butene copolymer, methyl methacrylate copolymer, SBR copolymer, NBR copolymer, and the like.

  In addition, the said contact bonding layer can contain another additive as needed further. Further, in order to improve handling properties and transportability in the machine, a protective layer can be provided on the adhesive layer, and the protective layer can be removed before lamination and laminated.

(Support)
The support that can be used in the present invention is not particularly limited, and a known recording medium suitable for molding can be used.
As the support, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, olefin-based thermoplastic elastomer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, Polyester resin such as terephthalic acid-ethylene glycol-1,4-cyclohexanedimethanol copolymer, polyester-based thermal plastic elastomer, polyamide resin such as nylon 6, nylon 9, nylon 66, polyvinyl fluoride, polyvinylidene fluoride, poly Fluorine resin such as vinylidene trifluoride, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, acrylic resin, polyvinyl chloride, polystyrene, polycarbonate resin Etc. can be exemplified.
Examples of the acrylic resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) ) Resins such as acrylate copolymers and methyl (meth) acrylate-styrene copolymers (however, (meth) acrylate means acrylate or methacrylate) can be used alone or in a mixture of two or more.
Of these, polyethylene terephthalate, polycarbonate, polyester, cured vinyl chloride, polystyrene, and the like can be preferably exemplified because they are easy to mold and have excellent resistance to finished molded prints. Polyethylene terephthalate, polycarbonate and polyester are more preferable, and polyethylene terephthalate and polycarbonate are most preferable in that the various resistances of the molded article produced by the above method are excellent.
In addition, a paper support such as art paper, coated paper and plain paper, and a metal support such as an aluminum plate and a stainless plate can also be suitably used for the method for producing a molded printed material of the present invention.

The shape of the support that can be used in the present invention is not particularly limited as long as it can be molded, but is preferably a sheet. When a sheet-like support is used, the thickness is preferably 50 μm to 1,000 μm, more preferably 70 μm to 800 μm, more preferably 100 to 100 μm, although it depends on the material of the support and the molding process conditions. The thing of 500 micrometers is still more preferable.
Further, the support may be manufactured by combining a plurality of materials. For example, when a sheet-like support is used, either a single layer or a laminate in which two or more layers of different kinds of resins are laminated is used. It may be.

  Additives can be appropriately added to the support as necessary. Appropriate amounts of various additives can be added as long as they do not hinder the thermal behavior such as surface gloss and melting point. For example, UV stabilizers such as benzotriazole and benzophenone, light stabilizers such as hindered amine radical scavengers, lubricants such as silicone resins and waxes, colorants, plasticizers, heat stabilizers, antibacterial agents, antifungal agents , Antistatic agents and the like.

(Method for producing molded printed matter)
The method for producing a molded printed material according to the present invention includes (A) a step of forming an image on a support by an inkjet method using an actinic radiation curable ink composition, and (B) irradiating the image with actinic radiation. Curing the image, (C) obtaining a printed material having an image and a protective layer on a support by coating and / or laminating the cured image, and (D) vacuum forming the printed material. It includes a step of processing or pressure forming.
Further, the molded printed matter of the present invention is obtained by the above-described method for producing a molded printed matter of the present invention.
Hereinafter, each process will be described.

(A) Step of forming an image on a support by an ink jet method using an actinic radiation curable ink composition The ink jet method forms fine droplets of ink or the like with good reproducibility and blows them to a desired place. This is a method of landing droplets.
In order to form an image using the inkjet method, an inkjet recording apparatus described below can be suitably used.
In the present invention, an image is optical information including characters, figures, tables, and photographs, and may be black-and-white, mono-color, or full-color.

<Inkjet recording apparatus>
There is no restriction | limiting in particular as an inkjet recording device which can be used for this invention, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, as long as it is a known inkjet recording apparatus including a commercially available product, the ink composition and the surface coating composition on the support in the steps (A) and (B) of the method for producing a molded printed matter of the present invention are used. It is possible to discharge objects.
Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, a source tank, a supply pipe, a supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head each containing an ink composition and a surface coating composition. The piezo-type inkjet head has a multi-size dot of 1 to 100 pl, preferably 8 to 30 pl, preferably 320 × 320 to 4000 × 4000 dpi, more preferably 400 × 400 to 1600 × 1600 dpi, and even more preferably 720 × 720 dpi. It can drive so that it can discharge with the resolution of. In the present invention, dpi represents the number of dots per 2.54 cm.

  As described above, the radiation curable ink composition, such as the ink composition and the surface coating composition, desirably has a constant temperature for the discharged composition. Insulation and heating can be performed. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided near the supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

For discharging the composition using the ink jet recording apparatus, the ink composition and the surface coating composition are preferably heated to 25 to 80 ° C., more preferably 25 to 50 ° C. It is preferably performed after the viscosity of the composition is lowered to preferably 3 to 15 mPa · s, more preferably 3 to 13 mPa · s. In particular, it is preferable to use an ink composition having a viscosity at 25 ° C. of 50 mPa · s or less as the ink composition and the surface coating composition because the ink can be discharged satisfactorily. By using this method, high ejection stability can be realized.
Since the radiation curable ink composition and the radiation curable surface coating composition generally have a higher viscosity than the water-based ink usually used in ink jet recording inks, the viscosity variation due to temperature variation during ejection is large. Viscosity fluctuation of the composition has a great influence on the change of the droplet size and the change of the droplet discharge speed, thereby causing the image quality deterioration. Therefore, it is necessary to keep the temperature of the composition at the time of ejection as constant as possible. Therefore, in the present invention, the control range of the temperature of the composition is preferably set to ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and further preferably set to ± 1 ° C.

(B) Step of curing the image by irradiating the image with active radiation In the step (B), the image is cured by irradiating the image with active radiation.
The ink composition ejected on the support is cured by irradiation with actinic radiation. This is because the polymerization initiator contained in the ink composition is decomposed by irradiation with actinic radiation to generate radicals, acids, bases and other initiation species, and the function of the initiation species is a radical polymerizable compound and / or cationic polymerization. This is because a natural polymerization reaction occurs and is accelerated. At this time, if a sensitizer is present together with the polymerization initiator in the ink composition, the sensitizer in the system absorbs actinic radiation to be in an excited state, and promotes decomposition of the polymerization initiator by contacting with the polymerization initiator. And a more sensitive curing reaction can be achieved.

Here, α rays, γ rays, electron beams, X rays, ultraviolet rays, visible light, infrared rays, or the like can be used as the active radiation used. In the present invention, it is preferable to use an electron beam and ultraviolet rays, and it is more preferable to use ultraviolet rays.
Although the peak wavelength of actinic radiation is based also on the absorption characteristic of a sensitizer, it is preferable that it is 200-600 nm, for example, it is more preferable that it is 300-450 nm, and it is still more preferable that it is 350-420 nm.

In addition, the polymerization initiation system of the ink composition in the present invention has sufficient sensitivity even with low output actinic radiation. Therefore, it is appropriate that the exposure surface illuminance is preferably 10 to 4,000 mW / cm ² , more preferably 20 to 2,500 mW / cm ² .

Mercury lamps and gas / solid lasers are mainly used as actinic radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording inks. Yes. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jets.
Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 350 to 420 nm.
Incidentally, it is preferable that maximum illumination intensity of the LED on a recording medium is 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, particularly preferably 50 to 800 mW / cm ² .

The ink composition that can be used in the present invention is suitably irradiated with such actinic radiation for 0.01 to 120 seconds, more preferably for 0.1 to 90 seconds.
Actinic radiation irradiation conditions and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the composition discharge device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation with actinic radiation takes a certain period of time (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, still more preferably 0.01 to 0.15 seconds) after the droplets have landed. Will be done. In this way, by controlling the time from droplet landing to irradiation to an extremely short time, it is possible to prevent the droplets that have landed on the support from bleeding before curing. Further, since the ink can be exposed to a porous support before the ink penetrates to a deep portion where the light source does not reach, it is preferable because residual unreacted monomer can be suppressed.
Further, the curing may be completed by another light source that is not driven. WO99 / 54415 pamphlet discloses a method using an optical fiber and a method of applying a collimated light source to a mirror surface provided on the side surface of the head unit and irradiating the recording unit with UV light as an irradiation method. Curing methods can also be applied to the present invention.

By adopting the method as described above, the dot diameter of the landed ink can be kept constant even on various supports having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. By superimposing the inks in the order of low lightness, it becomes easier for the irradiation line to reach the lower ink, and good curing sensitivity, reduction of residual monomers, and improvement in adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.
In this manner, the ink composition that can be used in the present invention can form an image on the surface of the support by being cured with high sensitivity by irradiation with actinic radiation.

(Color image)
The ink composition that can be used in the method for producing a molded printed matter of the present invention may be used alone or in combination of two or more to form a color image.
The ink composition used in the method for producing a molded printed material according to the present invention preferably includes a plurality of color ink compositions. In order to form a full-color image, a magenta ink composition and a cyan ink composition are used. And a yellow ink composition, more preferably a magenta ink composition, a cyan ink composition, a yellow ink composition, a black ink composition, and a white ink composition. .

(C) A step of obtaining a printed matter having an image and a protective layer on a support by coating and / or laminating on the cured image. The protective layer may be formed on a part of the image. It may be formed on the entire image. Moreover, the protective layer may be provided in the whole printed matter, and may be provided in one part. For example, a protective layer may be provided specifically for an image portion that contacts the mold during molding or a portion with a high degree of deformation. Two or more protective layers may be formed.
The protective layer can be coated with a dot area of 10% or more with respect to the image area, and in that case, it is more preferably 50% or more. The halftone dot area represents the sum of dot areas in a state where dots are uniformly dispersed in an area provided with a protective layer.
The coating process and the laminating process are as described above.

(D) Step of vacuum forming or pressure forming the printed material As a device for vacuum forming or pressure forming the printed material, a known device can be used, and even if the device is integrated with the ink jet recording device. Another device may be used.
In the present invention, vacuum forming or pressure forming is performed, and vacuum / pressure forming is included in these.

<Vacuum forming, pressure forming, vacuum pressure forming>
Vacuum forming is a method in which a support on which an image has been formed is preheated to a temperature at which it can be thermally deformed in advance, and this is sucked into a mold by decompression and stretched while being compressed and cooled to the mold. In this method, the support on which the image is formed is preheated to a temperature at which it can be thermally deformed in advance, pressed from the opposite side of the mold, and then pressed and cooled on the mold. Vacuum / pressure forming is a method in which the pressure reduction and pressurization are performed simultaneously.

As the material of the support in the printed material for vacuum forming, pressure forming, or vacuum / pressure forming (hereinafter also referred to as vacuum forming), high degree of stretchability is required in the heated state, so polycarbonate, polyester, and cured vinyl chloride. Polystyrene and the like can be preferably exemplified, and polycarbonate and polyester are more preferable, and polycarbonate is most preferable in that the molding process is easy and various resistances of a molded product manufactured by vacuum molding or the like are excellent.
In addition, the thickness of the support in a printed matter that is subjected to vacuum / pressure forming (hereinafter also referred to as vacuum forming) is preferably 0.01 to 0.8 mm, more preferably 0.03 to 0.6 mm.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following description, “parts” means “parts by weight” unless otherwise specified.

The materials of the radically polymerizable composition used in the present invention are as shown below.
(Pigment)
・ IRGALITE BLUE GLVO (Cyan pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335 D (Magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (Black pigment, manufactured by Ciba Specialty Chemicals)
・ Taipek CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)

(monomer)
・ Fancrill 512A (FA-512A, manufactured by Hitachi Chemical Co., Ltd.)

・ NK ester AMP-10G (phenoxyethyl acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ N-Vinylcaprolactam (NVC, manufactured by ISP)
SR489D (Tridecyl acrylate, manufactured by Sartomer)
Actilane 421 (propoxylated neopentyl glycol diacrylate, manufactured by Akcros)

(Dispersant)
-Solsperse 32000 (dispersant, manufactured by Noveon)
-Solsperse 36000 (dispersant, manufactured by Noveon)
(Polymerization inhibitor, polymerization initiator, surfactant, sensitizer)
・ First cure ST-1 (polymerization inhibitor, manufactured by Chem First)
・ Lucirin TPO (photopolymerization initiator, manufactured by BASF)
・ Benzophenone (photopolymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Irgacure 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals)
・ Byk 307 (surfactant, manufactured by BYK Chemie)
-Firstcure ITX (sensitizer, manufactured by Chem First)

The materials of the cationically polymerizable composition used in the present invention are as shown below.
(Pigment)
・ IRGALITE BLUE GLVO (Cyan pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335 D (Magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (Black pigment, manufactured by Ciba Specialty Chemicals)
・ Taipek CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)
(Dispersant)
・ Solsperse 32000 (Noveon)
-Solsperse 36000 (Noveon)
(monomer)
・ OXT-221 (manufactured by Toagosei Co., Ltd.)

・ Cyacure UVR6105 (manufactured by Dow Chemical)

・ OXT-211 (manufactured by Toagosei Co., Ltd.)

・ OXT-212 (manufactured by Toagosei Co., Ltd.)

(Polymerization initiator)
・ CPI-100P (sulfonium salt, manufactured by San Apro)

・ Dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
(Surfactant)
Byk 307 (manufactured by BYK Chemie)

  Hereinafter, a mill base for a radical polymerizable ink composition was prepared.

(Preparation of cyan mill base A)
300 parts by weight of IRGALITE BLUE GLVO, 600 parts by weight of Actilane 421, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of magenta mill base B)
300 parts by weight of CINQUASIA MAGENTA RT-335 D, 600 parts by weight of Actilane 421, and 100 parts by weight of Solsperse 32000 were mixed with stirring to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of yellow mill base C)
300 parts by weight of NOVOPERM YELLOW H2G, 600 parts by weight of Actilane 421, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of black mill base D)
300 parts by weight of SPECIAL BLACK 250, 600 parts by weight of Actilane 421, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 7 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of white mill base E)
A pigment ink was obtained by stirring and mixing 500 parts by weight of Typek CR60-2, 450 parts by weight of NK ester AMP-10G, and 50 parts by weight of Solsperse 36000. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

  Hereinafter, a mill base for a cationic polymerizable ink composition was prepared.

(Preparation of cyan mill base F)
300 parts by weight of IRGALITE BLUE GLVO, 600 parts by weight of OXT-212, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of magenta mill base G)
300 parts by weight of CINQUASIA MAGENTA RT-335 D, 600 parts by weight of OXT-212, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of yellow mill base H)
300 parts by weight of NOVOPERM YELLOW H2G, 600 parts by weight of OXT-212, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 8 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Preparation of black mill base I)
300 parts by weight of SPECIAL BLACK 250, 600 parts by weight of OXT-212, and 100 parts by weight of Solsperse 32000 were stirred and mixed to obtain a pigment ink. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed using a zirconia bead having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 5 hours and 30 minutes.

(Preparation of white mill base J)
A pigment ink was obtained by stirring and mixing 500 parts by weight of Typek CR60-2, 450 parts by weight of OXT-212 and 50 parts by weight of Solsperse 36000. The pigment mill base was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

(Viscosity measurement method)
In this example, the viscosity was measured using a B-type viscometer: Brookfield LVDV-I (manufactured by Brookfield) at 25 ° C. and a rotor rotation speed of 10 to 30 rpm.

(Preparation of ink composition)
[Preparation of radical ink 1]
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 18 mPa · s.
(Cyan ink composition)
-Cyan mill base A 6.0 parts-N-vinyl caprolactam 25.0 parts-Fancryl 512A 35.4 parts-NK ester AMP-10G 20.0 parts-First cure ST-1 0.05 part-Lucirin TPO 8. 5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ Byk 307 0.05 parts

[Preparation of radical ink 2]
The following components were stirred with a high-speed water-cooled stirrer to obtain a magenta UV inkjet ink. The viscosity was 18 mPa · s.
(Magenta ink composition)
-Magenta mill base A 12.0 parts-N-vinylcaprolactam 25.0 parts-Funcryl 512A 29.4 parts-NK ester AMP-10G 20.0 parts-First cure ST-1 0.05 parts-Lucirin TPO 8. 5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ Byk 307 0.05 parts

[Preparation of radical ink 3]
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink. The viscosity was 18 mPa · s.
(Yellow color ink composition)
・ Yellow mill base A 12.0 parts ・ N-vinylcaprolactam 25.0 parts ・ Fancryl 512A 29.4 parts ・ NK ester AMP-10G 20.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8. 5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ Byk 307 0.05 parts

[Preparation of radical ink 4]
The following components were stirred with a high-speed water-cooled stirrer to obtain a black UV inkjet ink. The viscosity was 22 mPa · s.
(Black ink composition)
・ Black mill base A 6.0 parts ・ N-vinylcaprolactam 30.0 parts ・ Fancrile 512A 50.4 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8.5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ Byk 307 0.05 parts

[Preparation of radical ink 5]
The following components were stirred with a high-speed water-cooled stirrer to obtain a white UV inkjet ink. The viscosity was 24 mPa · s.
(White ink composition)
White mill base E 31.0 parts N-vinylcaprolactam 18.0 parts Funkrill 512A 26.4 parts NK ester AMP-10G 10.0 parts First cure ST-1 0.05 parts Lucirin TPO 8. 5 parts ・ Benzophenone 3.0 parts ・ Irgacure 184 2.0 parts ・ Byk 307 0.05 parts ・ Firstcure ITX 1.0 part

[Preparation of radical ink 6]
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 14 mPa · s.
(Cyan ink composition)
-Cyan mill base A 6.0 parts-N-vinylcaprolactam 25.0 parts-SR489D 55.4 parts-First cure ST-1 0.05 parts-Lucirin TPO 8.5 parts-Benzophenone 3.0 parts-Irgacure 184 2 .0 part ・ Byk 307 0.05 part

[Preparation of radical ink 7]
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 23 mPa · s.
(Cyan ink composition)
・ Cyan Mill Base A 6.0 parts ・ Fancrill 512A 65.4 parts ・ NK ester AMP-10G 15.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8.5 parts ・ Benzophenone 3.0 parts ・Irgacure 184 2.0 parts ・ Byk 307 0.05 parts

[Preparation of cationic ink 1]
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 30 mPa · s.
(Cyan ink composition)
Cyan Mill Base F 6.0 parts OXT-221 11.0 parts UVR6105 9.9 parts OXT-211 60.0 parts CPI-100P 12.0 parts Dibutoxyanthracene 1.0 parts Byk 307 0 .1 part

[Preparation of cationic ink 2]
The following components were stirred with a high-speed water-cooled stirrer to obtain a magenta UV inkjet ink. The viscosity was 33 mPa · s.
(Magenta ink composition)
-Magenta mill base G 12.0 parts-OXT-221 11.0 parts-Cycure UVR6105 11.9 parts-OXT-211 52.0 parts-CPI-100P 12.0 parts-Dibutoxyanthracene 1.0 part-Byk 307 0.1 part

[Preparation of cationic ink 3]
The following components were stirred with a high-speed water-cooled stirrer to obtain a yellow UV inkjet ink. The viscosity was 34 mPa · s.
(Yellow color ink composition)
・ Yellow Mill Base H 12.0 parts ・ OXT-221 11.0 parts ・ Cyracure UVR6105 11.9 parts ・ OXT-211 52.0 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ Byk 307 0.1 part

[Preparation of cationic ink 4]
The following components were stirred with a high-speed water-cooled stirrer to obtain a black UV inkjet ink. The viscosity was 31 mPa · s.
(Black ink composition)
・ Black Mill Base I 6.0 parts ・ OXT-221 11.0 parts ・ Cyracure UVR6105 9.9 parts ・ OXT-211 51.9 parts ・ CPI-100P 12.0 parts ・ Dibutoxyanthracene 1.0 part ・ Byk 307 0.1 part

[Preparation of cationic ink 5]
The following components were stirred with a high-speed water-cooled stirrer to obtain a white UV inkjet ink. The viscosity was 36 mPa · s.
(White ink composition)
・ White Mill Base J 30.0 parts ・ OXT-221 10.0 parts ・ Cyracure UVR6105 8.9 parts ・ OXT-211 40.0 parts ・ CPI-100P 10.0 parts ・ Dibutoxyanthracene 1.0 part ・ Byk 307 0.1 part

[Preparation of cationic ink 6]
The following components were stirred with a high-speed water-cooled stirrer to obtain a cyan UV inkjet ink. The viscosity was 30 mPa · s.
(Cyan ink composition)
-Cyan Mill Base F 6.0 parts-OXT-221 11.0 parts-UVR6105 9.9 parts-OXT-212 60.0 parts-CPI-100P 12.0 parts-Dibutoxyanthracene 1.0 part-Byk 307 0 .1 part

<Inkjet image recording method>
Next, recording on a recording medium was performed using an ink jet recording experimental apparatus having five piezo ink jet nozzles. The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV light was condensed to an exposure surface illuminance of 2,100 mW / cm ² , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium. . Further, the integrated light amount irradiated to the image was set to 6,000 mJ / cm ² . A HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) was used as the ultraviolet lamp. In the present invention, dpi represents the number of dots per 2.54 cm.
By the above method, the A4 size support (Teflex FT-3 (film thickness 50 μm, PET, manufactured by Teijin DuPont)) having an average film pressure of the cured film of 12 μm was applied to the radical inks cyan, magenta, yellow, and black. A color image printed matter 1 was prepared using ink (radical inks 1 to 4), and an average film pressure of a cured film was 12 μm by the above method using radical white ink (radical ink 5) on the drawing portion of the color image 1. A solid image was printed on the entire surface of the image portion to produce a color image 2.
Also, a color image printed matter 3 was prepared using the cationic inks cyan, magenta, yellow, and black ink (cationic inks 1 to 4). A solid image was printed on the drawing portion of the color image 3 using a cation white ink (cation ink 5) to produce a color image 4.
Further, in the color image 1, the color image 5 was prepared in the same manner except that the radical ink 6 was used instead of the radical ink 1, and the color image 6 was similarly prepared except that 7 was used instead of the radical ink 1. Produced. Further, in the color image 3, a color image 7 was produced in the same manner except that the cationic ink 6 was used instead of the cationic ink 1.

Example 1
<Preparation of coating material / Preparation of solvent-type coating agent (1)>
Urethane resin (Estane 5715, manufactured by Noveon) 27.5 parts Methyl cellosolve acetate 65.0 parts Cyclohexanone 7.5 parts Antifoaming agent (EFKA 2020, manufactured by Ciba Specialty Chemicals) 1.0 part The mixture was agitated with a mechanical stirrer and screen printed on the printed matter with a 250 mesh screen.
After screen printing, the sample was dried at 80 ° C. for 5 minutes to obtain the following sample for vacuum forming.

(Example 2)
<Preparation of coating material / Preparation of UV curable coating agent (1)>
Urethane acrylate 27.0 parts (Daiichi Kogyo Seiyaku New Frontier R-1213)
N-vinylcaprolactam 22.0 parts Fancryl 512A 25.95 parts NK ester AMP-10G 10.0 parts First cure ST-1 0.05 part Irgacure 184 10.0 parts Acrylic resin 5.00 parts (2-methacrylic acid 2- (Ethylhexyl / n-butyl methacrylate / butyl acrylate / 2-hydroxyethyl methacrylate copolymer, weight average molecular weight 50,000)
The above coating material was stirred with a high-speed water-cooled stirrer and screen-printed on the printed matter with a 350 mesh screen.
After screen printing, a UV irradiation device (manufactured by Nippon Batteries: metal halide lamp 120 W / cm) was used to adjust and irradiate the integrated light amount to 120 mJ / cm ² to obtain the following samples for vacuum forming.

(Example 3)
A sample for vacuum forming was prepared in the same manner as in Example 2 using the ultraviolet curable coating agent (2) obtained by removing the acrylic resin from the ultraviolet curable coating agent (1) of Example 2.

(Example 4)
<Preparation of laminate film (1)>
On a polypropylene film having a thickness of 25 μm (manufactured by Toray Industries, Inc., heat distortion temperature (load = 4.6 kgf / cm ² ) = 120 ° C.), a coating solution for a transfer protective layer having the following composition was solidified using a bar coater. Was applied at a rate of 5 g / m ² and dried to form a transfer protective layer. On the transfer protective layer, a coating solution for an adhesive layer having the following composition was applied using a bar coater so that the solid content was 5 g / m ² , dried to provide an adhesive layer, and a laminate film (1) Was made.

-Composition of coating liquid for transfer protective layer-
100 parts of core-shell styrene acrylic latex (manufactured by Hokko Chemical Co., Ltd .; HE-1335, solid content 45% by mass, soap-free type, Tg (core / shell) = − 41 ° C./107° C., mass ratio (core / shell) = 1 / 1)
Carnauba wax 15 parts (manufactured by Chukyo Yushi Co .; Cellosol 524, solid content 30% by mass, soap-free type, softening temperature = + 83 ° C.)
Silica particles 1 part Ion exchange water 34 parts

-Composition of coating solution for adhesive layer-
100 parts of polyester latex (manufactured by Unitika; KZA-7049, solid content 30% by mass, Tg = 48 ° C.)
Polyethylene oxide (molecular weight about 250,000) 0.4 part Anionic surfactant (AOT) 0.01 part (AOT: sodium bis (2-ethylhexyl) sulfosuccinate)
50 parts of ion-exchanged water The ink jet image surface and the adhesive layer surface of the laminate film (1) are overlaid and heated and pressurized under conditions of a roller set temperature of 130 ° C., a roller pressure of 15 kgf / cm ² , and a linear velocity of 8 mm / sec. (Lamination) was performed. After laminating, the laminate film (1) was peeled off from the substrate film, and the transfer protective layer was exposed on the surface.

(Example 5)
<Preparation of laminate film (2)>
On a polypropylene film having a thickness of 25 μm (manufactured by Toray Industries, Inc., heat distortion temperature (load = 4.6 kgf / cm ² ) = 120 ° C.), a coating solution for an adhesive layer having the following composition was solidified using a bar coater. Was applied so as to be 5 g / m ² and dried to provide an adhesive layer to prepare a laminate film (2).

-Composition of coating solution for adhesive layer-
100 parts of polyester latex (manufactured by Unitika; KZA-7049, solid content 30% by mass, Tg = 48 ° C.)
Polyethylene oxide (molecular weight about 250,000) 0.4 part Anionic surfactant (AOT) 0.01 part (AOT: sodium bis (2-ethylhexyl) sulfosuccinate)
50 parts of ion exchange water

The surface of the ink jet image and the surface of the adhesive layer of the laminate film (2) are superposed and heat-pressed (laminated) under the conditions of a roller set temperature of 130 ° C., a roller pressure of 15 kgf / cm ² , and a linear speed of 8 mm / sec. The following samples for vacuum forming were used.

(Comparative Example 1)
A sample for vacuum forming was prepared without performing the above coating material and lamination.

(Processing process evaluation method)
<Vacuum forming process test>
Vacuum forming was performed using a vacuum forming apparatus forming 300X (manufactured by Seiko Sangyo Co., Ltd.). The heater temperature was set so that the temperature of the support was 90 ° C., and the wooden mold shown in FIG. 1 was installed in the center of the vacuum table to perform vacuum forming. The formed printed matter was visually observed for cracks and white spots. In addition, the presence or absence of scratches on the surface was visually observed after vacuum forming. The results are shown in Table 1.

The evaluation criteria are as follows.
<Vacuum forming test>
○: No cracks or white spots are seen. △: A part of the image is cracked. ×: Part of the image is cracked.

<Injured>
○: No scratches on the surface △: Some scratches are seen on the surface ×: Many scratches are seen on the surface, and there are parts that appear white with reduced transparency

It is the schematic of the type | mold used for the vacuum forming process test.

Claims (9)

(A) a step of forming an image on a support by an inkjet method using an actinic radiation curable ink composition;
(B) irradiating the image with actinic radiation to cure the image;
(C) A step of obtaining a printed material having an image and a protective layer on a support by coating and / or laminating on the cured image, and (D) a step of vacuum forming or pressure forming the printed material. seen including,
The actinic radiation curable ink composition has only one ethylenically unsaturated double bond group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, and an N-vinyl group; In addition, the composition contains a monofunctional radically polymerizable monomer having a cyclic structure in an amount of 60% by weight or more,
The method for producing a printed material obtained by molding , wherein the support is selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyester . The method for producing a molded printed matter according to claim 1, wherein the actinic radiation curable ink composition contains N-vinyl lactams.   The method for producing a molded printed matter according to claim 1 or 2, wherein the actinic radiation curable ink composition contains a polyfunctional radical polymerizable monomer in an amount of 15% by weight or less based on the total amount of the ink composition. The method for producing a molded printed material according to any one of claims 1 to 3, wherein the coating material used for the coating process is an ultraviolet curable composition.   The ultraviolet curable composition has only one ethylenically unsaturated double bond group selected from the group consisting of acrylate group, methacrylate group, acrylamide group, methacrylamide group and N-vinyl group, and is cyclic The molded processed printed material according to claim 4, comprising 60% by weight or more of a monofunctional radically polymerizable monomer having at least one group having a structure and 10% by weight or more of N-vinyl lactams. Production method.   The method for producing a molded printed material according to any one of claims 2 to 5, wherein the N-vinyllactam contained in the active radiation curable ink composition is a compound represented by the following formula (I): .

(In formula (I), n represents an integer of 1 to 5)   The method for producing a molded printed matter according to any one of claims 2 to 6, wherein the N-vinyl lactam contained in the actinic radiation curable ink composition is N-vinyl caprolactam.   The method for producing a molded printed matter according to any one of claims 1 to 7, wherein the actinic radiation curable ink composition has a viscosity at 25 ° C of 5 to 40 mPa · s. A printed matter obtained by the method for producing a shaped printed matter according to any one of claims 1 to 8 .

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