CATIONIC PHOTOCURABLE COMPOSITION, PAINT, ARTICLE WITH PHOTOCURED COATING, AND INK

Abstract

The present invention provides a cationic photocurable composition, a paint, an article of manufacture with photocured coating, and an ink. The cationic photocurable composition comprises A1; and/or A2; B: an epoxy compound; and C: a cationic initiator. On this basis, in one aspect, when the cationic photocurable composition of the present invention is subsequently used as a paint, the wet adhesion between the coating formed of the paint to a substrate film interface is better, and the coating also has excellent abrasion resistance. In another aspect, when subsequently used as an ink in intaglio printing, the described cationic photocurable composition can also more effectively avoid the occurrence of plate fogging.

##STR00001##

Claims

1. A cationic photocurable composition, wherein the cationic photocurable composition comprises the following components: component A1: ##STR00046## component A2: ##STR00047## component B: an epoxy compound; and component C: a cationic initiator; wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently represent C.sub.1 to C.sub.6 alkyl; the cationic photocurable composition comprises 50 to 70 parts by weight of the component A1, 10 to 30 parts by weight of the component A2, 5 to 25 parts by weight of the component B, and 1 to 10 parts by weight of the component C, and the sum of the parts by weight of the component A1 and the component A2 is 65 to 95 parts.

2. The cationic photocurable composition according to claim 1, wherein the cationic photocurable composition comprises 50 to 70 parts by weight of the component A1, 10 to 25 parts by weight of the component A2, 5 to 25 parts by weight of the component B, and 1 to 5 parts by weight of the component C, and the sum of the parts by weight of the component A1 and the component A2 is 70 to 90 parts.

3. The cationic photocurable composition according to claim 1, wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently represent C.sub.1 to C.sub.3 alkyl.

4. The cationic photocurable composition according to claim 1, wherein R.sub.1 and R.sub.2 are the same, and R.sub.3 and R.sub.4 are the same.

5. The cationic photocurable composition according to claim 1, wherein the component A1 is ##STR00048##

6. The cationic photocurable composition according to claim 1, wherein the component A2 is ##STR00049##

7. The cationic photocurable composition according to claim 1, wherein the epoxy compound is selected from one or more of alicyclic epoxy compounds, aromatic epoxy compounds, or monofunctional oxetanes.

8. The cationic photocurable composition according to claim 1, wherein the cationic initiator is selected from onium salts.

9. The cationic photocurable composition according to claim 8, wherein the onium salt is selected from one or more of diaryliodonium salts of phosphoric acid, triarylsulfonium salts of phosphoric acid, or triarylsulfonium salts of antimonic acid.

10. The cationic photocurable composition according to claim 1, wherein the cationic photocurable composition further comprises component D: a sensitizer.

11. The cationic photocurable composition according to claim 10, wherein the component D has a mass percentage of 0.1 to 5% in the cationic photocurable composition.

12. The cationic photocurable composition according to claim 10, wherein the component D is selected from one or more of thioxanthone compounds, xanthone compounds, acridine compounds, anthracene compounds, or coumarin compounds; more preferably, anthracene compounds and/or thioxanthone compounds.

13. The cationic photocurable composition according to claim 1, wherein the cationic photocurable composition further comprises component E: a colorant.

14. The cationic photocurable composition according to claim 13, wherein the component E has a mass percentage of 2 to 20% in the photocurable resin composition.

15. The cationic photocurable composition according to claim 13, wherein the colorant is selected from inorganic pigment and/or organic pigment; wherein the organic pigment is selected from one or more of perylenes, phthalocyanine dyes, cyanine pigments, naphthalocyanine pigments, nitroso pigments, azo pigments, diazo pigments, diazo condensation pigments, basic dye pigments, basic blue pigments, indigo pigments, phloxin pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, carbazole dioxazine violet pigments, alizarin lake pigments, phthaldiamide pigments, carmine lake pigments, tetrachloroisoindolinone pigments, perinone pigments, anthraquinone pigments, or quinophthalone pigments; and the inorganic pigment is selected from one or more of metal oxides, silicon oxides, carbon black pigments, metal sulfides, or metal chlorides.

16. A paint, wherein the paint comprises the cationic photocurable composition according to claim 1.

17. An article with photocured coating, comprising a substrate layer and a photocured coating coated on at least a portion of the substrate layer, wherein the photocured coating is formed from the cationic photocurable composition according to claim 1 by radiation curing.

18. The article with photocured coating according to claim 17, wherein the substrate layer is a metal substrate layer or a plastic substrate layer.

19. The article with photocured coating according to claim 17, wherein the radiation curing is performed under a radiation source, wherein the radiation source is selected from one or more of ultraviolet light, visible light, infrared light, electron beam, or laser.

20. An ink, wherein the ink comprises the cationic photocurable composition according to claim 13.

Description

DESCRIPTION OF EMBODIMENTS

[0044] Hereinafter, the present invention will be further described in detail with reference to specific examples, which cannot be understood as a limitation to the protection scope of the present invention.

1. Preparation of the Composition

[0045] According to the formulations shown in Examples 1-8 in Table 1, the raw materials were stirred at a constant speed for 1 hour using a high-speed stirrer under a yellow light lamp condition, then ground using a sand grinder, and then filtered through a filter screen with a particle size of 1 m, to obtain a composition. Unless otherwise specified, the quantities in each example are based on parts by weight.

TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Comparative Comparative Comparative Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 1 2 3 4 5 6 A1 50 55 60 70 75 A1 60 65 A1 70 70 45 A2 25 10 10 20 15 5 10 10 10 10 A2 20 20 15 35 A3 70 A4 70 A5 70 A6 70 B1 10 15 5 7 2 15 10 10 10 10 B2 15 10 10 B3 10 10 10 5 5 5 8 8 5 5 5 5 5 C1 3 3 3 3 3 3 3 3 C2 3 3 3 3 3 3 D 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 indicates data missing or illegible when filed

##STR00036##

[0046] B1: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate

[0047] B2: 2,2-[(1-methylethylene)bis(4,1-phenylenecarboxaldehyde)]bisoxirane

[0048] B3: 3-benzyloxymethyl-3-ethyloxetane

[0049] C1: 4-isobutyl-4-methyldiphenyliodonium hexafluorophosphate

[0050] C2: 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate

[0051] D: PSS-306 (9,10-diethoxy-2-ethylanthracene, a sensitizer)

1. Curing Performance Test

[0052] The photocurable compositions were sampled on various substrates and applied with a 10 #wire rod to obtain a coating with a thickness of about 8 m. The coating films were exposed to irradiation from a mercury lamp (RW-LED-YT200gl) light source at a temperature of 25 C. and a humidity of 50% RH for 2 seconds, with an energy of 100 mj/cm.sup.2. The film formation by curing was observed and evaluated by the finger touch method. The results are shown in Table 2 below.

[0053] The evaluation criteria for the finger touch method were as follows: [0054] 1. Oily and not cured; [0055] 2. Oily surface and cured bottom; [0056] 3. Sticky surface, with relatively heavy fingerprints after touching; [0057] 4. Essentially dry surface, being slightly astringent and having light fingerprints after touching; [0058] 5. Fully cured, having smooth surface, without fingerprints after touching.

2. Wet Adhesion Test

[0059] The photocurable composition was sampled on various substrates and applied with a 10 #wire rod to obtain a coating with a thickness of about 8 m. The coating film was exposed to irradiation from a mercury lamp (RW-LED-YT200gl) light source at a temperature of 25 C. and a humidity of 50% RH, with an energy of 100 mj/cm.sup.2. After it was completely cured, the coating was post-baked at 80 C. for 30 min, then immersed in room temperature water for 2 h. The adhesion was tested by the cross-cut (100-grid) method, according to the following evaluation criteria: [0060] Level 0: The cut edge was completely smooth without one grid falling off; [0061] Level 1: There was a little coating peeling off at the intersection of incisions, with the affected cross-cut areas of not greater than 5%; [0062] Level 2: There was coating peeling off at the intersection of incisions and/or along the edge of incisions, with the affected areas of greater than 5% but not greater than 15%; [0063] Level 3: The coating was partially or completely peeled off in large fragments along the cut edge, and/or partially or completely peeled off on different parts of the grids, with the affected cross-cut areas of greater than 15% but not greater than 35%; [0064] Level 4: The coating was peeled off in large fragments along the cut edge, and/or some grids were partially or completely peeled off, with the affected cross-cut areas of greater than 35% but not greater than 65%; [0065] Level 5: The degree for peeling off exceeded Level 4.

3. Scratch Resistance Test

[0066] The photocurable composition was sampled on various substrates and applied with a 10 #wire rod to obtain a coating with a thickness of about 8 m. The coating film was exposed to irradiation from a mercury lamp (RW-LED-YT200gl) light source at a temperature of 25 C. and a humidity of 50% RH, with an energy of 100 mj/cm.sup.2. After it was completely cured, the cured film was rubbed back and forth with a #0000 steel wool ball, with a load of 500 g and a friction distance of 5 to 6 cm. The number of back and forth frictions at the time that the cured film was rubbed to have any traces was used to make the evaluation. The larger the value, the better the scratch resistance is.

TABLE-US-00002 TABLE 2 Curing performance Wet adhesion Scratch resistance Aluminum Aluminum Aluminum PP PE PET Tinplate Plate PP PE PET Tinplate Plate PP PE PET Tinplate Plate Ex. 1 5 5 5 5 5 0 0 0 0 0 1230 1216 1661 1489 1504 Ex. 2 5 5 5 5 5 0 0 0 0 0 1265 1244 1675 1503 1519 Ex. 3 5 5 5 5 5 0 0 0 0 0 1480 1467 1814 1635 1768 Ex. 4 5 5 5 5 5 0 0 0 0 0 1372 1360 1725 1624 1695 Ex. 5 5 5 5 5 5 0 0 0 0 0 1298 1290 1697 1525 1558 Ex. 6 5 5 5 5 5 0 0 0 0 0 1400 1377 1753 1600 1621 Ex. 7 5 5 5 5 5 0 0 0 0 0 1335 1305 1712 1561 1595 Ex. 8 5 5 5 5 5 0 0 0 0 0 1430 1401 1796 1647 1712 Comparative 5 5 5 5 5 2 3 2 2 2 1200 1160 1400 1270 1305 Ex. 1 Comparative 3 1 4 4 4 2 3 1 1 1 1038 1013 1089 1053 1070 Ex. 2 Comparative 3 3 4 4 4 3 3 2 2 2 723 704 753 822 796 Ex. 3 Comparative 3 3 4 4 4 3 3 2 2 2 809 785 858 928 830 Ex. 4 Comparative 3 3 4 4 4 3 3 2 2 2 868 831 879 982 952 Ex. 5 Comparative 3 3 3 3 3 3 3 1 1 1 682 636 766 704 726 Ex. 6

2. Preparation Of Gravure Ink

[0067] According to the formulations shown in Examples 1-8 in Table 3, the raw materials were stirred at a constant speed for 1 hour using a high-speed stirrer under a yellow light condition, then ground using a sand grinder, and then filtered through a filter screen with a particle size of 1 m, to obtain a gravure ink composition. Unless otherwise specified, the quantities in each example are based on parts by weight.

TABLE-US-00003 TABLE 3 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Comparative Comparative Comparative Comparative Comparative Comparative Comparative 1 2 3 4 5 6 7 8 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 A1 50 60 55 65 75 A1 55 60 A1 65 65 40 65 A2 20 10 10 20 15 5 10 10 10 10 10 A2 20 10 15 35 A3 65 A4 65 A5 65 A6 65 B1 10 15 5 7 2 10 10 10 10 10 15 B2 15 10 10 B3 10 10 10 5 5 5 8 8 5 5 5 5 5 C1 4 4 4 4 4 4 4 4 4 C2 4 4 4 4 4 4 D 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 E 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 A1: [00037]A1: [00038]A1: [00039]A2: [00040]A2: [00041]A3: [00042]A4: [00043]A5: [00044]A6: [00045]B1: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate B2: 2,2-[(1-methylethylene)bis(4,1-phenylenecarboxaldehyde)]bisoxirane B3: 3-hydroxymethyl-3-ethyloxetane C1: 4-isobutyl-4-methyldiphenyliodonium hexafluorophosphate C2: 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate D: PSS-306 (9,10-diethoxy-2-ethylanthracene, a sensitizer) E: inorganic carbon black (Clariant Chemicals (China) Ltd.)

2. Curing and Drying Speed Test

[0068] The ink to be tested was printed using a Sotech solvent-free gravure printer (model: A380), wherein an LED lamp with a wavelength of 385 nm was added to the machine as a radiation light source. The ink to be tested was transferred to a PET film (common industrial film FP2, Lucky Group Corporation) by the gravure printer, wherein the printing thickness was set to 5 m, and the irradiation intensity of the LED light source was 20 w/cm.sup.2.

[0069] After the light exposure, it was left for 24 hours, and the surface curing status was evaluated according to the finger touch method in the paint film drying time test standard GB/T 1728-1979 (that is, touching the coating lightly with the finger, and confirming the surface dryness by smooth and non-sticky surface without fingerprints when pressed. The drying speed was expressed as the maximum linear speed that achieves the surface drying effect, in m/min.

3. Performance Evaluation

[0070] The linear speeds on the gravure printer were set to 220 m/min and 150 m/min, respectively. The PET film was used as the substrate, the printing thickness was set to 5 m, and the irradiation intensity of the 385 nm LED light source was 20 w/cm.sup.2. After exposure, it was left for 24 hours, and the layout fogging and adhesion of the cured coating were then evaluated.

(1) Coating Adhesion Test

[0071] According to GB/T9286-1998 Scratch Test of Paint and Varnish Film, the adhesion on the substrate was tested by cross-cut (100-grid scratching knife) method using QFH paint film grid-scratching instrument. The specific procedure was as follows:

[0072] The knife tool that complies with GB/T9286-1998 Scratch Test of Paint and Varnish Film was used to cut on the coating surface, to ensure that the scratching reaches the substrate surface each time. The coating surface was cleaned with a soft brush, a tape was applied on the coating such that the tape was in full contact with the coating, and the tape was finally torn from the coating surface, to evaluate the results. [0073] Level 0: The cut edge was completely smooth without one grid falling off; [0074] Level 1: There was a little coating peeling off at the intersection of incisions, with the affected cross-cut areas of not greater than 5%; [0075] Level 2: There was coating peeling off at the intersection of incisions and/or along the edge of incisions, with the affected areas of greater than 5% but not greater than 15%; [0076] Level 3: The coating was partially or completely peeled off in large fragments along the cut edge, and/or partially or completely peeled off on different parts of the grids, with the affected cross-cut areas of greater than 15% but not greater than 35%; [0077] Level 4: The coating was peeled off in large fragments along the cut edge, and/or some grids were partially or completely peeled off, with the affected cross-cut areas of greater than 35% but not greater than 65%; [0078] Level 5: The degree for peeling off exceeded Level 4.

(2) Layout Fogging Test

[0079] A printed product was obtained by printing on a PET film using the gravure printer at a printing speed of 220 m/min, irradiating at an intensity of 20 w/cm.sup.2 by 385 nm LED light source, and being left for 24 hours after exposure. The amount of ink (i.e., degree of layout fogging) attached to the blank area (non-image area) of the printed film obtained was visually evaluated according to the following criteria: [0080] 5: No ink transfer was observed in the non-image area. [0081] 4: Slight ink transfer was observed in a small region (less than 5%) of the non-image area. [0082] 3: Ink transfer was observed in the middle region (less than 5% to 10%) of the non-image area. [0083] 2: Ink transfer was observed in a large region (10% or more) of the non-image region. [0084] 1: Ink transfer was observed over the entire non-image area.

TABLE-US-00004 TABLE 4 Curing and drying speed Adhesion Layout fogging Example 1 210 0 5 Example 2 220 0 5 Example 3 240 0 5 Example 4 240 0 5 Example 5 235 0 5 Example 6 235 0 5 Example 7 220 0 5 Example 8 240 0 5 Comparative Example 1 235 3 5 Comparative Example 2 200 0 4 Comparative Example 3 170 2 3 Comparative Example 4 190 1 3 Comparative Example 5 180 2 3 Comparative Example 6 150 0 2 Comparative Example 7 220 3 4

[0085] It can be seen from the performance evaluation results in Table 4 that, the cationic photocurable composition of the present invention has excellent curing performances, can well solve the layout fogging problem in the gravure printing ink, and has strong application prospects.

[0086] The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, and improvement made within the spirit and principle of the invention shall be included within the scope of the invention.