JP6967624B2 - Printed matter and its manufacturing method - Google Patents

Description

The present invention relates to a printed matter and a method for producing the same, and more particularly to a printed matter having excellent adhesion, stain resistance and scratch resistance, and a method for producing the same.

In recent years, decoration has been performed using active energy ray-curable ink. Since the active energy ray-curable ink is cured by irradiation with active energy rays, ejection defects such as nozzle clogging due to volatilization and drying of water and organic solvent occur as in the case of conventional organic solvent-based inks and water-based inks. It is difficult and quick-drying, so it has the advantage of improving productivity. However, the active energy ray-curable ink has a large volume shrinkage at the time of curing, and since it dries quickly, a large internal stress remains in the film. There was a problem that it was difficult to obtain adhesion to materials. The following studies have been made so far on this issue.

Japanese Patent Application Laid-Open No. 2010-229281 (Patent Document 1) describes a thermosetting type having excellent adhesion to an ultraviolet curable ink layer by blending a certain amount of a polyfunctional acrylate monomer in a base paint made of a polyester resin and an amino resin. It describes providing a coating composition. Japanese Patent Application Laid-Open No. 2008-142701 (Patent Document 2) is a pre-coated metal having excellent adhesion to a UV ink coating film by blending a certain amount of an epoxidized polybutadiene resin with a hydroxyl group-containing paint composed of a hydroxyl group-containing resin and a cross-linking agent. It is described as providing the coating film forming method for this. Although the inventions described in Patent Document 1 and Patent Document 2 can secure a certain degree of adhesion to the active energy ray-curable ink, there is room for improvement.

The applicant has also been considering it so far. For example, Japanese Patent Application Laid-Open No. 2018-79400 (Patent Document 3) describes that the adhesiveness of a print layer can be improved by using an undercoat paint containing an acrylic resin having a specific crosslinkable functional group. Japanese Unexamined Patent Publication No. 2019-77090 (Patent Document 4) describes that the adhesiveness of a printed layer can be improved by a coating layer containing a polyester resin having an alicyclic hydrocarbon structure as a main component. Japanese Unexamined Patent Publication No. 2019-162732 (Patent Document 5) describes that the adhesiveness of the printed layer can be improved by a coating layer containing a reaction product of a polyester resin, a melamine resin and a polyfunctional acrylate.

Japanese Unexamined Patent Publication No. 2010-22281 Japanese Unexamined Patent Publication No. 2008-142701 Japanese Unexamined Patent Publication No. 2018-79400 Japanese Unexamined Patent Publication No. 2019-77090 Japanese Unexamined Patent Publication No. 2019-162732

Further, in the case of the ink finish specification, the undercoat coating film is exposed in the portion where printing is not performed. At this time, there is a problem that the film, which is soft and easily adheres to ink, has insufficient hardness and is easily damaged, and pollutants and the like are easily adhered to the film.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a printed matter having excellent adhesion, stain resistance and scratch resistance, and a method for producing the printed matter.

As a result of diligent studies to achieve the above object, the present inventor uses an imino group type amino resin as the coating film forming resin of the undercoat paint to obtain a printing layer formed from an active energy ray-curable ink. We have found that it is possible to form an undercoat coating film layer having excellent stain resistance and scratch resistance while sufficiently ensuring adhesiveness, and have completed the present invention.

That is, the printed matter of the present invention has an undercoat coating film layer containing an imino group type amino resin as a coating film forming resin and a printing layer formed of an active energy ray-curable ink on the surface of a heat-resistant substrate. It is characterized by.

In a preferred example of the printed matter of the present invention, the amount of the imino group type amino resin in the total resin contained in the undercoat coating film layer is in the range of 3 to 20% by mass.

In another preferred example of the printed matter of the present invention, the undercoat coating layer further contains one or more coating film-forming resins selected from the group consisting of self-crosslinking acrylic resins, acrylic polyol resins, and polyester polyol resins. ..

（式中、Ｒ^１は、水素原子又は炭素数が１〜８のアルキル基であり、Ｒ^２は、水素原子又はメチル基である）で表される（メタ）アクリルモノマーの重合体、及び／又は上記式（１）で表される（メタ）アクリルモノマーと該（メタ）アクリルモノマー以外のエチレン性不飽和基を有するモノマー及び／又はオリゴマーとを共重合させたアクリル樹脂共重合体である。 In another preferred example of the printed matter of the present invention, the self-crosslinking acrylic resin has the following formula (1).

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom or a methyl group), and / or a polymer of a (meth) acrylic monomer represented by the above. Alternatively, it is an acrylic resin copolymer obtained by copolymerizing a (meth) acrylic monomer represented by the above formula (1) with a monomer having an ethylenically unsaturated group other than the (meth) acrylic monomer and / or an oligomer.

（式（３）中、Ｒ^３は水素原子又はメチル基であり、ｎは１〜３の整数である。）で表されるラジカル重合性モノマー及び／又は下記式（４）：

（式（４）中、Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素数２〜４のアルキレン基であり、Ｒ^４が炭素数２のアルキレン基である場合はｎが２〜５の整数であり、Ｒ^４が炭素数３のアルキレン基である場合はｎが１〜３の整数であり、Ｒ^４が炭素数４のアルキレン基である場合はｎが１〜２の整数である。）で表されるラジカル重合性モノマーを含有する。 In another preferred example of the printed matter of the present invention, the active energy ray-curable ink is based on the following formula (3):

(In the formula (3), R ³ is a hydrogen atom or a methyl group, and n is an integer of 1 to 3), and the radically polymerizable monomer and / or the following formula (4) :.

(In the formula (4), R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group having 2 to ^{4 carbon atoms, and when R 4} is an alkylene group having 2 carbon atoms, n is 2 to 5 When R ⁴ is an alkylene group having 3 carbon atoms, n is an integer of 1 to 3, and when R ⁴ is an alkylene group having 4 carbon atoms, n is an integer of 1 to 2. It contains a radically polymerizable monomer represented by.).

In another preferred example of the printed matter of the present invention, the gel fraction of the undercoat coating film layer is 75% or more.

Further, in the method for producing a printed matter of the present invention, the surface of a heat-resistant substrate is coated with an undercoat paint containing an imino-based type amino resin as a coating film-forming resin, and then baked and cured to form an undercoat coating film layer. Then, the surface of the formed undercoat coating film layer is printed with an active energy ray-curable ink and then cured by irradiation with active energy rays to form a printed layer.

In a preferred example of the method for producing a printed matter of the present invention, the printed matter having the cured printed matter is heated in the range of 70 to 300 ° C.

According to the present invention, it is possible to provide a printed matter having excellent adhesion, stain resistance and scratch resistance, and a method for producing the printed matter.

Hereinafter, the printed matter of the present invention and the method for producing the printed matter will be described in detail. The printed matter of the present invention is a printed matter having an undercoat coating layer and a printing layer on a substrate, and the method for producing a printed matter of the present invention is a step of forming an undercoat coating layer on the surface of a substrate (coating film forming step). And a step of forming a print layer on the undercoat coating layer (print layer forming step).

In the printed matter of the present invention, the base material is a heat-resistant base material, and specifically, the heat-resistant material that can withstand the baking hardening treatment of the undercoat coating film layer and the heat treatment of the printed matter applied as necessary. It is preferable that the base material has. Examples of such materials include metals such as iron, stainless steel, aluminum, copper, titanium and their alloys, cement, concrete, gypsum, calcium silicate, calcium carbonate, marble, artificial marble, glass, ceramics and the like. It may be a combination of two or more of these materials. Further, the surface of the base material may be subjected to pretreatment such as degreasing treatment, chemical conversion treatment, polishing, etc., sealer, primer coating and the like. The surface of the base material may be smooth, may have irregularities, or may be a three-dimensional object. In the present invention, by using a base material having such a material and properties, it can be suitably used especially for furniture, building materials, and metal accessories.

In the printed matter of the present invention, the undercoat coating film layer is formed on a part or the whole of the surface of the base material. Here, the undercoat coating film layer can be formed by coating the surface of the base material with the undercoat paint and then baking and curing it in the coating film forming step.

The undercoat coating film layer contains a coating film forming resin. Here, the coating film forming resin is a component that remains as a resin constituting the coating film, and is, for example, an acrylic resin, a silicone resin, an acrylic silicone resin, a styrene acrylic copolymer resin, a polyester resin, a fluorine resin, a rosin resin, and a petroleum resin. , Kumaron resin, phenol resin, urethane resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid resin, vinyl resin, amino resin (melamine resin, urea resin) , Guanamin resin and the like are also included), ketimine resin and the like. In the undercoat coating film layer, the amount of the coating film forming resin is, for example, in the range of 50 to 100% by mass, preferably 70% by mass to 100% by mass. The amount of the coating film-forming resin in the undercoat paint is, for example, 5 to 90% by mass, preferably 10 to 80% by mass. The coating film forming resin may be used alone or in combination of two or more.

The undercoat coating layer contains an imino group type amino resin, preferably an imino group type melamine resin, as the coating film forming resin. By using an imino group type amino resin, an undercoat coating film layer having excellent stain resistance and scratch resistance is formed while sufficiently ensuring adhesion to the print layer formed from the active energy ray-curable ink. be able to.

Amino resin is generally a general term for polymers having a large amount of nitrogen in the form of an amino group. Usually, it is a thermosetting resin in which a starting material having an amino group (-NH ₂ ) is reacted with an aldehyde (mainly formaldehyde) to generate a highly reactive monomer, which is addition-polymerized. Amino resins include melamine resin (starting material is melamine), urea resin (starting material is urea), guanamine resin (starting material is guanamines such as benzoguanamine), and thiourea resin and aniline resin depending on the starting material. Etc. are also known. In general, nylon-type polyamide resins, polyurethane resins, acrylamide resins and the like are not classified as amino resins.

Further, the monomer produced by the reaction of the starting material having an amino group (-NH ₂ ) with an aldehyde has an amino group having one hydrogen as an amino group (that is, an imino group -NHR; where R is here. (Methylol group or alkyl etherified methylol group), amino group having no hydrogen and having a group selected from a methylol group and an alkyl etherified methylol group (-NR ₂ ; where each R is a methylol group or an alkyl). It has an etherified methylol group) and the like, and amino resins are classified according to the type of amino group of this monomer. In general, those having a large amount of imino group-NHR (where R is a methylol group or an alkyl etherified methylol group) are referred to as an imino group type amino resin, and amino group-NR ₂ (where each R is methylol). Those having a large amount of a group or an alkyl etherified methylol group are referred to as a methylol-type amino resin, and those having a large amount of an amino group -NR ₂ (where each R is an alkyl etherified methylol group) are referred to as a methylol type amino resin. It is called a full alkyl type amino resin.

Specific examples of the imino group type amino resin include Cymel 202, 207, 213, 253, 254, 325, 327, 701, 703, 712, Mycoat 508 (all manufactured by Ornex), Nicarac BL-60, MS. -001, MX-410, MX-706, MX-730, MX-750, MZ-351 (all manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned. Of these, Cymel 325, 327, 703 and Nicarax MX-730 are particularly preferable.

The amount of the imino group type amino resin in the total resin contained in the undercoat film layer is preferably in the range of 3 to 20% by mass, more preferably 5 to 20% by mass, and further preferably 5 to 15% by mass. be. The imino group type amino resin may be used alone or in combination of two or more.

The undercoat coating layer further preferably contains one or more types of coating film-forming resins selected from the group consisting of self-crosslinking acrylic resins, acrylic polyol resins, and polyester polyol resins. By combining these coating film forming resins with imino group type amino resins, the adhesiveness with ink can be improved. In particular, the self-crosslinking type acrylic resin has a high effect of improving stain resistance and scratch resistance (or hardness) when combined with an imino group type amino resin.

The total amount of the coating film-forming resin composed of the self-crosslinking acrylic resin, the acrylic polyol resin and the polyester polyol resin in the total resin contained in the undercoat coating film layer is preferably 30 to 95% by mass, more preferably 50. It is in the range of ~ 90% by mass. The self-crosslinked acrylic resin, the acrylic polyol resin, and the polyester polyol resin may be used alone or in combination of two or more.

In the present specification, the acrylic resin is a polymer of acrylic acid esters or methacrylic acid esters, and is, for example, one of the (meth) acrylic monomers selected from acrylic acid, methacrylic acid and its esters, amides, nitriles and the like. Examples thereof include a polymer obtained by polymerizing a seed or a plurality of species, and further include a polymer obtained by polymerizing a (meth) acrylic monomer and a non- (meth) acrylic monomer such as styrene. Here, the term (meth) acrylic monomer means a methacrylic monomer or an acrylic monomer. Here, the acrylic polyol resin is an acrylic resin having a plurality of hydroxyl groups. The acrylic polyol resin can be easily obtained, for example, by using a monomer having a hydroxyl group in the synthesis of the acrylic resin.

In the present specification, the polyester resin is a resin composed of a polymer in which ester bonds are repeated as an indispensable part of the main chain, and is obtained by, for example, a reaction between a polyvalent carboxylic acid and a polyhydric alcohol. .. Here, the polyester polyol resin is a polyester resin having a plurality of hydroxyl groups.

The self-crosslinking acrylic resin is a resin having a self-crosslinking functional group in the acrylic resin skeleton as a substrate, whereby the self-crosslinkable functional groups form crosslinks by baking after the undercoat coating ( Here, cross-linking between self-crosslinking functional groups includes cross-linking between the same functional groups and cross-linking between different types of functional groups), whereby a cured coating film having excellent hardness and scratch resistance is obtained. Can be formed as an undercoat coating layer.

（式中、Ｒ^１は、水素原子又は炭素数が１〜８のアルキル基であり、記号＊は、アクリル樹脂骨格への結合点である）で表される官能基を有することが好ましく、更には、式（２）で表される官能基に加えて、該官能基に対して反応性を示す官能基（例えば、水酸基、アミノ基、アミド基、イミド基、アルコキシメチル基等）を有していてもよい。この式（２）で表される自己架橋性官能基どうしの熱処理（焼付）による架橋の機序は公知の通りであり、熱処理により式中のＲ^１（水素原子又はアルキル基）の脱離や、それと同時に引き起こされる脱水や、それに引き続きホルムアルデヒド（ＣＨ_２Ｏ）が脱離されることにより、最終的に−ＮＨ−ＣＨ_２−ＮＨ−の結合が生じることによるものであることが確認されている。 The self-crosslinking type acrylic resin has the following formula (2): as a self-crosslinking functional group.

It is preferable to have a functional group represented by (in the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the symbol * is a bond point to the acrylic resin skeleton). Has a functional group (for example, a hydroxyl group, an amino group, an amide group, an imide group, an alkoxymethyl group, etc.) that exhibits reactivity with the functional group in addition to the functional group represented by the formula (2). May be. The equation (2) the mechanism of crosslinking by heat treatment of each other self-crosslinkable functional group (baking) represented by are known as, elimination of R ¹ in the formula ^(a hydrogen atom or an alkyl group) Ya by heat treatment It has been confirmed that this is due to the dehydration caused at the same time and the subsequent _{elimination of formaldehyde (CH 2} O), resulting in the final _{binding of -NH-CH 2-NH-.}

In the above formula (2), R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group may be a straight chain or a branched chain, and an alkyl group having 1 to 4 carbon atoms is preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group and the like. The alkyl group may be unsubstituted or substituted, but is preferably an unsubstituted alkyl group. Examples of the substituent of the alkyl group include halogen and the like.

The amount of the functional group represented by the above formula (2) contained in the self-crosslinking acrylic resin is, for example, 3 to 20% by mass, preferably 5 to 15% by mass from the viewpoint of sufficient curing by baking.

（式中、Ｒ^１は、水素原子又は炭素数が１〜８のアルキル基であり、Ｒ^２は、水素原子又はメチル基である）で表される（メタ）アクリルモノマーの重合体又は上記式（１）で表される（メタ）アクリルモノマーと該（メタ）アクリルモノマー以外のエチレン性不飽和基を有するモノマー及び／又はオリゴマーとを共重合させたアクリル樹脂共重合体のいずれか一方であるか、又はその両方からなることが好ましい。 The self-crosslinking acrylic resin has the following formula (1).

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom or a methyl group), or a polymer of a (meth) acrylic monomer represented by the above formula. It is one of an acrylic resin copolymer obtained by copolymerizing a (meth) acrylic monomer represented by (1) with a monomer having an ethylenically unsaturated group other than the (meth) acrylic monomer and / or an oligomer. It is preferably composed of or both.

In the above formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group may be a straight chain or a branched chain, and an alkyl group having 1 to 4 carbon atoms is preferable. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group and the like. The alkyl group may be unsubstituted or substituted, but is preferably an unsubstituted alkyl group. Examples of the substituent of the alkyl group include halogen and the like. Further, in the above formula (1), R ² is a hydrogen atom or a methyl group, and is preferably hydrogen.

Specific examples of the (meth) acrylic monomer represented by the above formula (1) preferably include Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methylolacrylamide and the like. Be done.

Examples of the monomer and / or oligomer having an ethylenically unsaturated group other than the (meth) acrylic monomer represented by the above formula (1) include acrylic acid, methyl acrylate, ethyl acrylate, and isopropyl acrylate. N-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Examples thereof include n-hexyl, 2-hydroxyethyl methacrylate, and styrene.

Specific examples of the self-crosslinking acrylic resin include Dianal SE5661, SE5456, SE5102, SE5482, RE1616, LR691 (all manufactured by Mitsubishi Rayon Co., Ltd.) and the like.

The number average molecular weight (Mn) of the self-crosslinking acrylic resin, the acrylic polyol resin, and the polyester polyol resin is preferably 3,000 to 50,000, more preferably 10,000, from the viewpoint of adhesion to ink and performance as a coating film. The weight average molecular weight (Mw) is preferably 1000 to 20000, more preferably 50,000 to 150,000, and the glass transition temperature (Tg) is preferably -30 to 90 ° C, more preferably −. It is 20 to 60 ° C.

In the present specification, the number average molecular weight and the weight average molecular weight are values measured by gel permeation chromatography, and polystyrene is used as a standard substance.

In the present specification, the glass transition temperature (Tg) means a temperature calculated by using the following FOX formula.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
In the above FOX equation, Tg is the glass transition temperature (K) of the polymer composed of n kinds of monomers, and Tg (1, 2, i, n) is the glass transition temperature (K) of the homopolymer of each monomer. Yes, W (1, 2, i, n) is the mass fraction of each monomer, and W1 + W2 + ... + Wi + ... + Wn = 1.

The acrylic polyol resin and the polyester polyol resin preferably have a hydroxyl value of 1 to 200 mgKOH / g. When the hydroxyl value of these resins is within the specified range, sufficient curability can be ensured to show good coating film performance. The hydroxyl value can be measured according to JIS K 0070. If the hydroxyl value of these resins is less than 1 mgKOH / g, sufficient curability may not be obtained. On the other hand, if the hydroxyl value of these resins is larger than 200 mgKOH / g, the number of cross-linking points increases and the internal stress increases, so that the adhesion to the substrate or the coating film may deteriorate.

The undercoat coating layer can contain pigments. Specific examples of pigments include colored pigments such as titanium dioxide, iron oxide and carbon black, extender pigments such as silica, talc, mica, calcium carbonate and barium sulfate, zinc, zinc phosphate, aluminum phosphate and zinc molybdate. Examples thereof include rust preventive pigments such as barium metaborate and hydrocarbumite, bright pigments such as aluminum, nickel, chromium, tin, copper, silver, platinum, gold and stainless steel, and scaly pigments such as glass flakes and graphite.

In the undercoat coating film layer, the amount of the pigment is, for example, in the range of 0 to 50% by mass. The amount of the pigment in the undercoat paint is, for example, in the range of 0 to 50% by mass, preferably 1 to 30% by mass. The pigment may be used alone or in combination of two or more.

In addition to resins and pigments, the undercoat coating layer and undercoat paint include water, organic solvents, desiccants, antioxidants, reaction catalysts, dispersants, defoamers, dehydrating agents, leveling agents, antisettling agents, and anti-sagging agents. An agent, an adhesive-imparting agent such as a silane coupling agent, an algae-proofing agent, an antifungal agent, a preservative, an ultraviolet absorber, a radical trapping agent and the like may be appropriately blended as needed. The undercoat paint can be prepared by mixing various components appropriately selected as required.

The coating means using the undercoat paint is not particularly limited, and known painting means such as air spray, airless spray, curtain flow, roll coater, roller curtain, die coater, flow coater, electrostatic coating and the like can be used. The amount of the undercoat paint applied is, for example, ² to 80 g / m 2 per coating. When increasing the coating amount, it is possible to perform multiple coatings (overcoating).

The undercoat coating film layer is formed by coating the surface of the base material with the undercoat paint and then baking and curing the undercoat paint in the coating film forming step. Baking can be performed by a known method. As the baking conditions, if the undercoat paint can be sufficiently cured, it can be appropriately adjusted, but usually, the maximum temperature at which the substrate is reached is 150 to 240 ° C. for 20 seconds to 60 minutes, more specifically. The temperature is 210 ° C. for about 60 seconds. It is preferable that the undercoat coating layer is sufficiently cured at this stage so that the print layer formed from the active energy ray-curable ink does not move, crack or peel off due to subsequent heat treatment or the like. It is also possible to form a print layer on the semi-cured undercoat coating layer with an active energy ray-curable ink and then perform heat treatment to sufficiently cure the print layer. The degree of curing can be specified, for example, as a gel fraction known in the art, and can be confirmed by a solvent rubbing test or the like. In the present specification, a gel fraction of 75% or more in the undercoat coating film layer can be defined as at least a "cured" state, preferably a gel fraction exceeding 80%, more preferably. It is often cured so that the gel fraction is 90% or more, and more preferably 95% or more and cured so as to approach 100%. The gel fraction can be adjusted by changing the baking conditions. For example, the gel is immersed in tetrahydrofuran at a temperature of about 23 ° C. for about 48 hours, filtered and dried to apply a coating equivalent to uncured. It can be determined from the ratio of the mass of the residual coating film from which the film has been removed to the mass of the original coating film.

The undercoat coating film layer has a thickness of, for example, 5 to 40 μm.

In the printed matter of the present invention, the printed layer is formed from an active energy ray-curable ink. Here, the print layer is formed at least on a part or the whole of the surface of the undercoat film layer. The print layer is formed by printing on the surface of the undercoat coating film layer obtained in the coating film forming step with an active energy ray-curable ink and then curing the surface by irradiation with active energy rays in the print layer forming step. can. This makes it possible to apply various designs. Further, since the undercoat coating film layer is excellent in stain resistance and scratch resistance, even if there is a part where printing is not performed on the undercoat coating film layer, the undercoat coating film layer may be scratched or contaminants may be present. It is possible to suppress the adhesion.

In the printing layer forming step, printing is performed on at least a part or the whole surface of the undercoat coating film layer using the active energy ray-curable ink. As used herein, the active energy ray-curable ink means an ink composition that can be cured by irradiation with active energy rays such as ultraviolet rays, visible light, and electron beams.

The active energy ray-curable ink used in the print layer forming step contains a polymerizable compound and a photopolymerization initiator.

The polymerizable compound is via a functional group (for example, a polymerizable unsaturated group such as a carbon-carbon double bond constituting an acryloyl group, a methacryloyl group, a vinyl group or an allyl group) that exhibits reactivity when irradiated with active energy rays. It is a compound that causes a polymerization reaction. The polymerizable compound may be used alone or in combination of two or more. The amount of the polymerizable compound in the active energy ray-curable ink is preferably 50 to 95% by mass.

The polymerizable compound is classified into a monofunctional polymerizable compound or a polyfunctional polymerizable compound. Here, as the monofunctional polymerizable compound, a monofunctional polymerizable monomer having one functional group exhibiting reactivity when irradiated with active energy rays (for example, a monofunctional polymerizable monomer having one polymerizable unsaturated group) or activity. Examples thereof include a monofunctional polymerizable oligomer having one functional group exhibiting reactivity when irradiated with energy rays (for example, a monofunctional polymerizable oligomer having one polymerizable unsaturated group). Examples of the polyfunctional polymerizable compound include a polyfunctional polymerizable monomer having two or more functional groups exhibiting reactivity when irradiated with active energy rays (for example, a polyfunctional polymerizable monomer having two or more polymerizable unsaturated groups) and an activity. Examples thereof include a polyfunctional polymerizable oligomer having two or more functional groups exhibiting reactivity when irradiated with energy rays (for example, a polyfunctional polymerizable oligomer having two or more polymerizable unsaturated groups).

Specific examples of the monofunctional polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxykipropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-. Hydroxyhexyl (meth) acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, stearyl (meth) acrylate, acryloyl morpholine, tridecyl (meth) acrylate, lauryl (Meta) Acrylate, dimethylacrylamide, hydroxyethylacrylamide, diethylacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide, diacetoneacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N- Methylolacrylamide, N-vinylcaprolactam, decyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, isodecyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meta) acrylate, dicyclopentenyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, octyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butyl Cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, EO (ethylene oxide) modified 2-ethylhexyl (meth) acrylate, neopentyl glycol (meth) acrylic acid benzoic acid ester, N- Vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) ) Acrylate, cyclic trimethylol propaneformal (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate and the like.

Among the polyfunctional polymerizable monomers, 1,12-dodecanediol di (meth) is a specific example of the polyfunctional polymerizable monomer (bifunctional polymerizable monomer) having two functional groups exhibiting reactivity when irradiated with active energy rays. ) Acrylate, 1,10-decanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate , 1,9-Nonandiol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, , 4-Butandiol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, tricyclodecanedimethanol diacrylate, dimethylolcyclohexanediacrylate , Hydroxypivalate neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, PO (propylene oxide) modified neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di Examples thereof include (meth) acrylate, tripropylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate.

Specific examples of the polyfunctional polymerizable monomer (polyfunctional polymerizable monomer having three or more functional groups) having three or more functional groups exhibiting reactivity when irradiated with active energy rays include trimethyl propanetri (meth) acrylate and ethoxy. Trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, EO modification Examples thereof include diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and EO-modified dipentaerythritol hexa (meth) acrylate.

As used herein, the term (meth) acrylate means methacrylate or acrylate. Further, when the (meth) acrylate is prefixed with a plurality of prefixes such as di (meth) acrylate and tri (meth) acrylate, each (meth) acrylate portion is the same but different. May be good.

In the active energy ray-curable ink, the amount of the monofunctional polymerizable monomer is preferably 30 to 95% by mass. In the active energy ray-curable ink, the amount of the polyfunctional polymerizable monomer is, for example, 0 to 30% by mass, preferably 5 to 20% by mass.

The active energy ray-curable ink preferably contains a polymerizable oligomer as a polymerizable compound. The polymerizable oligomer is preferably an acrylate oligomer. The number of functional groups of the polymerizable oligomer is preferably 2 to 6, and the molecular weight of the polymerizable oligomer is preferably 2000 to 20000. Here, the molecular weight of the polymerizable oligomer is a polystyrene-equivalent weight average molecular weight.

Specific examples of the acrylate oligomer include urethane acrylate oligomer [acrylate oligomer having a plurality of urethane bonds (-NHCOO-)], amino acrylate oligomer [ _{acrylate oligomer having a plurality of amino groups (-NH 2} )], and epoxy acrylate oligomer [epoxy group]. An acrylate oligomer having a plurality of ester bonds [-SiO-], a silicone acrylate oligomer [an acrylate oligomer having a plurality of siloxane bonds (-SiO−)], an ester acrylate oligomer [an acrylate oligomer having a plurality of ester bonds (-COO−)], and a butadiene acrylate oligomer [butadiene unit. A plurality of acrylate oligomers] and the like. Among these, urethane acrylate oligomers are preferable.

Further, the following are known as acrylate oligomers.
Beam set 502H, beam set 505A-6, beam set 550B, beam set 575, beam set AQ-17 (manufactured by Arakawa Chemical Industry Co., Ltd.),
AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.),
CN910, CN959, CN963, CN964, CN965NS, CN966NS, CN969NS, CN980NS, CN981NS, CN982, CN983NS, CN985, CN991NS, CN996NS, CN2920, CN2921, CN9881NS, CN2920, CN2921, CN9881NS, CN8883NS, CN9801NS CN9028, CN9030, CN9178NS, CN9290, CN9893NS, CN929, CN989NS, CN968NS, CN9006NS, CN9010NS, CN9025, CN9026, CN9039, CN9062, CN9111NS, CN9029, CN8885NS, CN9013NS, CN97885NS, CN9013NS, CN9782NS CN971, CN972, CN975NS, CN9165 (manufactured by Sartmer),
U-2PPA, U-6LPA, U-10HA, U-10PA, UA-1100H, U-15HA, UA-53H, UA-33H, U-200PA, UA-200PA, UA-160TM, UA-290TM, UA- 4200, UA-4400, UA-122P (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.),
New Frontier R-1235, R-1220, RST-201, RST-402, R-1301, R-1304, R-1214, R-1302XT, GX-8801A, R-1603, R-1150D (Daiichi Kogyo Seiyaku) Made by the company),
EBECRYL204, EBECRYL205, EBECRYL210, EBECRYL215, EBECRYL220, EBECRYL230, EBECRYL244, EBECRYL245, EBECRYL264, EBECRYL265, EBECRYL270, EBECRYL280 / 15IB, EBECRYL284, EBECRYL285, EBECRYL294 / 25HD, EBECRYL1259, EBECRYL1290, KRM8200, EBECRYL4820, EBECRYL4858, EBECRYL5129, EBECRYL8210, EBECRYL8254, EBECRYL8301R, EBECRYL8307, EBECRYL8402, EBECRYL8405, EBECRYL8411, EBECRYL8465, EBECRYL8800, EBECRYL8804, EBECRYL8807, EBECRYL9260, EBECRYL9270, EBECRYL7735, EBECRYL8296, EBECRYL8452, EBECRYL8904, EBECRYL8311, EBECRYL8701, EBECRYL8667 (manufactured by Daicel-Orunekusu Co., Ltd.),
UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV-7650B, UV-6630B, UV-77000B, UV-7510B, UV- 7461TE,
UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3300B, UV-3310B, UV-3700B, UV6640B (manufactured by Nippon Synthetic Chemistry Co., Ltd.),
Art Resin UN-333, UN-350, UN-1255, UN-2600, UN-2700, UN-5590, UN-6060PTM, UN-6200, UN-6202, UN-6300, UN-6301, UN-7600, UN-7700, UN-99000PEP, UN-9200A, UN-3320HA, UN-3320HC, UN-904, UN-906S (manufactured by Negami Kogyo Co., Ltd.)

In the active energy ray-curable ink, the amount of the polymerizable oligomer is preferably 1 to 20% by mass, more preferably 5 to 15% by mass. The polymerizable oligomer may be used alone or in combination of two or more.

（式（３）中、Ｒ^３は水素原子又はメチル基であり、ｎは１〜３の整数である。）で表されるラジカル重合性モノマー及び／又は以下の式（４）：

〔式（４）中、Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素数２〜４のアルキレン基であり、Ｒ^４が炭素数２のアルキレン基である場合はｎが２〜５の整数であり、Ｒ^４が炭素数３のアルキレン基である場合はｎが１〜３の整数であり、Ｒ^４が炭素数４のアルキレン基である場合はｎが１〜２の整数である。〕で表されるラジカル重合性モノマーを含むことが好ましい。 Further, in the printed matter of the present invention, from the viewpoint of improving the adhesion to the undercoat coating film layer, the active energy ray-curable ink is described by the following formula (3):

(In the formula (3), R ³ is a hydrogen atom or a methyl group, and n is an integer of 1 to 3), and the radically polymerizable monomer and / or the following formula (4):

[In the formula (4), R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group having 2 to ^{4 carbon atoms, and when R 4} is an alkylene group having 2 carbon atoms, n is 2 to 5 When R ⁴ is an alkylene group having 3 carbon atoms, n is an integer of 1 to 3, and when R ⁴ is an alkylene group having 4 carbon atoms, n is an integer of 1 to 2. .. ] It is preferable to contain a radically polymerizable monomer represented by.

The compounds represented by the above formulas (3) and (4) are hydroxyl group-containing (meth) acrylates, but have an acryloyloxy group (CH ₂ = CHCOO−) or a methacryloyloxy group (CH ₂ = CCH ₃ COO−). It has a structure derived from a ring-opened product of ε-caprolactone or a structure derived from an alkylene oxide such as ethylene oxide or propylene oxide between the and hydroxy groups, whereby printing on a substrate (undercoat coating layer) can be performed. The adhesiveness of the layer can be improved. The content of such a radically polymerizable monomer is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and 5 to 10% by mass in the total mass of the ink composition. Is even more preferable.

In the above formula (3), R ³ is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Further, in the above formula (3), n is an integer of 1 to 3, preferably 2 to 3, and even more preferably 2. The compound represented by the above formula (3) can be obtained by, for example, caprolactone-modifying hydroxyethyl acrylate by a conventional method, and a commercially available product can be preferably used. Specific examples thereof include a reaction product of hydroxyethyl (meth) acrylate and ε-caprolactone, which may be used alone or in combination of two or more.

Further, in the above formula (4), R ³ is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Further, in the above formula (4), R ⁴ is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and is an ethylene group (−CH ₂ CH ₂ −). Is preferable. Further, in the above formula (4), ^{n is an integer of 2 to 5 when R 4} is an alkylene group having 2 carbon atoms, and ^{n is 1 to 3 when R 4} is an alkylene group having 3 carbon atoms. When R ⁴ is an alkylene group having 4 carbon atoms, n is an integer of 1 to 2. In the above formula (4), when R ⁴ is an alkylene group having 4 carbon atoms, 4-hydroxybutyl acrylate is particularly suitable. Such a compound can be obtained, for example, by modifying hydroxyethyl acrylate with an alkylene oxide by a conventional method, and a commercially available product can be preferably used. Specific examples thereof include 4-hydroxybutyl acrylate, polyoxyethylene monoacrylate, polyoxypropylene monoacrylate, and polyoxybutylene monoacrylate, which may be used alone or in combination of two or more. good.

The photopolymerization initiator used in the active energy ray-curable ink has an action of initiating the polymerization of the above-mentioned polymerizable compound by being irradiated with the active energy ray. The amount of the photopolymerization initiator is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 15% by mass in the ink. If the content of the photopolymerization initiator is less than 1% by mass, the printed layer may be poorly cured, and if it exceeds 25% by mass, precipitates may be generated at low temperatures and ink ejection may become unstable. be. Further, in order to accelerate the initiation reaction of the photopolymerization initiator, it is also possible to use an auxiliary agent such as a photosensitizer in combination.

Examples of the photopolymerization initiator include benzophenone-based compounds, acetophenone-based compounds, thioxanthone-based compounds, and phosphine oxide-based compounds. From the viewpoint of curability, the wavelength of the activated energy ray to be irradiated and the absorption of the photopolymerization initiator. It is preferable that the wavelengths overlap as much as possible. In particular, the photopolymerization initiator preferably contains an acylphosphine oxide-based initiator from the viewpoint of improving the yellowing resistance during heating. Although the printed film of the acylphosphine oxide-based initiator is more likely to yellow than other initiators when cured by irradiation with active energy rays, its transparency is improved by the subsequent heat treatment. The photopolymerization initiator may be used alone or in combination of two or more.

Specific examples of the photopolymerization initiator include
2,2-dimethoxy-1,2-diphenylethane-1-one,
1-Hydroxy-cyclohexyl-phenyl-ketone,
2-Hydroxy-2-methyl-1-phenylpropane-1-one,
Benzophenone,
1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one,
2-Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propan-1-one,
Phenylglycylic acid methyl ester,
2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one,
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone,
2-Dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one,
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphinoxide,
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)],
Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime),
2,4-Diethylthioxanthone,
2-Isopropylthioxanthone,
2-Chlorothioxanthone and the like can be mentioned.

Among these, from the viewpoint of ink curability, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphinoxide, 2,4,6-trimethylbenzoyl-diphenyl -Phosphinoxide and 2,4-diethylthioxanthone are preferable, and from the viewpoint of improving yellowing resistance during heating, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, bis (2,) 6-Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide are preferred, with 2,4,6-trimethylbenzoyl-diphenyl-phosphine. Oxides are particularly preferred.

The active energy ray-curable ink preferably contains either an ultraviolet absorber or a radical scavenger, or both an ultraviolet absorber and a radical scavenger.

The ultraviolet absorber has an effect of absorbing ultraviolet rays and preventing deterioration due to ultraviolet rays. Examples of the ultraviolet absorber include cyanoacrylate compounds, benzophenone compounds, benzoate compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, benziliden camphor compounds, inorganic fine particles and the like, and among them, ultraviolet absorption has a shorter wavelength. The hydroxyphenyltriazine-based compound in the above is preferable from the viewpoint of the curability of the ink. From the viewpoint of curability, it is preferable that the wavelength of the activated energy ray to be irradiated and the absorption wavelength of the ultraviolet absorber do not overlap as much as possible.

As a specific example of the ultraviolet absorber,
2,4-Dihydroxybenzophenone,
2-Hydroxy-4-methoxybenzophenone,
2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-Hydroxy-4-octoxybenzophenone,
2-Hydroxy-4-dodecyloxybenzophenone-2-hydroxy-4-benzyloxybenzophenone,
Bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane,
2,2'-Dihydroxy-4-methoxybenzophenone,
2,2'-Dihydroxy-4,4'-dimethoxybenzophenone,
2,2', 4,4'-tetrahydroxybenzophenone,
2-Hydroxy-4-methoxy-2'-carboxybenzophenone,
2- (2'-Hydroxy-5'-methylphenyl) benzotriazole 2- [2'-hydroxy-3', 5'-bis (α, α- (dimethylbenzyl) phenyl] benzotriazole,
2- (2'-Hydroxy-3', 5'-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole,
2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole,
2- (2'-Hydroxy-3', 5'-di-t-amylphenyl) benzotriazole,
2- (2'-Hydroxy-5'-t-octylphenyl) benzotriazole,
2,2'-Methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-2-yl) phenol],
Condensate of methyl-3- [3-t-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenyl] propionate with polyethylene glycol,
2- (2-Hydroxyphenyl) benzotriazole,
2- (2'-Hydroxy-5'-methylphenyl) benzotriazole,
2,6-di-t-butylphenyl-3', 5'-di-t-butyl-4'-hydroxybenzoate,
Hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and the like can be mentioned.

In the active energy ray-curable ink, the amount of the ultraviolet absorber is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.2 to 0.2% by mass from the viewpoint of weather resistance. It is preferably in the range of 5% by mass. If the amount of UV absorber is too large, the print layer may not be sufficiently cured. The ultraviolet absorber may be used alone or in combination of two or more, but the ultraviolet absorber preferably contains at least two types of ultraviolet absorbers. By using a plurality of types of ultraviolet absorbers having different structures, the effect of the ultraviolet absorber can be further sustained.

The radical scavenger can capture free radicals and the like to improve photostability. Further, a substance having a function of reacting with a free radical and preventing a polymerization reaction from occurring (so-called polymerization inhibitor) is also included in the radical scavenger. Examples of the radical scavenger include hindered amine compounds, hydroquinone compounds, phenol compounds, phenothiazine compounds, nitroso compounds, N-oxyl compounds and the like, and hindered amine light stabilizers (HALS) are particularly preferable.

Specific examples of the radical trapping agent include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 1- {2- (3- (3,5-di-t-butyl-4-). Hydroxyphenyl) propionyloxy) ethyl} -2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro {4. 5} Hindered amine compounds such as decane-2,4-dione, phenol, o-, m- or p-cresol, 2-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol 2,6-di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol, 4- Phenolic compounds such as t-butyl-2,6-dimethylphenol, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, 2,5-di-t-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone , Trimethylhydroquinone 4-methylbenzcatechin, t-butylhydroquinone, 3-methylbenzcatechin, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, benzoquinone, t-butyl-p -Hydroquinone compounds such as benzoquinone, 2,5-diphenyl-p-benzoquinone, phenothiazine compounds such as phenothiazine, nitroso such as N-nitroso-N-phenylhydroxylamine ammonium, N-nitroso-N-phenylhydroxylamine aluminum salt, etc. System compounds, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidin-N-oxyl, 4-methoxy-2 , 2,6,6-Tetramethyl-piperidin-N-oxyl and other N-oxyl compounds and the like can be mentioned.

In the active energy ray-curable ink, the amount of the radical scavenger is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.2 to 10% by mass from the viewpoint of weather resistance. It is preferably in the range of 5% by mass. Too much radical scavenger can cause poor curing. The radical scavenger may be used alone or in combination of two or more.

The active energy ray-curable ink usually contains a colorant such as a dye or a pigment, but from the viewpoint of weather resistance, it is preferable to contain a pigment. For example, it is also possible to make a metallic ink by using a metal pigment or a pearl pigment. The content of the colorant is, for example, 0.1 to 15% by mass in the ink. Further, the colorant may be used alone or in combination of two or more.

Specific examples of colorants include
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 32, 34, 35, 36, 37, 41, 42, 43, 49, 53, 55, 60, 61, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 123, 124, 126, 127, 128, 129, 130, 133, 138, 139, 150, 151, 152, 153, 154, 155, 165, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 191, 193, 194, 199, 205, 206, 209, 212, 213, 214, 215, 219,
C. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 20, 21, 24, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 52, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58, 60: 1, 63, 64: 1, 68, 81: 1, 83, 88, 89, 95, 101, 104, 105, 108, 112, 114, 119, 122, 123, 136, 144, 146, 147, 149, 150, 164, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 216, 220, 220, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 269, 270, 271, 272, 279,
C. I. Pigment Violet 1, 2, 3, 3: 1, 3: 3, 5: 1, 13, 15, 16, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50,
C. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 24, 24: 1, 25, 26, 27, 28, 29, 36, 56, 60, 61, 62, 63, 75, 79, 80,
C. I. Pigment Green 1, 4, 7, 8, 10, 15, 17, 26, 36, 50,
C. I. Pigment Brown 5, 6, 23, 24, 25, 32, 41, 42,
C. I. Pigment Black 1,6,7,9,10,11,20,26,28,31,32,34,
C. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28,
Examples include aluminum flakes, glass flakes, hollow particles and the like.

Among these, from the viewpoint of weather resistance and color reproducibility of the print layer,
C. I. Pigment Black 7,
C. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 28,
C. I. Pigment Red 101, C.I. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 254, C.I. I. Pigment Red 282,
C. I. Pigment Violet 19,
C. I. Pigment White 6,
C. I. Pigment Yellow 42, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 213 is preferable.

From the viewpoint of ejection stability, the pigment particles dispersed in the ink preferably have a volume average particle diameter of 0.05 to 0.4 μm and a volume maximum particle diameter of 0.2 to 1 μm. If the volume average particle diameter is larger than 0.4 μm and the volume maximum particle diameter is larger than 1 μm, it tends to be difficult to stably eject the ink. The volume average particle size and the volume maximum particle size can be measured by a measuring device using a dynamic light scattering method.

The active energy ray-curable ink may further contain a pigment dispersant, if necessary, in order to disperse the pigment. The content of the pigment dispersant is, for example, 0.1 to 5% by mass in the ink. Further, the pigment dispersant may be used alone or in combination of two or more.

As a specific example of the above pigment dispersant,
ANTI-TERRA-U, ANTI-TERRA-U100,
ANTI-TERRA-204, ANTI-TERRA-205,
DISPERBYK-101, DISPERBYK-102,
DISPERBYK-103, DISPERBYK-106,
DISPERBYK-108, DISPERBYK-109,
DISPERBYK-110, DISPERBYK-111,
DISPERBYK-112, DISPERBYK-116,
DISPERBYK-130, DISPERBYK-140,
DISPERBYK-142, DISPERBYK-145,
DISPERBYK-161, DISPERBYK-162,
DISPERBYK-163, DISPERBYK-164,
DISPERBYK-166, DISPERBYK-167,
DISPERBYK-168, DISPERBYK-170,
DISPERBYK-171, DISPERBYK-174,
DISPERBYK-180, DISPERBYK-182,
DISPERBYK-183, DISPERBYK-184,
DISPERBYK-185, DISPERBYK-2000,
DISPERBYK-2001, DISPERBYK-2008,
DISPERBYK-2009, DISPERBYK-2020,
DISPERBYK-2025, DISPERBYK-2050,
DISPERBYK-2070, DISPERBYK-2096,
DISPERBYK-2150, DISPERBYK-2155,
DISPERBYK-2163, DISPERBYK-2164,
BYK-P104, BYK-P104S, BYK-P105,
BYK-9076, BYK-9077, BYK-220S, BYKJET-9150, BYKJET-9151 (all manufactured by Big Chemie Japan),
Solspece3000, Solspece5000,
Solsperse9000, Solsperse11200,
Solsperse13240, Solsperse13650,
Solsperse13940, Solsperse16000,
Solsperse17000, Solsperse18000,
Solspace 20000, Solspace 21000,
Solspece24000SC, Solspece24000GR,
Solsperse 26000, Solsperse 27000,
Solspece28000, Solspece32000,
Solspece32500, Solspece32550,
Solsperse32600, Solsperse33000,
Solsperse34750, Solsperse35100,
Solsperse35200, Solsperse36000,
Solspece36600, Solspece37500,
Solspece38500, Solspece39000,
Solsperse41000, Solsperse54000,
Solsperse55000, Solsperse56000,
Solsperse71000, Solsperse76500,
Solsperse X300 (above, manufactured by Lubrizol),
Disparon DA-7301, Disparon DA-325, Disparon DA-375, Disparon DA-234 (all manufactured by Kusumoto Kasei Co., Ltd.),
Floren AF-1000, Floren DOPA-15B, Floren DOPA-15BHFS, Floren DOPA-17HF, Floren DOPA-22, Floren DOPA-33, Floren G-600, Floren G-700, Floren G-700AMP, Floren G-700DMEA, Floren G-820, Floren G-900, Floren GW-1500, Floren KDG-2400, Floren NC-500, Floren WK-13E, (all manufactured by Kyoeisha Chemical Co., Ltd.),
TEGO Dispers 610, TEGO Dispers 610S,
TEGO Dispers 630, TEGO Dispers 650,
TEGO Dispers 652, TEGO Dispers 655,
TEGO Dispers 662C, TEGO Dispers 670,
TEGO Dispers 685, TEGO Dispers 700,
TEGO Dispers 710, TEGO Dispers 740W,
LIPOTIN A, LIPOTIN BL,
LIPOTIN DB, LIPOTIN SB (above, manufactured by Evonik Degusa),
PB821, PB822, PN411, PA111 (all manufactured by Ajinomoto Fine Techno Co., Ltd.),
Texahole 963, Texahole 964, Texahole 987, Texahole P60, Texahole P61, Texahole P63, Texahole 3250, Texahole SF71, Texahole UV20, Texahole UV21 (all manufactured by Cognis),
Examples thereof include BorchiGenSN88 and BorchiGen0451 (all manufactured by Bocious).

The active energy ray-curable ink may further contain a surface conditioner from the viewpoint of improving wettability and the like. As used herein, the surface conditioner means a substance that has a hydrophilic part and a hydrophobic part in the molecular structure and can adjust the surface tension of the ink by adding it.

Specific examples of the surface conditioner that can be used for the active energy ray-curable ink include anionic surface conditioners such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene. Nonionic surface conditioners such as alkylallyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surface conditioners such as alkylamine salts and quaternary ammonium salts, acrylic surface conditioners, Examples include silicon-based surface conditioners and fluorine-based surface conditioners. In particular, silicon-based surface conditioners and acrylic surface conditioners are preferable, and commercially available products such as Big Chemie, Evonik, and Toray Dow Corning can be used. Further, in the case of a silicone-based surface conditioner, it is preferably a polyether-modified silicone oil and the HLB is 7.6 to 12.

The amount of the surface conditioner in the active energy ray-curable ink can be appropriately selected depending on the purpose of use, but is preferably 0.01 to 1% by mass in the ink, for example. The surface conditioner may be used alone or in combination of two or more.

As a specific example of the above surface conditioner,
BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-325, BYK-326, BYK- 330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-370, BYK-375, BYK-377, BYK-378, BYK-381, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK- 3455, BYK-3550, BYK-3560, BYK-3565, BYK-3760, BYK-DYNWET 800N, BYK-SILCLEAN 3700, BYK-SILCLEAN 3701, BYK-SILCLEAN 3720, BYK-UV3500, BYK-UV3500, BYK- BYK-UV3530, BYK-UV3535, BYK-UV3570, BYK-UV3575, BYK-UV3576 (all manufactured by Big Chemie Japan),
TEGO Flow 300, TEGO Flow 370, TEGO Flow 425, TEGO Flow ATF 2, TEGO Flow ZFS 460, TEGO Glide 100, TEGO Glide 110, TEGO Glide 110, TEGO Glide 130, TEGO TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 482, TEGO GlideA 115, TEGO GlideB 1484, TEGO Glide B 1484, TEGO Glide ZG 400
501W ADDITIVE, FZ-2104, FZ-2110, FZ-2123, FZ-2164, FZ-2191, FZ-2203, FZ-2215, FZ-2222, FZ-5609, L-7001, L-7002, L-7604 , OFX-0193, OFX-0309 FLUID, OFX-5221 FLUID, SF 8410 FLUID, SH3771, SH 3746 FLUID, SH 8400 FLUID, SH 8700 FLUID, Y-7006 (all manufactured by Toray Dow Corning).
KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-640, KF-642, KF-643, KF-644, KF-945, KF-6004, KF- Examples thereof include 6011, KF-6012, KF-6015, KF-6017, KF-6020, KF-6204, X-22-2516, X-22-4515 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

Among these, from the viewpoint of structure and HLB, 501W ADDITIVE, FZ-2104, FZ-2123, FZ-2215, L-7002, OFX-0309 FLUID, OFX-5221 FLUID, SH 8400 FLUID, KF-351A, KF- 353, KF-355A, KF-615A, KF-642, KF-644, KF-6004, KF-6011, KF-6204 are preferable.

Other components of active energy ray-curable ink include antioxidants, plasticizers, rust preventives, solvents, non-reactive polymers, fillers, defoamers, charge controllers, stress relievers, penetrants, and guides. Additives such as a light material, a bright material, a magnetic material, and a phosphor may be used as needed.

The active energy ray-curable ink is obtained by mixing various components appropriately selected as necessary and, if necessary, using a filter having a pore size of about 1/10 or less of the nozzle diameter of the inkjet printhead to be used. It can be prepared by filtering the resulting mixture.

The viscosity of the active energy ray-curable ink at 40 ° C. is preferably 5 to 25 mPa · s, and more preferably 5 to 20 mPa · s. When the ink viscosity at 40 ° C. is within the above-specified range, good ejection stability can be obtained. The ink viscosity can be measured using a cone plate type viscometer.

The surface tension of the active energy ray-curable ink at 25 ° C. is preferably 20 to 35 mN / m, and more preferably 23 to 33 mN / m. When the ink surface tension at 25 ° C. is within the above-specified range, good ejection stability can be obtained. The ink surface tension can be measured by the plate method.

In the print layer forming step, printing is preferably performed by an inkjet printing method, but is not limited to this, and various types such as a gravure printing method, an offset printing method, a flexographic printing method, a screen printing method, and a coater method are used. It can also be done by a printing method.

In the present specification, printing means applying ink on an object by a printing means, and is not limited to those intended to color the object or draw characters, images, etc., and the surface of the object. It is also included that the purpose is to coat the target or to perform a surface treatment on the target. In the present specification, the ink used for the inkjet printing method is also referred to as an inkjet ink.

Various inkjet printers can be used for inkjet printing. Examples of the inkjet printer include an inkjet printer that ejects an ink composition by a charge control method or a piezo method. Further, a large-sized inkjet printer, specifically, an inkjet printer for printing on an article produced on an industrial line can also be preferably used.

In the print layer forming step, the curing of the ink layer is preferably performed by irradiation with light having a peak wavelength in the range of 350 nm or more and 400 nm or less. Here, as the light source, a high-pressure mercury lamp, a metal halide lamp, an LED lamp or the like can be used, but an LED lamp is preferable. Further, it is preferable that the wavelength of the active energy ray irradiated to cure the ink layer overlaps with the absorption wavelength of the photopolymerization initiator. The integrated light intensity of the active energy rays is preferably in the range of ^{100 to 2000 mJ / cm 2.}

The printed matter of the present invention may further include a surface protective layer. Here, the surface protective layer can be formed by a step of forming the surface protective layer so as to cover the print layer obtained in the print layer forming step. In the present specification, this step is referred to as a surface protective layer forming step.

In the printed matter of the present invention, the surface protective layer is formed so as to cover at least the printed layer. When there is a portion of the surface such as the base material or the undercoat coating film layer where the printing layer does not exist, the surface protective layer may be formed on the surface of the base material or the undercoat coating film layer.

From the viewpoint of weather resistance, the surface protective layer preferably contains either an ultraviolet absorber or a radical scavenger, or both an ultraviolet absorber and a radical scavenger. The surface protective layer may be a resin, a colorant, an antioxidant, a plasticizer, a rust preventive, a filler, a charge control agent, a light guide material, a bright material, a magnetic material, a phosphor, a wax, etc., as required. Can be included.

The surface protective layer is formed, for example, by paint or ink. The paints and inks for the surface protective layer include organic solvent-based paints and inks that use an organic solvent as the main solvent, water-based paints and inks that use water as the main solvent, photocurable paints and inks that use polymerizable compounds, and powders. Various paints and inks such as paints are available. In the printed matter of the present invention, the surface protective layer is preferably formed by an active energy ray-curable ink. Examples of the components that can be used in the active energy ray-curable ink for the surface protective layer include components that can be used in the active energy ray-curable ink used in the above-mentioned print layer forming step. For the formation of the surface protective layer, various coating means, printing means and curing means can be used in the same manner as in the formation of the undercoat coating film layer and the printing layer described above.

The active energy ray-curable ink for the surface protective layer is preferably a clear ink. In the present specification, the clear ink has a light transmittance of 80% or more in the wavelength range of 380 to 800 nm when a film having a thickness of 30 μm is formed. In the present specification, the light transmittance is measured according to JIS K7361-1: 1997 "Plastic-Test method for total light transmittance of transparent material-Part 1: Single beam method".

The active energy ray-curable ink for the surface protective layer can be subjected to surface finishing such as gloss-like and matte-like by appropriately selecting the ejection conditions for inkjet printing and the subsequent curing conditions. For example, if the ink is ejected and then cured after a while (after the ink has spread), the surface of the printed matter can be finished in a glossy manner, and the ink dots remain lenticular (the ink dots remain independent). ) Once cured, the surface of the printed matter can be finished in a matte finish. Further, by forming a thick portion in the clear layer, it is possible to give a texture and a three-dimensional effect according to the design applied to the base. In order to form a thickened portion on the clear layer, a method of increasing the amount of ink ejected or laminating the clear layer can be mentioned. Further, it is also possible to perform lenticular printing. For example, by ejecting clear ink in a dome shape on a print layer composed of two or more colors to form a clear layer, it is possible to provide a printed matter whose image changes depending on a viewing angle.

The surface protective layer is preferably a clear layer, and when the thickness is 30 μm, the light transmittance in the wavelength range of 380 to 800 nm is preferably 80% or more, and further preferably 90% or more. preferable.

The thickness of the surface protective layer is preferably in the range of 5 to 400 μm, and the difference between the minimum thickness and the maximum thickness in the surface protective layer is preferably 50 μm or more.

As described above, the method for producing a printed matter of the present invention includes a step of forming an undercoat coating film layer on the surface of a substrate (coating film forming step) and a step of forming a printing layer on the undercoat coating film layer (printing layer forming step). ) And.

In the method for producing a printed matter of the present invention, the coating film forming step is a step of coating the surface of a heat-resistant substrate with an undercoat paint and then baking and curing to form an undercoat coating film layer. Here, the undercoat coating film layer is formed on a part or the whole of the surface of the base material. The details of the coating film forming step in the method for producing a printed matter of the present invention are as described in the printed matter of the present invention.

In the method for producing a printed matter of the present invention, in the printing layer forming step, the surface of the undercoat coating layer obtained in the coating film forming step is printed with an active energy ray-curable ink and then irradiated with active energy rays. This is a process of curing to form a printed layer. In the printing layer forming step, printing is performed on at least a part or the whole surface of the undercoat coating film layer using the active energy ray-curable ink. The details of the print layer forming step in the method for producing a printed matter of the present invention are as described in the printed matter of the present invention.

The method for producing a printed matter of the present invention can further include a surface protective layer forming step. In the surface protective layer forming step, the surface protective layer is formed so as to cover at least the printed layer. When there is a portion of the surface such as the base material or the undercoat coating film layer where the printing layer does not exist, the surface protective layer may be formed on the surface of the base material or the undercoat coating film layer. The details of the surface protective layer forming step in the method for producing a printed matter of the present invention are as described in the printed matter of the present invention.

The method for producing a printed matter of the present invention is further obtained in a printed matter having a printed layer obtained in the printed layer forming step (that is, a printed matter having an undercoat coating layer and a printed layer on a substrate) or a surface protective layer forming step. A step (heat treatment step) of heating a printed matter having a surface protective layer to be obtained (that is, a printed matter having an undercoat coating layer, a printed layer and a surface protective layer on a substrate) can be included. This can solve the problems of odor and stickiness of the print layer and the surface protective layer, and can also improve the adhesiveness of the print layer and the surface protective layer. Here, the heat treatment is performed in the range of, for example, 70 ° C to 300 ° C.

Hereinafter, the method of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Synthesis of acrylic resin>
(Resin 1)
In a reaction vessel equipped with a stirrer, thermometer, reflux cooler, and dropping tank, 20 parts of butanol, 5 parts of T-SOL100FLUID (manufactured by Tonen General Petroleum Co., Ltd., aromatic mixed solvent), and 5.75 parts of xylene were placed. After heating and stirring to reach 110 ° C., 7.5 parts of Nn-butoxymethylacrylamide, 21.3 parts of styrene, 13.2 parts of butyl acrylate, 7 parts of methyl methacrylate, 1 part of acrylic acid, and Niper A mixture of 0.9 parts of BMT-K40 (mixture of organic peroxide manufactured by Nichiyu Co., Ltd.) was placed in a dropping tank and dropped over 4 hours.
After completion of the dropping, the dropping tank was washed with 1 part of T-SOL100FLUID, and a mixture of 1 part of Niper BMT-K40 and 1.5 parts of T-SOL100FLUID was added dropwise over 1 hour while maintaining 110 ° C. ..
After completion of the dropping, the dropping tank was washed with 0.5 part of T-SOL100FLUID, further stirred at 110 ° C. for 1.5 hours, and then cooled. After that, 14.35 parts of T-SOL100FLUID is added and stirred, and the self-crosslinked acrylic resin 1 having a functional group represented by the formula (2) (hereinafter, this may be simply referred to as “resin 1” or the like. ) Was obtained (Table 1).

(Resin 2 and 3)
In the same procedure as for resin 1, each raw material is placed in a reaction vessel in the formulation shown in Table 1 below to carry out a reaction, and the target self-crosslinking type having no functional group represented by the formula (2) is carried out. An acrylic resin 2 and a non-self-crosslinked acrylic resin 3 were obtained.

<Preparation of undercoat paint>
According to the formulation shown in Table 2 below, the mixture was prepared with stirring and sufficiently homogenized to obtain undercoat paints 1 to 13 (hereinafter, this may be simply referred to as "paint 1" or the like).

<Preparation of active energy ray-curable inkjet ink>
Each raw material is mixed according to the ink composition formulation of each color shown in Table 3 below, the obtained mixture is kneaded with a bead mill to homogenize, and finally filtered with a filter, and the active energy ray-curable inkjet ink 1 of each color is used. , And 2. Formulations in Table 3 are shown by weight.
The viscosity, surface tension, and specific density of the obtained inks of each color with respect to water at 4 ° C. were measured.

<Measurement of gel fraction of undercoat film layer>
The undercoat paints 1 to 13 prepared according to Table 1 above are each applied to a SUS304 board using an air spray, and then they are baked and cured under the undercoat paint baking conditions shown in Table 4 to obtain a film thickness of about 15 μm. An undercoat coating film layer was obtained. Then, the coating film was peeled off from the SUS304 plate, and the mass (Wc) of the coating film was measured. Then, the coating film was immersed in tetrahydrofuran and left at 25 ° C. for 48 hours, and then the residual coating film filtered through a 200 mesh stainless steel wire mesh was dried at 110 ° C. for 60 minutes to obtain the mass (Wd) of the residual coating film. Was measured, and the gel fraction (% by mass) was determined according to the following formula.
Gel fraction (% by mass) = (Wd / Wc) x 100

<Pencil hardness>
The undercoat paints 1 to 13 prepared according to Table 1 above are each applied to a SUS304 board using an air spray, and then they are baked and cured under the undercoat paint baking conditions shown in Table 4 to obtain a film thickness of about 15 μm. An undercoat coating film layer was obtained.
Each of the obtained undercoat coating film layers was tested according to JIS K5600-5-4 (pencil method), and the pencil hardness was evaluated according to the following criteria.
◎: H or higher ○: F
Δ: HB
×: B or less

<Stain resistance>
The undercoat paints 1 to 13 prepared according to Table 1 above are each applied to a SUS304 board using an air spray, and then they are baked and cured under the undercoat paint baking conditions shown in Table 4 to obtain a film thickness of about 15 μm. An undercoat coating film layer was obtained.
Each of the obtained undercoat coating film layers was colored with an oil-based black marker, and then the marker was wiped off with a cloth impregnated with butanol. The condition of the wiped surface was visually confirmed according to the following criteria, and the stain resistance was evaluated.
⊚: The colored part of the oil-based marker cannot be identified. ○: The oil-based marker is not colored, but the colored part can be identified. ×: The colored part of the oil-based marker remains.

<Adhesiveness>
First, the undercoat paints 1 to 13 prepared according to Table 1 above are each applied to a SUS304 board using an air spray, and then they are baked and cured under the undercoat paint baking conditions shown in Table 4, so that the film thickness is about the same. Each 15 μm undercoat coating film layer was obtained. Then, a solid image of each color of ink sets 1 and 2 is printed on the surface of each of the obtained undercoat coating layers using an inkjet printer equipped with the active energy ray-curable inkjet ink prepared in Table 3 above. Then, the ink was cured by irradiating the active energy rays with an ultraviolet LED lamp having a main emission wavelength of 385 nm to form a print layer having a film thickness of about 8 μm. The combinations of the undercoat paint and the active energy ray-curable inkjet ink are shown in Table 4.
Then, in accordance with JIS K5600-5-6 (cross-cut method), each print layer is cut into a grid pattern of 100 squares at 1 mm intervals, a peeling test is performed using an adhesive tape, and the residual rate after the peeling test is performed. Was determined, and the adhesiveness was evaluated according to the following criteria.
⊚: 100/100 (number of cut parts remaining after the test / total number of cut parts before the test)
◯: 95/100 to 99/100
Δ: 85/100 to 94/100
×: 84/100 or less

<Evaluation result>
The above evaluation results are shown in Table 4.

As is clear from the evaluation results in Table 4, Examples 1 to 14 containing the predetermined imino group type amino resin are excellent in stain resistance and pencil hardness of the undercoat coating film layer, and are the inks of the printing layer. The result was excellent adhesion. However, Comparative Examples 1 and 2 containing no predetermined imino group type amino resin were inferior to the above results.

Further, in the comparison of the adhesiveness test in Examples 1 to 14, the printed matter obtained in Example 7 whose evaluation result was not sufficient was subjected to a post-baking step under the condition of 160 ° C./20 minutes. In Example 15, the result that the adhesiveness was improved was obtained.

Claims (7)

A printed matter having a primer coating layer containing an imino group type amino resin as a coating resin and a printing layer formed from an active energy ray-curable ink containing a colorant on the surface of a heat-resistant substrate. A printed matter , wherein the undercoat coating layer further contains one or more types of coating film-forming resins selected from the group consisting of a self-crosslinking acrylic resin, an acrylic polyol resin, and a polyester polyol resin. The printed matter according to claim 1, wherein the amount of the imino group type amino resin in the total resin contained in the undercoat coating film layer is in the range of 3 to 20% by mass. The self-crosslinking acrylic resin has the following formula (1).

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² is a hydrogen atom or a methyl group), and / or a polymer of a (meth) acrylic monomer represented by the above. Alternatively, it is an acrylic resin copolymer obtained by copolymerizing a (meth) acrylic monomer represented by the above formula (1) with a monomer having an ethylenically unsaturated group other than the (meth) acrylic monomer and / or an oligomer. The printed matter according to claim 1 or 2 , wherein the printed matter is characterized by. The active energy ray-curable ink has the following formula (3):

(In the formula (3), R ³ is a hydrogen atom or a methyl group, and n is an integer of 1 to 3), and the radically polymerizable monomer and / or the following formula (4) :.

(In the formula (4), R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group having 2 to ^{4 carbon atoms, and when R 4} is an alkylene group having 2 carbon atoms, n is 2 to 5 When R ⁴ is an alkylene group having 3 carbon atoms, n is an integer of 1 to 3, and when R ⁴ is an alkylene group having 4 carbon atoms, n is an integer of 1 to 2. The printed matter according to any one of claims 1 to 3 , which contains a radically polymerizable monomer represented by ()). The printed matter according to any one of claims 1 to 4 , wherein the gel content of the undercoat coating film layer is 75% or more. The surface of the heat-resistant substrate is coated with an undercoat paint containing an imino-based type amino resin as a coating film-forming resin, and then baked and cured to form an undercoat coating layer, and then the formed undercoat coating. A method for producing a printed matter, wherein the surface of a layer is printed with an active energy ray-curable ink containing a colorant and then cured by irradiation with active energy rays to form a printed matter. A method for producing a printed matter, wherein the layer further contains one or more kinds of coating film-forming resins selected from the group consisting of a self-crosslinking acrylic resin, an acrylic polyol resin, and a polyester polyol resin. The method for producing a printed matter according to claim 6 , wherein the printed matter including the cured printed matter is heated in the range of 70 to 300 ° C.