COATING AGENT FOR FILM, LAMINATE, AND METHOD FOR MANUFACTURING PRINTED ARTICLE

Abstract

An object of the present invention is to provide a coating agent for a film that can exhibit sufficient adhesion to a film even when the active energy ray-curable ink is used. The present invention provides a coating agent for a film including a compound (a) having two or more (meth)acryloyl groups and an isocyanate group.

Claims

1. A coating agent for a film comprising a compound (a) having two or more (meth)acryloyl groups and an isocyanate group.

2. The coating agent for a film according to claim 1, wherein the coating agent for a film is an active energy ray-curable anchor coating agent.

3. The coating agent for a film according to claim 1, wherein an acrylic equivalent of the coating agent for a film is 100 g/eq or more and 450 g/eq or less.

4. The coating agent for a film according to claim 1, wherein an isocyanate content of the coating agent for a film is 2 mass % or more and 10 mass % or less.

5. The coating agent for a film according to claim 1, wherein the compound (a) has a urethane bond.

6. The coating agent for a film according to claim 1, wherein a weight-average molecular weight of the compound (a) is 1,000 or more and 5,000 or less.

7. The coating agent for a film according to claim 1, wherein the compound (a) is contained in an amount of 70 mass % or more and 100 mass % or less.

8. The coating agent for a film according to claim 1, wherein the compound (a) has a structure obtained by reacting (meth)acrylate having a hydroxyl group, a polyol compound, and a polyisocyanate compound, and in the compound (a), a content of the isocyanate group is 0.9 mol or more and 2.2 mol or less with respect to 1 mol of the hydroxyl group.

9. The coating agent for a film according to claim 8, wherein the polyol compound is polyester polyol.

10. The coating agent for a film according to claim 1, further comprising a urethane compound (b).

11. The coating agent for a film according to claim 10, wherein the compound (b) has a (meth)acryloyl group.

12-15. (canceled)

16. The coating agent for a film according to claim 1, wherein a viscosity at 25° C. and a rotation speed of 0.5 rpm is 30 Pa-s or more and 200 Pa-s or less.

17. A laminate comprising a cured layer of the coating agent for a film described in claim 1 on at least one surface of the film.

18. The laminate according to claim 17, wherein an area ratio of a carbon-carbon double bond/a carbonyl group in the cured layer by Raman spectrometry measurement is 0.5 or more and 2.5 or less.

19. A method for manufacturing a printed article, the method comprising a step of transferring the coating agent for a film described in claim 1 and an active energy ray-curable ink to a film and then irradiating the film with an active energy ray.

20. (canceled)

21. The method for manufacturing a printed article according to claim 19, wherein the active energy ray-curable ink contains a compound (e) having an ethylenically unsaturated group and having at least one functional group selected from the group consisting of an amino group, a hydroxyl group, and an acidic group.

22. The method for manufacturing a printed article according to claim 19, wherein the active energy ray-curable ink includes a plurality of colors including an active energy ray-curable white ink, and in the step of transferring the active energy ray-curable ink to the film, the active energy ray-curable white ink is first transferred.

23. The method for manufacturing a printed article according to claim 19, wherein the coating agent for a film is transferred to the film in a pattern.

24-26. (canceled)

Description

EXAMPLES

[0079] Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited thereto.

[0080] <Measurement of Weight-Average Molecular Weight>

[0081] The weight-average molecular weight of the compound (a) was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase. The compound (a) prepared in each of examples and comparative examples was diluted with tetrahydrofuran so as to have a concentration of 0.25 mass %, the diluted solution was stirred at 100 rpm for 5 minutes with a mix rotor (MIX-ROTAR VMR-5, manufactured by AS ONE CORPORATION) to be dissolved, and the solution was filtered through a 0.2 μm filter (Z227536-100 EA, manufactured by SIGMA Corporation) to obtain a filtrate as a measurement sample. As GPC, HLC-8220 (manufactured by Tosoh Corporation) was used, as a column, TSKgel SuperHM-H (manufactured by Tosoh Corporation), TSKgel SuperHM-H (manufactured by Tosoh Corporation), and TSKgel SuperH 2000 (manufactured by Tosoh Corporation) were connected in this order, and as RI detection, an RI detector built in the GPC was used. An injection amount was 10 μL, an analysis time was 30 minutes, a flow rate was 0.4 mL/min, and a column temperature was 40° C. A calibration curve was prepared using a polystyrene standard, and the weight-average molecular weight of the sample was calculated.

[0082] <Measurement of Viscosity>

[0083] A cylinder spindle No. 4 was attached to a B-type viscometer DV-II manufactured by Brookfield (BROOKFIELD), and the viscosity of the coating agents 1 to 18 at 25° C. and 0.5 rpm was measured.

[0084] <Measurement of Acrylic Equivalent>

[0085] For the coating agents 1 to 18, a 1 wt. % solution of CDCl.sub.3 was prepared, 0.05 wt. % of tetramethylsilane as an internal standard was added to seal the solution, and .sup.1H-NMR measurement was performed. The molar ratio was determined from the integration ratio of the peak (δ=5.8 to 6.5) of the (meth)acrylic group and the peak (δ=−0.05 to +0.05) of the methyl group of tetramethylsilane as an internal standard, and the number of moles of the acrylic group in the coating agent was calculated to calculate the acrylic equivalent.

[0086] <Preparation of Active Energy Ray-Curable Ink>

[0087] [Black Ink 1]

[0088] A mixture of 12 parts by mass of a copolymer of methacrylic acid, methyl methacrylate, and styrene (acid value: 95 mg KOH/mg), 40 parts by mass of M340 (containing a hydroxyl group) manufactured by Miwon Specialty Chemical Co., Ltd. as polyfunctional (meth)acrylate, 26 parts by mass of M262 manufactured by Miwon Specialty Chemical Co., Ltd., 18 parts by mass of Mogul E manufactured by Cabot Corporation as a black pigment, 2 parts by mass of MICRO ACE P-8 manufactured by Nippon Talc Co., Ltd. as an extender pigment, 1 part by mass of Disper BYK 2013 manufactured by BYK Co., Ltd. as a dispersant, and 1 part by mass of KTL-4N manufactured by KITAMURA LIMITED as wax was kneaded with a three-roll mill to obtain a black ink 1.

[0089] [Black Ink 2]

[0090] A mixture of 30 parts by mass of DAISODAP (registered trademark) K manufactured by Osaka Soda Company as diallyl phthalate resin, 25 parts by mass of M600 (containing a hydroxyl group) manufactured by Miwon Specialty Chemical Co., Ltd. as polyfunctional (meth)acrylate, 23 parts by mass of M3130 manufactured by Miwon Specialty Chemical Co., Ltd., 18 parts by mass of Mogul E manufactured by Cabot Corporation as a black pigment, 2 parts by mass of MICRO ACE P-8 manufactured by Nippon Talc Co., Ltd. as an extender pigment, 1 part by mass of Disper BYK 2013 manufactured by BYK Co., Ltd. as a dispersant, and 1 part by mass of KTL-4N manufactured by KITAMURA LIMITED as wax was kneaded with a three-roll mill to obtain a black ink 2.

[0091] [White Ink 3]

[0092] A mixture of 7 parts by mass of a copolymer of methacrylic acid, methyl methacrylate, and styrene (acid value: 95 mg KOH/mg), 23 parts by mass of M340 (containing a hydroxyl group) manufactured by Miwon Specialty Chemical Co., Ltd. as polyfunctional (meth)acrylate, 23 parts by mass of M262 manufactured by Miwon Specialty Chemical Co., Ltd., 45 parts by mass of TIPAQUE CR58-2 manufactured by Ishihara Sangyo Kaisha, Ltd. as a white pigment, 1 part by mass of Disper BYK 111 manufactured by BYK Co., Ltd. as a dispersant, and 1 part by mass of KTL-4N manufactured by KITAMURA LIMITED as wax was kneaded with a three-roll mill to obtain a white ink 3.

[0093] <Film Used>

[0094] Film 1: 12 μm-thick PET film (E5102 manufactured by TOYOBO CO., LTD.), with a corona treatment layer

[0095] Film 2: 12 μm-thick PET film (FS 2000 manufactured by FUTAMURA CHEMICAL CO., LTD.), without a surface treatment

[0096] Film 3: 12 μm-thick PET film (PTM manufactured by UNITIKA LTD.), with an easily adhesive coating layer

[0097] Film 4: 12 μm-thick barrier film/PET film laminate (1011HG SBR2 manufactured by TORAY ADVANCED FILM CO., LTD.)

[0098] Film 5: 15 μm-thick polyamide film (ON manufactured by UNITIKA LTD.) with a corona treatment layer.

[0099] <Printing Test>

[0100] A configuration common to the following printing methods 1 to 5 will be described. CI-8 manufactured by Comexi was used as a flexible packaging lithographic printing machine capable of installing up to 7 blanket cylinders. In the following printing methods 1 to 5, the installation positions of the seven blanket cylinders are referred to as a first cylinder, a second cylinder, a third cylinder, a fourth cylinder, a fifth cylinder, a sixth cylinder, and a seventh cylinder in order from the upstream side in the traveling direction of the film to be printed. Although the installation position of the blanket cylinder not mentioned in each printing method is not impression-throw-in, color printing can be performed by installing the transfer step of cyan, magenta, and yellow inks at the installation position not mentioned.

[0101] In common with the following printing methods 1 to 5, TAC-VT4 manufactured by Toray Industries, Inc. was used as a waterless lithographic printing plate. The printing speed was 150 m/min. In addition, electron beam irradiation was performed under conditions of an acceleration voltage of 110 kV and an irradiation dose of 30 kGy.

[0102] [Printing Method 1]

[0103] In the printing method 1, a printed image was a mirror image for back printing. A waterless lithographic printing plate of which the entire surface was a printing portion and a coating agent prepared according to the corresponding example or comparative example were set in the first cylinder, the black ink was set in the third cylinder, and the coating agent and the active energy ray-curable ink were transferred onto the film in this order in a wet-on-wet manner. The amount of ink supplied was adjusted so that the reflection density of a black solid part in the printed article was 1.8 by a reflection densitometer (SpectroEye manufactured by GretagMacbeth). Then, the coating agent and the active energy ray-curable ink were cured by electron beam irradiation.

[0104] [Printing Method 2]

[0105] In the printing method 2, a printed image was a mirror image for back printing. A waterless lithographic printing plate of which the entire surface was a printing portion and a coating agent prepared according to a corresponding example or comparative example were set in the first cylinder, only the coating agent was printed on a film, and then cured by electron beam irradiation, and the film was once wound up. The wound film was again set in a flexible packaging lithographic printing machine, a black ink was set in the third cylinder, and only the active energy ray-curable black ink was transferred in the same amount of ink supplied as in Printing Method 1. Then, the active energy ray-curable ink was cured by electron beam irradiation.

[0106] [Printing Method 3]

[0107] In the printing method 3, the printed image was a normal image for surface printing. A waterless lithographic printing plate of which the entire surface was a printing portion and a coating agent prepared according to a corresponding example or comparative example were set in the first cylinder, the white ink 3 was set in the second cylinder, and the black ink was set in the third cylinder. The coating agent, the white ink and the black ink were transferred onto the film in this order in a wet-on-wet manner. The amount of ink supplied was adjusted so that the reflection density of a black solid part in the printed article was 1.8 by a reflection densitometer (SpectroEye manufactured by GretagMacbeth). Then, the coating agent and the active energy ray-curable ink were cured by electron beam irradiation.

[0108] [Printing Method 4]

[0109] In the printing method 4, a printed image was a mirror image for back printing. A waterless lithographic printing plate in which a position corresponding to a printing portion of a black ink was patterned in a solid printing portion and a coating agent prepared according to the corresponding example were set in the first cylinder, and the black ink was set in the third cylinder. The coating agent and the active energy ray-curable ink were transferred onto the film in this order in a wet-on-wet manner. The amount of ink supplied was adjusted so that the reflection density of a black solid part in the printed article was 1.8 by a reflection densitometer (SpectroEye manufactured by GretagMacbeth). Then, the coating agent and the active energy ray-curable ink were cured by electron beam irradiation.

[0110] [Printing Method 5]

[0111] In the printing method 5, the printed image was a normal image for surface printing. The white ink 3 was set in the second cylinder, a black ink was set in the third cylinder, a waterless lithographic printing plate of which the entire surface was a printing portion, and a coating agent prepared in each example were set in the seventh cylinder. The active energy ray-curable ink and the coating agent were transferred onto the film in this order in a wet-on-wet manner. The amount of ink supplied was adjusted so that the reflection density of a black solid part in the printed article was 1.8 by a reflection densitometer (SpectroEye manufactured by GretagMacbeth). Then, the coating agent and the active energy ray-curable ink were cured by electron beam irradiation.

[0112] <Evaluation of Adhesion>

[0113] (Laminate Peeling Strength)

[0114] A mixed laminate adhesive (TAKELAC A 626/TAKENATE A-50, manufactured by Mitsui Chemicals, Inc.) was applied to the back printed article (Examples 1 to 23, Comparative Examples 4 and 5) obtained by the printing test so as to have a film thickness of 3.0 g/m.sup.2, and the back printed article was stacked with a 60 μm-thick unstretched polypropylene film (CPP) (ZK-297, manufactured by TORAY ADVANCED FILM CO., LTD.). Thereafter, aging was performed at 40° C. for 3 days to obtain a laminate sample. The black solid part in the laminate sample was cut into a strip shape with a width of 15 mm, and the strip was peeled off at 90° at 300 mm/min using a Tensilon universal tester (RTG-1210 manufactured by ORIENTEC CORPORATION) to measure the peeling strength.

[0115] When the peeling strength was less than 1.0 N/15 mm, the adhesion was insufficient, when the peeling strength was 1.0 N/15 mm or more and less than 1.5 N/15 mm, the adhesion was slightly good, when the peeling strength was 1.5 N/15 mm or more and less than 2.0 N/15 mm, the adhesion was good, when the peeling strength was 2.0 N/15 mm or more and less than 3.0 N/15 mm, the adhesion was considerably good, and when the peeling strength was 3.0 N/15 mm or more, the adhesion was determined to be extremely good.

[0116] (Fracture Mode)

[0117] In addition, the state at the time of peeling (fracture mode) was also observed. In the laminate sample having a multilayer structure, an interlayer where breakage occurs at the time of peeling corresponds to a portion where adhesion is the weakest. The fracture mode includes breakage of the film, peeling between the film and the coating layer, and peeling between the coating layer and the ink layer, and the case of breakage of the film is more preferable from the viewpoint of adhesion. Here, the “coating layer” refers to a layer formed by curing a coating agent.

[0118] In Comparative Examples 2 and 3, since the coating agent could not be sufficiently cured as described later, the adhesion was not evaluated.

[0119] (Cellophane Tape Peeling)

[0120] An optional range of 30 mm×18 mm in the ink film of the surface printed article (Examples 24 and 25, Comparative Example 1) was evaluated by cellophane tape peeling using “CELLOTAPE” (registered trademark) No. 405 (width 18 mm) manufactured by Nichiban Co., Ltd.

[0121] A: Ink film was not peeled off.

[0122] B: Most of ink film was peeled off.

[0123] <Evaluation of Abrasion Resistance of Printed Article>

[0124] An optional range of 3 cm×3 cm in the ink film of the surface printed article was rubbed back and forth 20 times with a nail, and the degree of scratches was evaluated.

[0125] A: No scratches due to nails were observed.

[0126] B: Ink was completely peeled off along nail mark, and film was exposed.

[0127] <Evaluation of Curability of Coating Agent>

[0128] In the printing method 1, curability was evaluated at optional five positions where the black ink was not printed, that is, the coating agent was the outermost layer.

[0129] A: When palpated at all points, uncured material did not adhere to palpated area and was cured.

[0130] B: When palpated at any point, uncured material adhered to palpated area and was not completely cured.

[0131] <Evaluation of Storage Stability of Coating Agent>

[0132] The coating agent was stored in a sealed container at normal pressure around 25° C. for 1 week, and then the presence or absence of gelation was determined by visual observation, fluidity at the time of inclination, and palpation with a spatula.

[0133] A: No gelation was observed.

[0134] B: Gelation was partially observed.

[0135] C: Coating agent was completely gelled.

[0136] <Gloss Measurement of Non-Printing Portion of Printed Article>

[0137] 60 degree specular glossiness of the non-printing portion of the printed article, that is, a portion where the coating agent was the outermost layer was measured in accordance with the provision of JIS Z8741-1997 using a precision gloss meter (GM-26PRO manufactured by MURAKAMI COLOR RESEARCH LABORATOR). The gloss was evaluated poor when the gloss value was 60 or less, good when the gloss value was 90 or more, and excellent when the gloss value was 120 or more.

[0138] <Raman Spectroscopic Measurement of Outermost Surface of Printed Article>

[0139] With respect to a portion where the coating agent was the outermost layer, such as a non-printing portion of the printed article, a cross section of any one portion was cut out with a microtome, and Raman spectrometry was performed using a Raman spectrometer (T-64000 manufactured by HORIBA/Jobin Yvon) and a detector CCD (1024×256 manufactured by HORIBA/Jobin Yvon). The measurement was performed under the conditions of an objective lens of 100 times, a beam diameter of 1 μm, and a slit of 100 μm, and argon ion laser (wavelength: 514.5 nm) was used as a light source. Regarding the carbon-carbon double bond of the ethylenically unsaturated group derived from the reaction residue of the (meth)acryloyl group with a peak observed in the range of 1600 to 1650 cm.sup.−1, and the carbonyl group of the (meth)acryloyl group with a peak observed in the range of 1650 to 1750 cm.sup.−1, the peak area was measured for each, and the area ratio of carbon-carbon double bond/carbonyl group was calculated.

[0140] <Raw Materials, Compounds, and the Like Used>

[0141] Hydroxyl group-containing (meth)acrylate 1: 2-hydroxyethyl acrylate “LIGHT ESTER” (registered trademark) HOA (manufactured by Kyoeisha Chemical Co., Ltd.)

[0142] Hydroxyl group-containing (meth)acrylate 2: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “Miramer” (registered trademark) M340 (manufactured by Miwon Specialty Chemical Co., Ltd.)

[0143] Polyisocyanate compound 1: “Coronate” (registered trademark) HX (manufactured by Tosoh Corporation)

[0144] Polyisocyanate compound 2: Isocyanate group-terminated urethane resin “TAKENATE” (registered trademark) A-65 (manufactured by Mitsui Chemicals, Inc.)

[0145] Polyol compound 1: Polypropylene glycol “PREMINOL” (registered trademark) 5001F (manufactured by AGC Inc.)

[0146] Polyol compound 2: Polyester polyol “VYLON” (registered trademark) 220 (manufactured by Toyobo Co., Ltd.)

[0147] Compound (b) 1: Urethane isocyanate containing neither acryloyl group nor polyester structure (“ECOAD” (registered trademark) EA-N373A)

[0148] Compound (b) 2: Urethane acrylate (“ARONIX” (registered trademark) UA-306T manufactured by Kyoeisha Chemical Co., Ltd.) containing acryloyl group but not containing polyester structure

[0149] Compound (b) 3: Urethane acrylate “ARONIX” (registered trademark) M-1200 (manufactured by Toagosei Co., Ltd.) containing an acryloyl group and a polyester structure,

[0150] White pigment (c): Titanium oxide (“TIPAQUE” (registered trademark) CR58-2 manufactured by Ishihara Sangyo Kaisha, Ltd.)

[0151] Wax (d): Polyethylene wax (“Hi-Wax” (registered trademark) 320P manufactured by Mitsui Chemicals, Inc.)

[0152] Diluting agent: Trimethylolpropane acrylate ethylene oxide adduct (“Miramer” (registered trademark) M3130 manufactured by Miwon Specialty Chemical Co., Ltd.)

[0153] Solvent: Ethyl acetate

Examples 1 to 16

[0154] (Coating Agent 1 to 11)

[0155] (Meth)acrylate having a hydroxyl group, a polyisocyanate compound, and a polyol compound were mixed at a ratio shown in Tables 1 and 2, and reacted by heating and stirring at 60° C. for 6 hours to produce a compound (a), which was used as a coating agents 1 to 11. As a result of checking the molecular structure of each compound (a) of the coating agents 1 to 11 by 1H NMR, it was found that any compound (a) included a compound (a) having two or more (meth)acryloyl groups and an isocyanate group.

[0156] The acrylic equivalents of the coating agents 1 to 11, the isocyanate content of the coating agent, and the weight-average molecular weight of the compound (a) are shown in Tables 1 and 2.

[0157] (Coating Agents 12 and 13)

[0158] (Meth)acrylate having a hydroxyl group, a polyisocyanate compound, and a polyol compound were mixed at a ratio shown in Table 3, and reacted by heating and stirring at 60° C. for 6 hours to produce a compound (a). Furthermore, a diluting agent or a solvent was added to the obtained compound (a) at a ratio shown in Table 3, and the mixture was stirred and mixed at 60° C. for 1 hour. These compositions were used as coating agents 12 and 13. As a result of checking the molecular structure of each compound (a) of the coating agents 12 and 13 by 1H NMR, it was found that any compound (a) included a compound (a) having two or more (meth)acryloyl groups and an isocyanate group.

[0159] The acrylic equivalents of the coating agents 12 and 13, the isocyanate content of the coating agent, and the weight-average molecular weight of the compound (a) are shown in Table 3.

[0160] (Coating Agents 14 to 16)

[0161] (Meth)acrylate having a hydroxyl group, a polyisocyanate compound, and a polyol compound were mixed at a ratio shown in Table 4, and reacted by heating and stirring at 60° C. for 6 hours to produce a compound (a). Furthermore, a compound (b) was added to the obtained compound (a) at a ratio shown in Table 4, and the mixture was stirred and mixed at 60° C. for 1 hour. These compositions were used as coating agents 14 to 16. As a result of checking the molecular structure of each compound (a) of the coating agents 14 to 16 by 1H NMR, it was found that any compound (a) included a compound (a) having two or more (meth)acryloyl groups and an isocyanate group.

[0162] The acrylic equivalents of the coating agents 14 and 16, the isocyanate content of the coating agent, and the weight-average molecular weight of the compound (a) are shown in Table 4.

TABLE-US-00001 TABLE 1 Coating agent 1 2 3 4 5 6 Composition Compound (Meth)acrylate 1 having hydroxyl group 46 58 31 13 9 58 (parts by (a) (Meth)acrylate 2 having hydroxyl group — — — 11 6 — mass) Polyisocyanate compound 1 45 31 33 27 16 — Polyisocyanate compound 2 — — — — 13 31 Polyol compound 1 — — — — — — Polyol compound 2 9 11 36 49 56 11 Physical Acrylic equivalent (g/eq) 252 200 374 444 717 200 properties Isocyanate content (mass %) 4.7 0.8 2.3 2.5 2.0 1.7 Weight-average molecular weight of compound (a) 1500 2900 4200 7400 11200 2200 Viscosity (Pa .Math. s) 33 52 78 156 211 38

TABLE-US-00002 TABLE 2 Coating agent 7 8 9 10 11 Composition Compound (Meth)acrylate 1 having hydroxyl group 50 41 39 35 — (parts by (a) (Meth)acrylate 2 having hydroxyl group — — — — 23 mass) Polyisocyanate compound 1 40 50 53 58 77 Polyisocyanate compound 2 — — — — — Polyol compound 1 — — — — — Polyol compound 2 10 9 8 7 — Physical Acrylic equivalent (g/eq) 232 283 297 331 422 properties Isocyanate content (mass %) 3.1 7.5 9.3 13.0 5.3 Weight-average molecular weight of compound (a) 1600 1400 1100 1100 750 Viscosity (Pa .Math. s) 33 30 26 21 8

TABLE-US-00003 TABLE 3 Coating agent 12 13 Composition Compound (Meth)acrylate 1 having 30 30 (parts by (a) hydroxyl group mass) (Meth)acrylate 2 having — — hydroxyl group Polyisocyanate 29 29 compound 1 Polyisocyanate — — compound 2 Polyol compound 1 — — Polyol compound 2  6  6 Diluting agent 35 — Solvent — 35 Physical Acrylic equivalent (g/eq) 192  387  properties Isocyanate content (mass %)   3.1   3.0 Weight-average molecular weight of 1400  1500  compound (a) Viscosity (Pa .Math. s) 13  7

TABLE-US-00004 TABLE 4 Coating agent 14 15 16 17 18 Composition Compound (Meth)acrylate 1 having hydroxyl group 30 30 30 30 31 (parts by (a) (Meth)acrylate 2 having hydroxyl group — — — — — mass) Polyisocyanate compound 1 29 29 29 29 33 Polyisocyanate compound 2 — — — — — Polyol compound 1 — — — — — Polyol compound 2 6 6 6 6 36 Compound Compound (b) 1 35 — — — — (b) Compound (b) 2 — 35 — — — Compound (b) 3 — — 35 — — white pigment (c) — — — 35 — Wax (d) — — — — 1 Physical Acrylic equivalent (g/eq) 387 187 279 387 378 properties Isocyanate content (mass %) 6.6 3.1 3.0 3.0 2.3 Weight-average molecular weight of compound (a) 1400 1400 1400 1400 4200 Viscosity (Pa .Math. s) 25 42 71 45 78

[0163] Using the prepared coating agents 1 to 16, film 1, and ink 1, a printed article was prepared by the printing method 1. As the diluting agent and solvent were small, the isocyanate content of the compound (a) was high, and the acrylic equivalent was also small, the coating agent reacted with the film and the active energy ray-curable ink, and the adhesion tended to increase. In addition, as the viscosity of the coating agent was lower, the glossiness of the non-printing portion of the printed article tended to be higher, but in Examples 9 to 14 having a lower viscosity, scattering of the coating agent in the printer was observed. The results are shown in Tables 5 and 6.

TABLE-US-00005 TABLE 5-1 Examples 1 2 3 4 Coating agent 1 2 3 4 Film 1 1 1 1 Black ink 1 1 1 1 Printing method 1 1 1 1 Curability of coating agent A A A A Storage stability of coating A A A A agent Laminate peeling strength 3.8 1.5 3.4 2.2 (N/15 mm) Fracture mode Printing Peeling Printing Peeling film between film between breakage film/ breakage coating coating layer/ink layer Glossiness 117 107 96 73 Area ratio of carbon-carbon 0.8 1.5 0.5 0.5 double bond/carbonyl group

TABLE-US-00006 TABLE 5-2 Examples 5 6 7 8 Coating agent 5 6 7 8 Film 1 1 1 1 Black ink 1 1 1 1 Printing method 1 1 1 1 Curability of coating agent A A A A Storage stability of coating A A A A agent Laminate peeling strength 1.5 1.4 3.3 3.6 (N/15 mm) Fracture mode Peeling Peeling Printing Printing between between film film coating film/ breakage breakage layer/ink coating layer Glossiness 55 116 114 122 Area ratio of carbon-carbon 0.4 1.4 1.0 0.7 double bond/carbonyl group

TABLE-US-00007 TABLE 6-1 Examples 9 10 11 12 Coating agent 9 10 11 12 Film 1 1 1 1 Black ink 1 1 1 1 Printing method 1 1 1 1 Curability of coating agent A A A A Storage stability of coating B C A A agent Laminate peeling strength 3.3 2.5 2.0 1.4 (N/15 mm) Fracture mode Printing Peeling Peeling Peeling film between between between breakage coating film/ film/ layer/ink coating coating layer layer Glossiness 125 126 130 130 Area ratio of carbon-carbon 0.7 0.5 0.3 1.7 double bond/carbonyl group

TABLE-US-00008 TABLE 6-2 Examples 13 14 15 16 Coating agent 13 14 15 16 Film 1 1 1 1 Black ink 1 1 1 1 Printing method 1 1 1 1 Curability of coating agent A A A A Storage stability of coating A B A A agent Laminate peeling strength 1.1 2.6 3.1 3.1 (N/15 mm) Fracture mode Peeling Peeling Printing Printing between between film film film/ coating breakage breakage coating layer/ink layer Glossiness 132 125 115 96 Area ratio of carbon-carbon 0.9 1.1 0.6 0.7 double bond/carbonyl group

Example 17

[0164] A printed article was prepared in the same manner as in Example 1 except that the printing method was changed to the printing method 2. Although the adhesion was lower than that in the printing method 1, the printing density tended to improve from 1.8 to 2.0. The results are shown in Table 7.

Examples 18 to 21

[0165] A printed article was prepared in the same manner as in Example 1 except that the films were changed as shown in Table 7. The adhesion with the coating agent varied depending on the film, and films containing many polar groups on the surface, such as a film having a corona treatment layer, a film having an easily adhesive layer, and a transparent vapor deposition film, tended to exhibit good adhesion. The results are shown in Table 7.

Example 22

[0166] A printed article was prepared in the same manner as in Example 1 except that the black ink 1 was changed to the black ink 2. The adhesion with the coating agent varied depending on the active energy ray-curable ink, and the ink 1 containing a polar group had better adhesion than that of the ink 2. The results are shown in Table 7.

Example 23

[0167] (Coating Agent 17)

[0168] (Meth)acrylate having a hydroxyl group, a polyisocyanate compound, and a polyol compound were mixed at a ratio shown in Table 4, and reacted by heating and stirring at 60° C. for 6 hours to produce a compound (a). Furthermore, a white pigment (c) was added to the obtained compound (a) at a ratio shown in Table 4, and the mixture was stirred and mixed at 60° C. for 1 hour. This composition was used as a coating agent 17. As a result of checking the molecular structure of each compound (a) of the coating agent 17 by 1H NMR, it was found that a compound (a) having two or more (meth)acryloyl groups and an isocyanate group was included.

[0169] A printed article was prepared in the same manner as in Example 1 except that the printing method was changed to the printing method 4 by using the coating agent 17. The coating agent was transferred only to a portion corresponding to the image, and hiding property by white was checked. The adhesion was as good as 2.2 N/15 mm.

TABLE-US-00009 TABLE 7-1 Examples 17 18 19 20 Coating agent 1 1 1 1 Film 1 2 3 4 Black ink 1 1 1 1 Printing method 2 1 1 1 Laminate peeling strength 1.2 1.4 2.7 4.2 (N/15 mm) Fracture mode Peeling Peeling Peeling Printing between between between film coating film/ film/ breakage layer/ink coating coating layer layer Print density 2.0 1.8 1.8 1.8 Glossiness 115 110 114 117 Area ratio of carbon-carbon 0.5 0.7 0.8 0.7 double bond/carbonyl group

TABLE-US-00010 TABLE 7-2 Examples 21 22 23 Coating agent 1 1 17 Film 5 1 1 Black ink 1 2 1 Printing method 1 1 4 Laminate peeling strength 4.1 2.5 2.2 (N/15 mm) Fracture mode Printing Peeling Peeling film between between breakage coating coating layer/ink layer/ink Print density 1.8 1.8 1.8 Glossiness 114 113 — Area ratio of carbon-carbon 0.7 0.7 — double bond/carbonyl group

Example 24

[0170] A printed article was prepared in the same manner as in Example 1 except that the printing method was changed to the printing method 3. Since Example 24 is a printed article obtained by surface printing, cellophane tape peeling and abrasion resistance of the printed article were evaluated. The ink/coating layer and the coating layer/film were strongly adhered to each other, and no peeling due to the cellophane tape or peeling due to nail rubbing was observed at all.

Example 25

[0171] (Coating Agent 18)

[0172] (Meth)acrylate having a hydroxyl group, a polyisocyanate compound, and a polyol compound were mixed at a ratio shown in Table 4, and reacted by heating and stirring at 60° C. for 6 hours to produce a compound (a). Furthermore, wax (d) was added to the obtained compound (a) at a ratio shown in Table 4, and the mixture was stirred and mixed at 60° C. for 1 hour. This composition was used as a coating agent 18. As a result of checking the molecular structure of each compound (a) of the coating agent 18 by 1H NMR, it was found that a compound (a) having two or more (meth)acryloyl groups and an isocyanate group was included.

[0173] A printed article was prepared in the same manner as in Example 24 except that the printing method was changed to the printing method 5 by using the coating agent 18 was used as a coating agent. That is, in Example 24, the coating agent was used as an anchor coat, but in Example 25, the coating agent was used as an overcoat agent for the entire printing surface. Since Example 25 is also a printed article obtained by surface printing, cellophane tape peeling and abrasion resistance of the printed article were evaluated. The ink/coating layer and the coating layer/film were strongly adhered to each other, and no peeling due to the cellophane tape or peeling due to nail rubbing was observed at all.

Comparative Example 1

[0174] A printed article was prepared in the same manner as in Example 20 except that the coating agent was not used. Since Comparative Example 1 is a printed article obtained by surface printing, cellophane tape peeling and abrasion resistance of the printed article were evaluated. The adhesion between the ink and the film was extremely low, and the ink was completely peeled off from the white ink as a base due to the cellophane tape peeling, and the abrasion resistance was also insufficient.

TABLE-US-00011 TABLE 8 Comparative Examples Example 24 25 1 Coating agent 1 18 Absent Film 1 1 1 Black ink 1 1 1 Printing method 3 5 3 Print density 1.8 1.8 1.8 Cellophane tape peeling A A B Abrasion resistance A A B Glossiness 115 91 — Area ratio of carbon-carbon 0.5 0.5 — double bond/carbonyl group

Comparative Examples 2 to 4

[0175] (Coating Agent 19)

[0176] A polyisocyanate compound 1 was used alone as a target to be compared with the compound (a), a diluting agent was added at a charging ratio shown in Table 9, and the mixture was stirred and mixed at 60° C. for 1 hour. This composition was used as a coating agent 19.

[0177] (Coating Agent 20)

[0178] Polyisocyanate compounds 1 and 2 and a polyol compound 1 were heated and stirred at 60° C. for 6 hours to react at the charging ratio shown in Table 9, and thereby a target to be compared with the compound (a) was prepared, and used as a coating agent 20.

[0179] (Coating Agent 21)

[0180] (Meth)acrylate 1 having a hydroxyl group and a polyol compound 1 were heated and stirred at 60° C. for 6 hours to react at the charging ratio shown in Table 9, and thereby a target to be compared with the compound (a) was prepared, and used as a coating agent 21.

TABLE-US-00012 TABLE 9 Coating agent 19 20 21 Composition Comparative (Meth)acrylate 1 having — — 80 (parts by target with hydroxyl group mass) compound (a) (Meth)acrylate 2 having — — — hydroxyl group Polyisocyanate 70 25 — compound 1 Polyisocyanate — 39 — compound 2 Polyol compound 1 — 36 20 Polyol compound 2 — — — Diluting agent 30 — — Physical Acrylic equivalent (g/eq) 447 0 145 properties Isocyanate content (mass %) 14.6 8.5 0.0 Weight-average molecular weight of target 700 7200 2000 to be compared with compound (a) Viscosity (Pa .Math. s) 1 195 2

[0181] Using the prepared coating agents 19 to 21, film 1, and ink 1, a printed article was prepared by the printing method 1. The coating agent 19 having no (meth)acryloyl group and no isocyanate group in the same compound was not completely cured. Further, the coating agent 20 having no (meth)acryloyl group was not cured at all due to insufficient sensitivity. In addition, the coating agent 21 had low adhesion to the film, and peeling was observed at the interface between the coating agent layer and the film. The results are shown in Table 10.

Comparative Example 5

[0182] Using the coating agents, film 1, and ink 1, a printed article was prepared by the printing method 1. The adhesion with the film was extremely low, and peeling was observed at the interface between the ink and the film.

TABLE-US-00013 TABLE 10 Comparative Examples 2 3 4 5 Coating agent 19 20 21 Absent Film 1 1 1 1 Black ink 1 1 1 1 Printing method 1 1 1 1 Curability of coating agent B B A — Storage stability of coating C A A — agent Laminate peeling strength — — 0.1   0.3 (N/15 mm) Fracture mode — — Peeling Peeling between between film/ film/ink coating layer Glossiness — — 133 — Area ratio of carbon-carbon — — 2.8 — double bond/carbonyl group