Cationic photocurable compositions, paints, products having a photocurable coating layer, inks

Abstract

The present invention provides a cationic photocurable composition, a paint, a product having a photocured coating layer, and an ink. The cationic photocurable composition comprises A1: 【Chemical formula 43】 TIFF2025518683000049.tif23155, and A2: 【Chemical formula 44】 TIFF2025518683000050.tif20154, B: an epoxy compound, and C: a cationic initiator. Based on this, when the cationic photocurable composition of the present invention is subsequently applied as a paint, the wet adhesion between the formed coating layer and the substrate film interface is more excellent, and the coating layer further has very excellent scratch resistance performance. In addition, when the above cationic photocurable composition is subsequently applied to gravure printing as an ink, the occurrence of mist problems can be more effectively avoided.

Description

Technical Field

[0001] This application is based on and claims priority to a Chinese application with CN application number 202210726411.3 and a filing date of June 24, 2022, and the entire disclosure content of the CN application is incorporated herein again. The present invention relates to the field of photocuring technology, specifically to cationic photocurable compositions, paints, products having a photocured coating layer, and inks.

Background Art

[0002] As the field of photocuring technology develops, cationic photocurable compositions have been attracting more and more attention from researchers in the production and application of products such as photocurable paints and photocurable inks. (1) Regarding the use of cationic photocurable compositions in photocurable paint products Plastic or metal materials are one of the commonly used materials in our life and industry. For example, they are widely applied in the packaging industry such as food, beverage packaging, and pharmaceutical packaging. However, the adhesion between the metal material and the photocured coating layer is poor, especially in a high-humidity environment (especially during the plum rain season in the south of China).

[0003] Among the prior arts, CN112574650A (Patent Document 1) discloses a cationic curable composition for a metal substrate. The composition includes a polyhydroxy resin, an epoxy compound, an oxetane group-containing compound, and a cationic initiator. The polyhydroxy resin is a polyester resin and / or a phenolic resin, and the molar ratio of the hydroxy group, the 3-member epoxy group, and the 4-member epoxy group is 1:(1 - 15):(1 - 25). The cationic curable composition can significantly improve the adhesion of the coating layer to the metal substrate, but does not mention the wet adhesion performance.

[0004] CN100473681C (Patent Document 2) discloses a novel method for surface treatment of plastic materials, the method comprising applying a composition to at least one surface of a plastic material and then polymerizing and / or crosslinking the surface to be treated by exposure to a radiation source and / or electron beam, the composition comprising 1 to 99 wt% of at least one polymerizable and / or at least partially polymerizable organic matrix A having an oxetane-reactive functional group (frA), and at least one polymerizable and / or at least partially polymerizable organic matrix B It contains 1 to 99 wt% of epoxy (α1) and / or acrylate (α2) and / or alkenyl ether (α3) and / or hydroxy (α4) reactive functional group (frB), a (copolymer) monomer, (copolymer) oligomer and / or (co)polymer, an effective amount of at least one cation or a cation and radical initiator system C, and selectively at least one sensitizer D and at least one pigment E, and has good adhesion to polypropylene (PP) plates. However, wet adhesion performance is not mentioned.

[0005] CN103781814A (Patent Document 3) discloses a photocurable resin composition containing (A) a polyol acrylate compound, (B) a compound having an acrylic acid group or a methacrylic acid group and a carboxyl group in the molecule, (C) a siloxane compound, and (D) a photoradical initiator, and exhibits good moisture resistance and scratch resistance on glass substrates and ITO substrates. However, no studies have been conducted on moisture resistance and scratch resistance on plastic substrates or metal substrates.

[0006] CN112574649A (Patent Document 4) discloses a cationic curable composition for a plastic substrate, which comprises a polyhydroxy resin, an epoxy compound, an oxetane group-containing compound, and a cationic initiator. The polyhydroxy resin is a polyester resin, an acrylic resin, and / or a phenolic resin, and in the cationic curable composition, the molar ratio of hydroxyl groups, 3-membered epoxy groups, and 4-membered epoxy groups is 1:(3~20):(1~25). This cationic curable composition can significantly improve the adhesion of the coating layer to the plastic substrate, but its wet adhesion performance is not mentioned.

[0007] Meanwhile, with the rapid development of Japan's flat panel display industry, the demand for plastic substrates is increasing in advanced fields such as liquid crystal displays, semiconductor lighting, semiconductor flexible circuit boards, and electronic equipment. However, compared to glass substrates, plastics are generally softer, have lower surface hardness, and are easily scratched, so a protective layer needs to be applied to their surface. Such a protective layer must have good scratch resistance while also possessing sufficient flexibility. Furthermore, such a coating layer should adhere well to the surface of the substrate to which it is applied. In particular, when plastic substrates are used in display devices such as LCDs and OLEDs, not only is good adhesion to the coating layer required, but good wet adhesion even under high humidity conditions (especially during the rainy season in southern Japan) is also required. Therefore, the adhesion of the interface between the metal or plastic substrate and the coating layer, especially preventing a decrease in wet adhesion between the substrate and the photocurable composition coating layer under high humidity conditions, is a major problem that needs to be solved in the application of metals or plastics.

[0008] (ii) Use of cationic photocurable compositions in photocurable ink products In conventional technology, when ink is applied to gravure printing, a mist problem occurs (in this invention, mist refers to the phenomenon in which ink on the printing plate that has not been sufficiently removed by the doctor blade is transferred to the substrate during printing, resulting in contamination of the substrate of the printed material).

[0009] As described above, conventional cationic photocurable compositions, when applied as coating material, suffer from problems such as reduced wet adhesion between the coating layer and the plastic or metal substrate film, and poor scratch resistance of the coating layer. On the other hand, conventional cationic photocurable compositions, when applied as ink materials, also suffer from mist problems. Therefore, there is a need to provide a new cationic curable composition to solve the above problems. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Chinese Patent Application Publication No. 112574650 Specification [Patent Document 2] Chinese Patent No. 100473681 Specification [Patent Document 3] Chinese Patent Application Publication No. 103781814 [Patent Document 4] Chinese Patent Application Publication No. 112574649 Specification [Overview of the project]

[0011] The main object of the present invention is to provide a cationic photocurable composition, paint, product having a photocurable coating layer, and ink in order to address the problems that arise when conventional cationic curable compositions are applied as coating layer materials, such as reduced wet adhesion between the coating layer and the plastic or metal substrate film interface, and poor scratch resistance of the coating layer, and the problem of mist that arises when conventional cationic curable compositions are applied as ink materials. In addition, the embodiments and features described herein may be combined with each other, as long as there is no contradiction. The present invention will be described in detail below with reference to the embodiments.

[0012] As described in the background section of the present invention, when a cation-curable composition in the prior art is applied as a coating layer material, problems such as a decrease in the wet adhesion between the coating layer and the plastic or metal substrate film interface, or poor scratch resistance of the coating layer exist. And when the cation-curable composition in the prior art is applied as an ink material, there is a problem of mist. To solve this problem, the present invention provides

[0013] A1:

[0014] [Chemical formula]

[0015] and A2:

[0016] [Chemical formula]

[0017] and (In the formula, R1, R2, R3, R4, and R5 each independently represent a C1-C6 alkyl group.) B: an epoxy compound, C: a cation initiator, and contains by weight, 50 to 70 parts of A1, 10 to 30 parts of A2, 5 to 25 parts of B, and 1 to 10 parts of C, and the total of the parts by weight of A1 and A2 is 65 to 95 parts, to provide a cationic photocurable composition.

[0018] The inventor of the present application has surprisingly found that when a compound represented by the general formula A1 is blended with a compound represented by the general formula A2 and an epoxy compound B in a predetermined number of parts by weight and used as a cationic photocurable composition, the composition has a lower viscosity, a faster curing rate, is insensitive to moisture, and further has excellent adhesion. Based on this, when the cationic photocurable composition of the present invention is subsequently applied as a paint (aqueous), the wet adhesion between the photocured coating layer formed thereby and the substrate film interface is more excellent. At the same time, the coating layer also has extremely excellent scratch resistance performance. In addition, it has been found that when the above cationic photocurable composition is subsequently applied to gravure printing as an ink (oil-based), the occurrence of mist problems can also be avoided. In the actual process, the cationic photocurable composition of the present invention is in 100 parts by weight, that is, the total number of parts by weight of all components in the cationic photocurable composition is 100 parts.

[0019] In one preferred embodiment, the cationic photocurable composition contains, in parts by weight, 50 to 70 parts of A1, 10 to 25 parts of A2, 5 to 25 parts of B, and 1 to 5 parts of C, and the total of the parts by weight of A1 and A2 is 70 to 90 parts. Based on this, when the cationic photocurable composition is subsequently applied as a paint, the wet adhesion between the photocured coating layer formed thereby and the substrate is further improved, and the scratch resistance performance of the photocured coating layer is also greatly improved. In addition, when the above cationic photocurable composition is subsequently applied to gravure printing as an ink, the problem of mist can be better avoided.

[0020] In one preferred embodiment, R1, R2, R3, R4, and R5 are each independently represent an alkyl group having 1 to 3 carbon atoms. Preferably, R1 and R2 are the same, and R3 and R4 are the same. Based on this, the raw materials are easier to obtain. More preferably, A1 is

[0021] [[ID=z16]]

Chemical formula

[0022] And A2 is,

[0023] [ka]

[0024] That is the case. In one preferred embodiment, the epoxy compound is one or more selected from the group consisting of alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, or monofunctional oxetanes.

[0025] For example, the alicyclic epoxy compound may be one or more selected from the group consisting of 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenoate, 3,4,3',4'-diepoxybicyclohexane, 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis(3,4-epoxycyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, 1-[1,1-bis(3,4-epoxycyclohexyl)]ethylbenzene, bis((3,4-epoxycyclohexyl)methyl)adipate, or bis(3,4-epoxycyclohexylmethyl) oxalate. The monofunctional oxetane may be one or more selected from the group consisting of 3-methylol-3-ethyloxetane, 3-benzyloxymethyl-3-ethyloxetane, 3-ethyl-3-phenoxymethyloxetane, or 3-ethyl-3-((octyloxy)methyl)oxetane. Aromatic epoxy compounds are compounds having an aromatic ring and an epoxy group in their molecule. Examples of aromatic epoxy compounds include aromatic ring-conjugated epoxy compounds having a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, etc. Among these, compounds having a bisphenol skeleton and / or a fluorene skeleton are preferred in order to achieve a higher refractive index of the product. Examples of aromatic epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene-based epoxy compounds, etc. Among these, bisphenol A type epoxy compounds and fluorene-based epoxy compounds, such as 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane are preferred. Alicyclic epoxy compounds are compounds that have at least one epoxy group bonded to an alicyclic ring within their molecule. Among these, compounds containing epoxycyclohexyl are preferred as alicyclic epoxy compounds. Furthermore, from the viewpoint of further improving the curing speed of the composition, polyfunctional alicyclic epoxy compounds having two or more alicyclic epoxy groups within their molecule are preferred. Moreover, it is preferable to use a compound having one alicyclic epoxy group within its molecule and an unsaturated double bond such as a vinyl group as the alicyclic epoxy compound.

[0026] In one preferred embodiment, the cationic initiator is selected from onium salts, preferably one or more onium salts selected from the group consisting of diaryliodonium salts of phosphoric acid, triarylsulfonium salts of phosphoric acid, or triarylsulfonium salts of antimony acid. Preferably, the diaryliodonium salt of phosphoric acid is one or more selected from the group consisting of 4,4'-dimethyldiphenyliodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, 4-isopropyl-4'-methyldiphenyliodonium hexafluorophosphate, 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, and 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate in a 25% propylene carbonate solution (25% refers to the mass fraction of the solvent in the solution), and preferably, the triarylsulfonium salt of phosphoric acid is 4-(phenylthio)phenyldi One or more selected from the group consisting of phenylsulfonium hexafluorophosphate, bis(4-(diphenylsulfonio)phenyl) sulfide-bishexafluorophosphate, or triphenylsulfonium hexafluorophosphate, a 50% propylene carbonate solution of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, and a 60% propylene carbonate solution of bis(4-(diphenylsulfonio)phenyl) sulfide-bishexafluorophosphate, preferably the triarylsulfonium salt of antimony acid is bis(4-t-butylphenyl) sulfonium It is one or more selected from the group consisting of hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluoroantimonate, or diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluoroantimonate, and a 50% propylene carbonate solution of diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate.

[0027] More preferably, the cationic photocurable composition of the present invention may contain, in addition to the polymerizable compounds component A1, component A2, and component B, other cationic monomers as needed, provided that they do not negatively affect the application effect of the composition, such as TCM-107, TCM-109, TCM-111, TCM-115, TCM-118, TCM-120 and / or THM-201, THM-202, THM-203, THM-204, THM-205 manufactured by Changzhou Strong Electronics New Materials Co., Ltd. THM206-1, THM207-1, THM-208, THM208-1, THM-209, THM209-1, THM-210, THM-211, THM-212, THM212-1, THM-213, THM-301, THM-401, THM-402, THM403-1, THM403-2, THM404-1, THM-405, THM-406, THM-407, THM-408, THM409-1, THM410-1, THM411-1, THM412-1, THM-413, etc. may be added further.

[0028] In one preferred embodiment, the cationic photocurable composition of the present invention may further contain, in addition to components A1, A2, B, and C, component D: a sensitizer, provided that it does not negatively affect the application effect of the composition, in order to further improve the photosensitivity of the composition or to satisfy the requirements for photocuring with long-wavelength light sources, particularly with UV-LED lamp sources. Preferably, D is 0.1 to 5% by mass relative to the cationic photocurable composition. Preferably, D is one or more selected from the group consisting of thioxanthone compounds, xanthone compounds, acridine compounds, anthracene compounds, and coumarin compounds, more preferably anthracene compounds and thioxanthone compounds, and even more preferably one or more selected from the group consisting of JRCure-1105(ITX) and JRCure-1106(DETX) manufactured by Tianjin Jiuri New Materials, and PSS303, PSS306, PSS510, PSS513, and PSS515 manufactured by Changzhou Strong Electronic New Materials Co., Ltd.

[0029] In one preferred embodiment, the cationic photocurable composition further comprises component E: a colorant (one or more pigments). The pigment may be an inorganic or organic pigment, and is not limited to any color, such as black, blue, brown, blue-green, green, white, purple, magenta, red, orange, and yellow, and mixtures thereof. Preferably, E is 2 to 20% by mass relative to the cationic photocurable composition.

[0030] The applicable organic pigments are perylene, f Taro Cyanine dyes (for example, f Taro Cyanine green, F Taro The inorganic pigments to be applied may include cyanine blue, cyanine pigments (Cy3, Cy5 and Cy7), naphthalocyanine pigments, nitroso pigments, azo pigments, diazo pigments, diazo condensation pigments, basic dye pigments, alkali blue pigments, indigo pigments, phloxine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, carbazoledioxazine violet pigments, alizarin lake pigments, phthalamide pigments, carmine lake pigments, tetrachloroisoindolinone pigments, perinone pigments, anthraquinone pigments and quinophthalone pigments, and mixtures of two or more of these or derivatives thereof. The inorganic pigments to be applied may also include metal oxides (e.g., titanium dioxide, conductive titanium dioxide, iron oxides (e.g., red iron oxide, yellow iron oxide, black iron oxide and transparent iron oxide) and aluminum oxides), silicon oxides, carbon black pigments, metal sulfides, metal chlorides, and mixtures of two or more of these.

[0031] In one preferred embodiment, in addition to components A to E described above, the cationic composition of the present invention may further contain organic and / or inorganic additives commonly used in the art, depending on the application environment of the product, including, but not limited to, fillers, leveling agents, dispersants, curing agents, surfactants, defoamers, and storage stabilizers, which can be easily selected by those skilled in the art according to their needs for their products, and a detailed explanation is omitted here. In one preferred embodiment, the specific manufacturing process of the above-described cationic photocurable composition of the present invention may refer to a general manufacturing method in the field of radiation-curable compositions. Typically, the manufacturing process involves compounding, pre-dispersion, polishing, and filtration (filtration through a screen of a predetermined size to obtain a product with a target particle size) under conditions of constant temperature, constant humidity, and shielding of the radiation source.

[0032] Furthermore, the viscosity (23±2℃) of the cationic photocurable composition of the present invention is not particularly limited. When the composition is subsequently applied to form a coating layer, the viscosity is usually appropriate to be 500 mPa·s or less, preferably 10 to 200 mPa·s. If the viscosity of the cationic photocurable composition exceeds 200 mPa·s or is less than 10 mPa·s, it may result in poor coverage and poor smoothness. Also, if the viscosity of the cationic photocurable composition exceeds 200 mPa·s or is less than 10 mPa·s, the stability of the composition during storage may be poor. The viscosity of the cationic photocurable composition may usually be controlled by thickeners or thinners, which can also be selected by those skilled in the art according to their needs for their products, and a detailed explanation is omitted here.

[0033] The present invention further provides a coating containing the cationic photocurable composition described above. Due to the reasons described above, when the cationic photocurable composition of the present invention is subsequently applied as a coating, the wet adhesion between the photocurable coating layer formed thereby and the substrate layer is superior. Furthermore, the coating layer also possesses excellent scratch resistance. The present invention further provides a product having a photocurable coating layer comprising a substrate layer and a photocurable coating layer, wherein the photocurable coating layer is coated on at least a portion of the substrate layer, and the photocurable coating layer is obtained by radiation curing the aforementioned cationic photocurable composition. Due to the reasons described above, the wet adhesion between the photocurable coating layer and the substrate layer interface of the present invention is superior. Furthermore, the coating layer also possesses excellent scratch resistance. When applying the cationic photocurable composition of the present invention to different types of substrate surfaces to produce a photocurable coating layer, the substrate used is not particularly limited, and examples include, but is not limited to, metal substrates and plastic substrates.

[0034] Preferably, the base layer is a metal base layer or a plastic base layer. More preferably, the plastic base layer is Poly The materials include propylene film (PP), polyethylene film (PE), polyester film (PET), etc., and the metal substrate layer is tinplate, aluminum plate, etc. When using the composition of the present invention, good adhesion can be obtained without corona treatment of the plastic substrate layer.

[0035] Furthermore, the cationic photocurable composition of the present invention is not particularly limited in terms of the form of the initiation energy source. By irradiation with energy such as ultraviolet light, visible light, infrared light, electron beams, and lasers, the radiation-curable composition of the present invention undergoes a polymerization reaction and achieves rapid curing. For example, the initiation energy source includes, but is not limited to, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury-xenon lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, deuterium lamps, chemical lamps, LED lamps, fluorescent lamps, tungsten lamps, Nd-YAG third-harmonic lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor-pumped solid-state lasers, and active light such as i-rays, h-rays, and g-rays with wavelengths of 200-500 nm. For curing the composition, electron beam, alpha, beta, gamma, X-ray, and neutron energy curing may also be used, preferably a mercury lamp ultraviolet lamp or UV-LED lamp with a wavelength range of 200 to 500 nm, and an irradiation energy of 20 to 1000 mJ / cm². 2 That is the case.

[0036] Without being particularly limited, those skilled in the art may perform the above coating by methods such as the dip method, air knife coating method, curtain coating method, roll coating method, die coating method, or wire bar coating method, but a detailed explanation is omitted here. Furthermore, the thickness of the cured coat layer of the pattern of the cationic photocurable composition of the present invention may vary as needed, preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm. A coat layer less than 0.1 μm thick may not be able to form uniformly or may be difficult to apply accurately according to the design, while a coat layer exceeding 20 μm thick may consume a large amount of composition, leading to increased costs, and may be difficult to apply uniformly, and the coat layer may become brittle and prone to separation. To further improve the above-mentioned excellent performance, in some preferred embodiments, the cationic photocurable composition is 50 to 55 parts

[0037] [ka]

[0038] And, 20-25 parts

[0039] [ka]

[0040] The composition also contains 5 to 15 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 55 to 65 parts

[0041] [ka]

[0042] And, parts 10-15

[0043] [ka]

[0044] The composition contains 10 to 15 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 65 to 70 parts

[0045] [ka]

[0046] And, parts 10-15

[0047] [ka]

[0048] The composition also contains 5 to 10 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 15 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 65 to 70 parts

[0049] [ka]

[0050] And, parts 15-25

[0051] [ka]

[0052] The composition also contains 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 50 to 60 parts

[0053] [ka]

[0054] And, parts 15-25

[0055] [ka]

[0056] The composition also contains 10 to 15 parts of 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane, 1 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 60 to 70 parts

[0057] [ka]

[0058] And 10-20 copies

[0059] [ka]

[0060] The composition also contains 10 to 15 parts of 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane, 1 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 55 to 65 parts

[0061] [ka]

[0062] And, parts 15-25

[0063] [ka]

[0064] The composition also contains 5 to 10 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 65 to 70 parts

[0065] [ka]

[0066] And 10-20 copies

[0067] [ka]

[0068] It also contains 1 to 3 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306.

[0069] The present invention further provides an ink comprising the cationic photocurable composition described above. Due to the aforementioned causes, the cationic photocurable composition of the present invention can better avoid the occurrence of mist problems when subsequently applied as an ink in gravure printing. To further improve the above-mentioned excellent performance, in some preferred embodiments, the cationic photocurable composition is 50 to 55 parts

[0070] [ka]

[0071] And, 20-25 parts

[0072] [ka]

[0073] The composition contains 5 to 15 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 50 to 60 parts

[0074] [ka]

[0075] And, parts 10-15

[0076] [ka]

[0077] The composition also contains 10-15 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5-10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1-5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 1-3 parts of PSS-306, and 3-5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 60-70 parts

[0078] [ka]

[0079] And, parts 10-15

[0080] [ka]

[0081] The composition also contains 5 to 10 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 15 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 60 to 70 parts

[0082] [ka]

[0083] And, parts 15-25

[0084] [ka]

[0085] The composition also contains 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 55 to 65 parts

[0086] [ka]

[0087] And, parts 10-15

[0088] [ka]

[0089] The composition contains 10 to 15 parts of 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane, 1 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 55 to 65 parts

[0090] [ka]

[0091] And 10-20 copies

[0092] [ka]

[0093] The composition contains 10 to 15 parts of 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane, 1 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 55 to 60 parts

[0094] [ka]

[0095] And, parts 15-25

[0096] [ka]

[0097] The composition contains 5 to 10 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition contains 60 to 70 parts

[0098] [ka]

[0099] And 10-20 copies

[0100] [ka]

[0101] It also contains 1 to 3 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black.

[0102] The present invention further provides the use of the aforementioned inks in gravure printing. Due to the aforementioned causes, the aforementioned inks of the present invention can better avoid the occurrence of mist problems when applied to gravure printing. [Modes for carrying out the invention]

[0103] The present application will be described in more detail below with reference to specific embodiments, and these embodiments should not be understood as limiting the scope of the claims of the present application. 1. Preparation of the composition According to the mixing ratios shown in Examples 1 to 8 in Table 1, the raw materials were stirred at a constant speed for 1 hour in a high-speed stirrer under yellow light lamp conditions, then polished in a polishing machine, and subsequently filtered through a screen with a particle size of 1 μm to obtain the composition. Unless otherwise specified, all numbers in each example are in parts by weight.

[0104] [Table 1]

[0105] [ka]

[0106] B1: 3,4-Epoxycyclohexylmethyl-3',4'-Epoxycyclohexylcarboxylate B2: 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxilan B3: 3-Benzyloxymethyl-3-ethyloxetane C1: 4-Isobutyl-4'-methyldiphenyliodonium hexafluorophosphate C2:4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate D: PSS-306 (9,10-diethoxy-2-ethylanthracene, sensitizer)

[0107] 1. Curability measurement The photocurable composition was collected and left on various substrates. It was then coated with a 10# wire bar to obtain a coating layer of approximately 8 μm. This coating was then exposed to light using a mercury lamp (RW-LED-YT200gl) under conditions of 25°C and 50% RH, with an irradiation time of 2 seconds and an energy of 100 mJ / cm². 2 The curing and film formation status was observed and evaluated using the finger touch method. The results are shown in Table 2 below. The evaluation criteria for the finger touch method are as follows: 1: It remained oily and did not harden. 2: The surface is oily, and the bottom layer is hardened. 3: The surface is sticky and leaves many fingerprints after touching it. 4. The surface is generally dry, feels slightly stiff to the touch, and shows faint fingerprints. 5: It hardens completely, the surface is smooth, and there are no fingerprints after touching it with your hand.

[0108] 2.Wet adhesion measurement The photocurable composition was collected and left on various substrates, then coated with a 10# wire bar to obtain a coating layer of approximately 8 μm. This coating was then exposed to light by irradiating it with a mercury lamp (RW-LED-YT200gl) under conditions of 25°C and 50% RH, with an irradiation energy of 100 mJ / cm². 2 After complete curing, the coating layer was dried at 80°C for 30 minutes, then immersed in room temperature water for 2 hours, and the adhesion strength was measured using the 100-grid method. The evaluation criteria are as follows.

[0109] Level 0: The edges of the cut are perfectly smooth, and no lattice is peeling. Level 1: The court layer peels slightly at the cross-cut intersection, but the affected cross-cut area does not exceed 5%. Level 2: There is delamination of the coat layer along the intersection and / or edges of the cut, but the affected crosscut area is greater than 5% but not greater than 15%. Level 3: The coating layer is partially or completely peeled off in the form of large fragments along the edges of the cut, and / or partially or completely peeled off in different parts of the grid, with the affected cross-cut area exceeding 15% but not exceeding 35%. Level 4: The coat layer peels off in the form of large fragments along the edges of the cut, and / or some lattice sections peel off partially or completely, with the affected cross-cut area exceeding 35% but not exceeding 65%. Level 5: The degree of peeling exceeds Level 4.

[0110] 3. Scratch resistance measurement The photocurable composition was collected and left on various substrates, then coated with a 10# wire bar to obtain a coating layer of approximately 8 μm. This coating was then exposed to light by irradiating it with a mercury lamp (RW-LED-YT200gl) under conditions of 25°C and 50% RH, with an irradiation energy of 100 mJ / cm². 2 After complete hardening, the hardened film is rubbed back and forth with a #0000 steel wool ball under a load of 500g and a friction distance of 5-6cm. The number of back-and-forth friction cycles until friction marks appear on the hardened film is evaluated, and a higher number indicates better scratch resistance.

[0111] [Table 2]

[0112] [Table 3]

[0113] 2. Preparation of gravure printing inks According to the mixing ratios shown in Examples 1 to 8 in Table 3, the raw materials were stirred at a constant speed for 1 hour in a high-speed stirrer under yellow light lamp conditions, then polished in a polishing machine, and subsequently filtered through a screen with a particle size of 1 μm to obtain the gravure printing ink composition. Unless otherwise specified, all numbers in each example are in parts by weight.

[0114] [Table 4]

[0115] [ka]

[0116] B1: 3,4-Epoxycyclohexylmethyl-3',4'-Epoxycyclohexylcarboxylate B2: 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxilan B3: 3-methylol-3-ethyloxetane C1: 4-Isobutyl-4'-methyldiphenyliodonium hexafluorophosphate C2:4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate D: PSS-306 (9,10-diethoxy-2-ethylanthracene, sensitizer) E: Inorganic carbon black (Clariant Chemical (China) Co., Ltd.)

[0117] 2. Curing and drying speed measurement The ink to be measured was printed using a Matsutoku solvent-free gravure printing press (model number: A380), and a 385nm wavelength LED lamp was added to the press as a radiation source. The ink to be measured was transferred onto a PET film (Rakukai's general industrial film FP2) using the gravure printing press, with a print thickness of 5μm and an LED light source irradiation intensity of 20w / cm². 2 I did. After light irradiation, the surface is left for 24 hours, and the surface hardening status is evaluated by referring to the finger touch method in the coating drying time measurement standard GB / T 1728-1979. That is, the surface is confirmed to be dry when the surface is smooth, non-sticky, and does not leave fingerprints when pressed, by lightly touching the coating layer with a finger. The drying rate is expressed as the maximum linear velocity (m / min) at which the surface drying effect is achieved.

[0118] 3. Performance Evaluation The linear speeds on the gravure printing press were set to 220 m / min and 150 m / min, respectively. A PET film was used as the substrate, the print thickness was set to 5 μm, and the illumination intensity of a 385 nm LED light source was set to 20 w / cm². 2 After exposure, the samples were left for 24 hours, and the mist and adhesion fastness of the hardened coating layer were evaluated.

[0119] (1) Measurement of coating layer adhesion strength Adhesion to the substrate was measured using the 100-grid cross-cut method and the QFH coating cross-cut apparatus, in accordance with "GB / T9286-1998 Scratch Experiment of Paint and Varnish Coatings". The specific procedure is as follows: Using a knife conforming to "GB / T9286-1998 Scratch Experiment of Paint and Varnish Coatings," the surface of the coating layer was cut, ensuring that each cut went through the substrate surface. The surface of the coating layer was then cleaned with a soft brush. Tape was then applied to the coating layer, ensuring that the tape made complete contact with the coating layer. Finally, the tape was peeled off the surface of the coating layer, and the results were evaluated.

[0120] Level 0: The edges of the cuts are perfectly smooth, and there is no peeling in any of the grid lines. Level 1: There is slight delamination of the court layer at the cross-cut intersection, but the affected cross-cut area is less than 5%. Level 2: There is delamination of the coat layer along the intersection and / or edges of the cut, but the affected crosscut area is between 5% and 15%. Level 3: The coating layer is partially or completely peeled off in the form of large fragments along the edges of the cut, and / or partially or completely peeled off in different parts of the grid, with the affected cross-cut area being between 15% and 35%. Level 4: The coating layer peels off in the form of large fragments along the edges of the cut, and / or some of the grid is partially or completely peeled off, with the affected cross-cut area being between 35% and 65%. Level 5: The degree of peeling exceeds Level 4.

[0121] (2) Mist measurement The image was printed onto PET film using a gravure printer at a printing speed of 220 m / min, and an illumination intensity of 20 w / cm² was used with a 385 nm LED light source. 2 The film was irradiated, left for 24 hours after exposure, and printed materials were obtained. The amount of ink (mist) adhering to the blank areas (non-image areas) of the obtained printed film was visually evaluated according to the following criteria. The evaluation criteria are as follows: 5: No ink transfer was observed in non-image areas. 4: Slight ink transfer was observed in small areas (less than 5%) of the non-image region. 3: Ink transfer was observed in a medium-sized area (5% to less than 10%) of the non-image region. 2: Ink transfer was observed in large areas (10% or more) of the non-image region. 1: Ink transfer was observed throughout the non-image area.

[0122] [Table 5]

[0123] As is clear from the performance evaluation results in Table 4, the cationic photocurable composition of the present invention exhibits excellent curing performance and effectively solves the mist problem in gravure printing inks, and is expected to be widely applied. The above are merely preferred embodiments of the present invention and are not intended to limit the present invention, and various modifications and changes to the present invention are possible for those skilled in the art. Any modifications, equivalence substitutions, improvements, etc., made without departing from the spirit and principles of the present invention should all be within the scope of protection of the present invention.

Claims

1. Ingredient A1: 【Chemistry 1】 and, Component A2: 【Chemistry 2】 and, (In the formula, R １ , R ２ , R ３ , R ４ , R ５ Each of them independently, C １ ~C ６ (Represents the alkyl group.) Component B: Epoxy compound, Component C: Cationic initiator, Includes, The epoxy compound comprises a monofunctional oxetane, A cationic photocurable composition comprising, by weight, 50 to 70 parts of component A1, 10 to 30 parts of component A2, 5 to 25 parts of component B, and 1 to 10 parts of component C, wherein the total parts by weight of component A1 and component A2 is 65 to 95 parts.

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

3. Said R １ 、said R ２ 、said R ３ 、said R ４ 、said R ５ each independently represents an alkyl group of C １ to C ３ The cationic photocurable composition according to claim 1, characterized in that

4. The component A1 is, 【Transformation 3】 And, The aforementioned component A2 is 【Chemistry 4】 The cationic photocurable composition according to claim 1, characterized in that it is the same as the one described in claim 1.

5. The epoxy compound may further include one or more selected from the group consisting of alicyclic epoxy compounds and aromatic epoxy compounds. The alicyclic epoxy compound is one or more selected from the group consisting of 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenoate, 3,4,3',4'-diepoxybicyclohexane, 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis(3,4-epoxycyclohexyl)-1,3-hexafluoropropane, bis(3,4-epoxycyclohexyl)methane, 1-[1,1-bis(3,4-epoxycyclohexyl)]ethylbenzene, bis((3,4-epoxycyclohexyl)methyl)adipate, and bis(3,4-epoxycyclohexylmethyl) oxalate. The monofunctional oxetane is one or more selected from the group consisting of 3-methylol-3-ethyloxetane, 3-benzyloxymethyl-3-ethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and 3-ethyl-3-((octyloxy)methyl)oxetane. The cationic photocurable composition according to claim 1, characterized in that the aromatic epoxy compound is selected from 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxiran.

6. The cationic initiator is selected from onium salts, and the onium salt is one or more selected from the group consisting of diaryliodonium salts of phosphoric acid, triarylsulfonium salts of phosphoric acid, and triarylsulfonium salts of antimony acid. The diaryliodonium salt of the phosphoric acid is one or more selected from the group consisting of 4,4'-dimethyldiphenyliodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, 4-isopropyl-4'-methyldiphenyliodonium hexafluorophosphate, and 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate. The triarylsulfonium salt of the phosphoric acid is one or more selected from the group consisting of 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide-bishexafluorophosphate, and triphenylsulfonium hexafluorophosphate. The cationic photocurable composition according to claim 1, characterized in that the triarylsulfonium salt of antimonic acid is one or more selected from the group consisting of bis(4-t-butylphenyl)sulfonium hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfidebishexafluoroantimonate, and diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate.

7. The aforementioned cationic photocurable composition further comprises component D: sensitizer, The component D is 0.1 to 5% by mass relative to the cationic photocurable composition. The cationic photocurable composition according to claim 1, characterized in that component D is one or more selected from the group consisting of thioxanthone compounds, xanthone compounds, acridine compounds, anthracene compounds, and coumarin compounds.

8. The aforementioned cationic photocurable composition further comprises component E: a colorant, The aforementioned component E is present in an amount of 2 to 20% by mass relative to the cationic photocurable composition. The coloring agent is selected from inorganic pigments and / or organic pigments. The aforementioned organic pigment is one or more selected from the group consisting of perylene, phthalocyanine dyes, cyanine pigments, naphthalocyanine pigments, nitroso pigments, azo pigments, diazo pigments, diazo condensation pigments, basic dye pigments, alkali blue pigments, indigo pigments, phloxine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, carbazoledioxazine violet pigments, alizarin lake pigments, phthalamide pigments, carmine lake pigments, tetrachloroisoindolinone pigments, perinone pigments, anthraquinone pigments, and quinophthalone pigments. The cationic photocurable composition according to claim 1, characterized in that the inorganic pigment is one or more selected from the group consisting of metal oxides, silicon oxides, carbon black pigments, metal sulfides, and metal chlorides.

9. A paint characterized by comprising the cationic photocurable composition described in any one of claims 1 to 7.

10. A product comprising a substrate layer and a photocurable coating layer, wherein the photocurable coating layer is coated on at least a portion of the substrate layer, The photocurable coating layer is characterized by being obtained by radiation curing a cationic photocurable composition according to any one of claims 1 to 7.

11. The said substrate layer is a metal substrate layer or a plastic substrate layer. The aforementioned plastic substrate layer is a polypropylene film, a polyethylene film, or a polyester film. The product having a photocurable coating layer according to claim 10, characterized in that the metal substrate layer is tinplate or aluminum plate.

12. The radiation hardening is carried out under a radiation source, and the radiation source is one or more selected from the group consisting of ultraviolet light, visible light, infrared light, electron beams, and lasers. The irradiation energy of the aforementioned radiation source is 20 to 1000 mJ / cm². ２ A product having a photocurable coating layer as described in 10, characterized in that it is the product described in 10.

13. An ink characterized by comprising the cationic photocurable composition described in claim 8.

14. Use of the ink described in claim 13 for gravure printing.

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