Cationic photocurable composition, paint, product having a photocured coating layer, ink

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 into this application 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 the plum rain season in the south of our country).

[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 phenol resin, and the molar ratio of the hydroxy group, the 3-membered epoxy group, and the 4-membered 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 no mention is made of the wet adhesion performance.

[0004] CN100473681C (Patent Document 2) discloses a novel method for surface treatment of plastic materials. The method includes applying a composition to at least one surface of a plastic material and then exposing it to a radiation source and / or an electron beam to polymerize and / or crosslink the surface to be treated. The composition contains 1 to 99 wt% of a polymerizable and / or at least partially polymerizable organic matrix A having at least one oxetane-reactive functional group (frA), 1 to 99 wt% of at least one polymerizable and / or at least partially polymerizable organic matrix B, (co)monomers, (co)oligomers, and / or (co)polymers having epoxy (α1) and / or acrylate (α2) and / or alkenyl ether (α3) and / or hydroxy (α4) reactive functional groups (frB), an effective amount of at least one cation or a cation and a radical initiator system C, optionally at least one sensitizer D and at least one pigment E, and has good adhesion on a polypropylene (PP) plate. However, the wet adhesion performance is not mentioned.

[0005] CN103781814A (Patent Document 3) discloses a photocurable resin composition. The composition contains (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 photo radical initiator, and has good moisture resistance adhesion and scratch resistance on a glass substrate and an ITO substrate. However, no relevant studies have been conducted on the wet adhesion and scratch resistance for plastic substrates or metal substrates.

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

[0007] Incidentally, with the rapid development of the flat panel display industry in our country, in advanced fields such as liquid crystal displays, semiconductor lighting, semiconductor flexible circuit boards, and electronic devices, the demand for plastic substrates is also increasing. However, compared with glass substrates, plastics are usually soft, have low surface hardness, and are easily scratched, so it is necessary to apply a protective layer on its surface. Such a protective layer requires sufficient flexibility while having good scratch resistance performance. In addition, such a coating layer should adhere well to the surface of the substrate to be coated. In particular, when the plastic substrate is used in display devices such as LCDs and OLEDs, not only good adhesion to the coating layer is required, but also good wet adhesion should be maintained under high humidity conditions (especially during the plum rain season in the southern part of our country). Therefore, the adhesion at the interface between the metal substrate or plastic substrate and the coating layer, especially not causing a decrease in the wet adhesion between the substrate and the coating layer of the photocurable composition under high humidity conditions, becomes the main problem to be solved in the application of metals or plastics.

[0008] (2) Regarding the use of the cationic photocurable composition in photocurable ink products In the prior art, when applying ink to gravure printing, a mist problem occurs (the mist referred to in the present invention means that during printing, the ink on the printing plate that cannot be sufficiently removed by the doctor blade is transferred to the object to be printed, resulting in the phenomenon that the substrate of the printed matter is contaminated).

[0009] When the cationic photocurable 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 interface of the plastic or metal substrate film, or poor scratch resistance of the coating layer exist. On the other hand, when the cationic photocurable composition in the prior art is applied as an ink material, there is further a problem of mist. Therefore, it is necessary to provide a new cationic curable composition to solve the above problems.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

[0011] The main object of the present invention is to provide a cationic photocurable composition, a paint, a product having a photocured coating layer, and an ink to solve the problems that when the cationic 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 interface of the plastic or metal substrate film, or poor scratch resistance of the coating layer exist, and the problem of mist that exists when the cationic curable composition in the prior art is applied as an ink material. Unless there is a contradiction, the examples in this application and the features in the examples may be combined with each other. Hereinafter, the present invention will be described in detail with reference to the examples.

[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, there are 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. 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 an alkyl group having 1 to 6 carbon atoms.) B: an epoxy compound, and C: a cation initiator, and including 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] Surprisingly, when the compound represented by the general formula A1 is blended with the compound represented by the general formula A2 and the 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 very 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 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 significantly 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]

Chemical formula

[0022] and A2 is

[0023] [Chemical formula]

[0024] . In one preferred embodiment, the epoxy compound is one or more selected from the group consisting of an alicyclic epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, or a monofunctional oxetane.

[0025] For example, the alicyclic epoxy compound may be one or more selected from the group consisting of 3,4-epoxycyclohexene methyl-3,4-epoxycyclohexenate, 3,4,3’,4’-diepoxy bicyclohexane, 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. The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. Examples of the aromatic epoxy compound include epoxy compounds of an aromatic ring conjugated system having a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, etc. Among them, in order to achieve a higher refractive index of the product, compounds having a bisphenol skeleton and / or a fluorene skeleton are preferable. Examples of the aromatic epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene-based epoxy compounds, etc. Among them, bisphenol A type epoxy compounds and fluorene-based epoxy compounds, such as 2,2’-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)] bisoxirane, are preferable. The alicyclic epoxy compound is a compound having at least one epoxy group bonded to an alicyclic ring in the molecule. Among them, as the alicyclic epoxy compound, a compound having epoxycyclohexyl is suitable. Also, from the viewpoint of further improving the curing rate of the composition, a polyfunctional alicyclic epoxy compound having two or more alicyclic epoxy groups in the molecule is preferable. Furthermore, a compound having one alicyclic epoxy group in the molecule and an unsaturated double bond such as a vinyl group is preferably used as the alicyclic epoxy compound.

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

[0027] More preferably, in addition to the polymerizable compounds of component A1, component A2 and component B, the cationic photocurable composition of the present invention may, on the premise that it does not negatively affect the application effect of the composition, optionally contain other cationic monomers, for example, TCM-107, TCM-109, TCM-111, TCM-115, TCM-118, TCM-120 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd. and / or THM-201, THM-202, THM-203, THM-204, THM-205, 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. manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd. may be further added.

[0028] In one preferred embodiment, the cationic photocurable composition of the present invention, in addition to component A1, component A2, component B, and component C, may further contain component D: a sensitizer in order to further improve the photosensitivity of the composition on the premise that it does not negatively affect the application effect of the composition, or to meet the requirements for photocuring with a long-wavelength light source, particularly photocuring with a UV-LED lamp source. Preferably, D is 0.1 to 5% by mass based on 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), JRCure-1106 (DETX) manufactured by Tianjin Jiuri New Materials, and PSS303, PSS306, PSS510, PSS513, PSS515 manufactured by Changzhou Qiangli 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 pigment or an organic pigment, and may have any color, such as black, blue, brown, teal, green, white, purple, magenta, red, orange, and yellow, and mixtures of these colors, but is not limited thereto. Preferably, E is 2 to 20% by mass based on the cationic photocurable composition.

[0030] Examples of the organic pigments applicable include perylene, phthalocyanine dyes (e.g., phthalocyanine green, phthalocyanine 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, fluorescein pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, carbazole dioxazine violet pigments, alizarin lake pigments, phthalamide pigments, carmine lake pigments, tetrachloroisoindolinone pigments, perinone pigments, anthraquinone pigments, quinophthalone pigments, etc., and mixtures of two or more of these or derivatives thereof may also be used. Examples of the inorganic pigments applicable 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 oxide), silicon oxide, carbon black pigment, metal sulfides, metal chlorides, etc., and mixtures of two or more of these may also be used.

[0031] In one preferred embodiment, in addition to the above components A to E, according to the requirements of the product application environment, organic and / or inorganic auxiliaries commonly used in this field may be further added to the cationic composition of the present invention as needed, for example, fillers, leveling agents, dispersants, curing agents, surfactants, defoaming agents, storage stabilizers, etc., but are not limited thereto, which can be easily selected by those skilled in the art according to the needs of their products, and detailed description is omitted here. In one preferred embodiment, the specific manufacturing process of the cationic photocurable composition of the present invention may refer to the general manufacturing methods in the field of radiation curable compositions. Typically, the manufacturing process undergoes compounding, preliminary dispersion, grinding, and filtration (filtering through a screen of a predetermined size to obtain a product with a target particle size) under the conditions of constant temperature and humidity and shielding from radiation light sources.

[0032] Furthermore, the viscosity (23 ± 2 °C) 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 appropriately 500 mPa·s or less, preferably 10 to 200 mPa·s. When the viscosity of the cationic photocurable composition exceeds 200 mPa·s or is less than 10 mPa·s, it may cause "poor coverage" and poor smoothness. Also, when the viscosity of the cationic photocurable composition exceeds 200 mPa·s or is less than 10 mPa·s, the stability during the storage process of the composition may be poor. The viscosity of the cationic photocurable composition may usually be controlled by a thickening agent or a thinning agent, which can also be selected by those skilled in the art according to their needs for their products, and detailed explanations are omitted here.

[0033] The present invention further provides a paint containing the above-mentioned cationic photocurable composition. Due to each of the above-mentioned reasons, when the cationic photocurable composition of the present invention is subsequently applied as a paint, the wet adhesion between the formed photocured coating layer and the substrate layer interface is more excellent. Also, the coating layer also has very excellent scratch resistance performance. The present invention further provides a product having a photocurable coating layer including a substrate layer and a photocurable coating layer, wherein the photocurable coating layer is coated on at least a partial region of the substrate layer, and the photocurable coating layer is formed by radiation-curing the above-described cationic photocurable composition. Due to each of the above-described causes, the wet adhesion between the photocurable coating layer of the present invention and the interface of the substrate layer is more excellent. Further, the coating layer also has very excellent scratch resistance performance. In addition, when manufacturing a photocurable coating layer by applying the cationic photocurable composition of the present invention to the surfaces of different types of substrates, the substrates to be used are not particularly limited, and examples include, but are not limited to, materials such as metal substrates and plastic substrates.

[0034] Preferably, the substrate layer is a metal substrate layer or a plastic substrate layer. More preferably, the plastic substrate layer is a polypropylene film (PP), a polyethylene film (PE), a polyester film (PET), etc., and the metal substrate layer is a tinplate, an aluminum plate, etc. When using the composition of the present invention, good adhesion can be obtained without corona-treating the plastic substrate layer.

[0035] Furthermore, the cationic photocurable composition of the present invention is not particularly limited with respect to the form of the initiation energy source, and by irradiating energy such as ultraviolet rays, visible light, infrared rays, electron beams, lasers, etc., the radiation-curable composition of the present invention can undergo a polymerization reaction and achieve rapid curing. For example, the initiation energy source includes, but is not limited to, active light rays such as a super-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a mercury-xenon lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a deuterium lamp, a chemical lamp, an LED lamp, a fluorescent lamp, a tungsten lamp, an Nd-YAG triple wavelength laser, a He-Cd laser, a nitrogen laser, a Xe-Cl excimer laser, a Xe-F excimer laser, a semiconductor-excited solid state laser, i-line, h-line, g-line, etc. having a wavelength of 200 to 500 nm. For the curing of the composition, electron beams, α-rays, β-rays, γ-rays, X-ray and neutron ray energy curing, etc. may further be used. Preferably, it is a mercury lamp ultraviolet lamp or a UV-LED lamp having a wavelength range of 200 to 500 nm, and the irradiation energy of the radiation source is 20 to 1000 mj / cm2 It is as follows.

[0036] Without particular limitation, those skilled in the art may perform the above coating by, for example, dip coating, air knife coating, curtain coating, roll coating, die coating, wire bar coating, etc., but detailed description is omitted here. Furthermore, the thickness of the cured coating layer of the pattern of the cationic photocurable composition of the present invention may vary according to actual needs, preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm. A coating layer with a thickness of less than 0.1 μm may not be formed uniformly, or may be difficult to apply accurately according to the design. A coating layer with a thickness exceeding 20 μm may consume a large amount of the composition, cause an increase in cost, and may be difficult to apply uniformly, and the coating layer may become brittle and prone to delamination. In order to further improve the above excellent performance, in some preferred embodiments, the cationic photocurable composition contains 50 to 55 parts of

[0037]

Chemical formula

[0038] and 20 to 25 parts of

[0039]

Chemical formula

[0040] and 5 to 15 parts of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 55 to 65 parts of

[0041]

Chemical formula

[0042] and 10 to 15 parts of

[0043] [Chem.]

[0044] and 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)phenyl diphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition comprises 65 to 70 parts of

[0045] [Chem.]

[0046] and 10 to 15 parts of

[0047] [Chem.]

[0048] and 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)phenyl diphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition comprises 65 to 70 parts of

[0049] [Chem.]

[0050] and 15 to 25 parts of

[0051] [Chemistry]

[0052] and 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 comprises 50 to 60 parts of

[0053] [Chemistry]

[0054] and 15 to 25 parts of

[0055] [Chemistry]

[0056] and 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 comprises 60 to 70 parts of

[0057] [Chemistry]

[0058] and 10 to 20 parts of

[0059] [Chemistry]

[0060] and 10 to 15 parts of 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxolane, 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 of

[0061] [Chemical formula]

[0062] and 15 to 25 parts of

[0063] [Chemical formula]

[0064] and 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)phenyl diphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306. Alternatively, the cationic photocurable composition contains 65 to 70 parts of

[0065] [Chemical formula]

[0066] and 10 to 20 parts of

[0067] [Chemical formula]

[0068] and 1 to 3 parts of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, and 1 to 3 parts of PSS-306.

[0069] The present invention further provides an ink containing the above-described cationic photocurable composition. Due to each of the above-described reasons, when the cationic photocurable composition of the present invention is subsequently applied to gravure printing as an ink, the occurrence of mist problems can be better avoided. In order to further improve the above excellent performance, in some preferred embodiments, the cationic photocurable composition contains 50 to 55 parts of

[0070]

Chemical formula

[0071] and 20 to 25 parts of

[0072]

Chemical formula

[0073] and 5 to 15 parts of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium 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 of

[0074]

Chemical formula

[0075] and 10 to 15 parts of

[0076] [Chemical formula]

[0077] and 10 to 15 parts of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition comprises 60 to 70 parts of

[0078] [Chemical formula]

[0079] and 10 to 15 parts of

[0080] [Chemical formula]

[0081] and 5 to 10 parts of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate, 5 to 15 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition comprises 60 to 70 parts of

[0082] [Chemical formula]

[0083] and 15 to 25 parts of

[0084] [Chemical formula]

[0085] and 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 of

[0086]

Chemical formula

[0087] and 10 to 15 parts of

[0088]

Chemical formula

[0089] and 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 of

[0090]

Chemical formula

[0091] and 10 to 20 parts of

[0092]

Chemical formula

[0093] and 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 comprises 55 to 60 parts of

[0094] [Chemical formula]

[0095] and 15 to 25 parts of

[0096] [Chemical formula]

[0097] and 5 to 10 parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexyl carboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black. Alternatively, the cationic photocurable composition comprises 60 to 70 parts of

[0098] [Chemical formula]

[0099] and 10 to 20 parts of

[0100] [Chemical formula]

[0101] and 1 to 3 parts of 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate, 5 to 10 parts of 3-benzyloxymethyl-3-ethyloxetane, 1 to 5 parts of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 1 to 3 parts of PSS-306, and 3 to 5 parts of inorganic carbon black.

[0102] The present invention further provides for the use of the ink described above in gravure printing. Due to each of the above-described reasons, the ink described above of the present invention can better avoid the occurrence of mist problems when applied to gravure printing.

Embodiments for Carrying Out the Invention

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

[0104]

Table 1

[0105]

Chemical Formula

[0106] B1: 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate B2: 2,2’-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane B3: 3-benzyloxymethyl-3-ethyloxetane C1: 4-Isobutyl-4'-methyldiphenyliodonium hexafluorophosphate C2: 4-(Phenylthio)phenyl diphenylsulfonium hexafluorophosphate D: PSS-306 (9,10-Diethoxy-2-ethylanthracene, sensitizer)

[0107] 1. Measurement of curability Collect the photocurable composition, leave it on various substrates, coat it with a 10# wire bar to obtain a coating layer of about 8 μm, and irradiate and expose the coating film with a mercury lamp (RW-LED-YT200gl) light source under the conditions of a temperature of 25 °C and a humidity of 50% RH. The irradiation time is 2 seconds and the energy is 100 mj / cm 2 And observe the curing and film-forming situation, and evaluate it by the finger-touch method. The results are shown in Table 2 below. The evaluation criteria of the finger-touch method are as follows. 1: Oily and not cured 2: The surface is oily and the bottom layer is cured 3: The surface is sticky and there are many fingerprints after touching with the hand 4: Basically, the surface is dry, a little astringent when touched with the hand, and the fingerprints are light 5: Completely cured, the surface is smooth, and there are no fingerprints after touching with the hand.

[0108] 2. Measurement of wet adhesion Collect the photocurable composition, leave it on various substrates, coat it with a 10# wire bar to obtain a coating layer of about 8 μm, and irradiate and expose the coating film with a mercury lamp (RW-LED-YT200gl) light source under the conditions of a temperature of 25 °C and a humidity of 50% RH. The irradiation energy is 100 mj / cm 2 After complete curing, dry the coating layer at 80 °C for 30 min, then immerse it in normal-temperature water for 2 h, and measure the adhesion by the 100-grid method. The evaluation criteria are as follows.

[0109] Level 0: The cut edge is completely smooth and none of the grids are peeled off. Level 1: The coating layer peels slightly at the intersection of the cuts, and the cross-cut area affected does not exceed 5%. Level 2: There is peeling of the coating layer along the intersection of the cuts and / or the edges of the cut surfaces, and the cross-cut area affected exceeds 5% but does not exceed 15%. Level 3: The coating layer is partially or completely peeled off in the form of large pieces along the edges of the cuts, and / or is partially or completely peeled off at different parts of the grid, and the cross-cut area affected exceeds 15% but does not exceed 35%. Level 4: The coating layer peels off in the form of large pieces along the edges of the cuts, and / or some of the grids are partially or completely peeled off, and the cross-cut area affected exceeds 35% but does not exceed 65%. Level 5: The degree of peeling exceeds Level 4.

[0110] 3. Measurement of Scratch Resistance Collect the photocurable composition and leave it on various substrates, apply it with a #10 wire bar to obtain a coating layer of about 8 μm, and expose the coating film with a mercury lamp (RW-LED-YT200gl) light source under the conditions of a temperature of 25°C and a humidity of 50% RH. The irradiation energy is 100 mj / cm 2 After complete curing, reciprocally rub the cured film with a #0000 steel wool ball, set the load to 500 g, set the friction distance to 5 - 6 cm, and evaluate it by the number of reciprocating rubs when friction marks appear on the cured film due to friction. The larger the numerical value, the better the scratch resistance performance.

[0111]

Table 2

[0112]

Table 3

[0113] 2. Preparation of Gravure Printing Ink 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 with a high-speed stirrer under yellow light lamp conditions, then polished with a polishing machine, and then filtered through a screen with a particle size of 1 μm to obtain a gravure printing ink composition. Unless otherwise specified, the numbers in each example are all in parts by weight.

[0114]

Table 4

[0115]

Chemical formula

[0116] B1: 3,4-Epoxycyclohexylmethyl-3’,4’-epoxycyclohexyl carboxylate B2: 2,2’-[(1-Methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane B3: 3-Methylol-3-ethyloxetane C1: 4-Isobutyl-4’-methyldiphenyliodonium hexafluorophosphate C2: 4-(Phenylthio)phenyl diphenylsulfonium hexafluorophosphate D: PSS-306 (9,10-Diethoxy-2-ethylanthracene, sensitizer) E: Inorganic carbon black (Clariant Chemicals (China) Co., Ltd.)

[0117] 2. Measurement of curing and drying speed The ink to be measured was printed with a Songde solventless gravure printing machine (model number: A380), and an LED lamp with a wavelength of 385 nm was added to the printing machine as a radiation light source. With the gravure printing machine, the ink to be measured was transferred onto a PET film (general industrial film FP2 of Lucky), the printing thickness was set to 5 μm, and the LED light source irradiation intensity was set to 20 w / cm 2 2. After light irradiation, leave it for 24 hours, and evaluate the surface curing status with reference to the finger-touch method in the standard for measuring the drying time of the coating film GB / T 1728-1979, that is, gently touch the coating layer with your finger, and confirm that the surface is dry when the surface is smooth, there is no stickiness, and no fingerprints are left even when pressed. The drying speed is expressed by the maximum linear speed (m / min) to achieve the effect of surface drying.

[0118] 3. Performance evaluation Set the linear speed on the gravure printing machine to 220 m / min and 150 m / min respectively, use a PET film as the substrate, set the printing thickness to 5 μm, and set the irradiation intensity of the 385 nm LED light source to 20 w / cm 2 After exposure, leave it for 24 hours, and evaluate the mist, adhesion fastness, etc. of the cured coating layer.

[0119] (1) Measurement of coating layer adhesion According to "GB / T9286-1998 Scratch Experiment of Paint and Varnish Coatings", the adhesion to the substrate was measured using the 100-grid cross-cut method and the QFH coating cross-cut device. The specific implementation method is as follows. Use a knife compliant with "GB / T9286-1998 Scratch Experiment of Paint and Varnish Coatings" to cut the surface of the coating layer, ensuring that each time it cuts through the substrate surface, clean the surface of the coating layer with a soft brush, then stick tape on the coating layer, ensuring that the tape is in complete contact with the coating layer, and finally, peel the tape from the surface of the coating layer and evaluate the results.

[0120] Level 0: The cut edges are completely smooth and there is no peeling in any grid. Level 1: There is a little peeling of the coating layer at the intersection of the cuts, but the cross-cut area affected is 5% or less. Level 2: There is peeling of the coating layer along the intersection of the cuts and / or the edges of the cuts, but the cross-cut area affected is more than 5% and 15% or less. Level 3: The coating layer is partially or completely peeled off in the form of large pieces along the cut edge and / or is partially or completely peeled off at different parts of the grid, and the cross-cut area affected is more than 15% and less than or equal to 35%. Level 4: The coating layer is peeled off in the form of large pieces along the cut edge and / or some grids are partially or completely peeled off, and the cross-cut area affected is more than 35% and less than or equal to 65%. Level 5: The degree of peeling exceeds that of Level 4.

[0121] (2) Mist measurement Print on a PET film at a printing speed of 220 m / min with a gravure printing machine, irradiate with an LED light source of 385 nm at an irradiation intensity of 20 w / cm 2 and leave it for 24 h after exposure to obtain a printed product. The amount of ink (mist) adhering to the blank part (non-image area) 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 the non-image area. 4: Slight ink transfer was observed in a small area (less than 5%) of the non-image area. 3: Ink transfer was observed in a medium area (5% to less than 10%) of the non-image area. 2: Ink transfer was observed in a large area (10% or more) of the non-image area. 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 has excellent curing performance, can well solve the mist problem in gravure printing inks, and has the prospect of being widely applied. The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, there are various changes and variations to the present invention. Any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and principles of the present invention should all be included within the protection scope of the present invention.

Claims

1. Component A1: 【Chemical Formula 39】 and Component A2: 【Chemical Formula 40】 and (wherein, R １ , R ２ , R ３ , R ４ , R ５ are each independently a C １ - C ６ alkyl group.) Component B: an epoxy compound, and Component C: a cationic initiator, and includes by weight, 50 to 70 parts of the said Component A1, 10 to 30 parts of the said Component A2, 5 to 25 parts of the said Component B, and 1 to 10 parts of the said Component C, and the sum of the parts by weight of the said Component A1 and the said Component A2 is 65 to 95 parts, a cationic photocurable composition characterized by the above.

2. by weight, the cationic photocurable composition includes 50 to 70 parts of the said Component A1, 10 to 25 parts of the said Component A2, 5 to 25 parts of the said Component B, and 1 to 5 parts of the said Component C, and the sum of the parts by weight of the said Component A1 and the said Component A2 is 70 to 90 parts, the cationic photocurable composition according to Claim 1, characterized by the above.

3. The said R １ , the said R ２ , the said R ３ , the said R ４ , the said R ５ are each independently a C １ - C ３ alkyl group, preferably, the said R １ and the said R ２ are the same, the said R ３ and the said R ４ are the same, more preferably, the said Component A1 is 【Chemical Formula 41】 and more preferably, the component A2 is [Chemical Formula 42] The cationic photocurable composition according to claim 1 or 2, characterized in that it is as described above.

4. The epoxy compound is at least one selected from the group consisting of an alicyclic epoxy compound, an aromatic epoxy compound, or a monofunctional oxetane, preferably, the alicyclic epoxy compound is at least one selected from the group consisting of 3,4-epoxycyclohexene methyl-3,4-epoxycyclohexenoate, 3,4,3',4'-diepoxy bicyclohexane, 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; preferably, the monofunctional oxetane is at least one 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; preferably, the aromatic epoxy compound is selected from 2,2'-[(1-methylethylene)bis(4,1-phenyleneoxymethylene)]bisoxirane. The cationic photocurable composition according to any one of claims 1 to 3.

5. The cationic initiator is selected from onium salts, and preferably, the onium salts are at least one selected from the group consisting of diaryliodonium salts of phosphoric acid, triarylsulfonium salts of phosphoric acid, or triarylsulfonium salts of antimonic 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, or 4-isobutyl-4'-methyldiphenyliodonium hexafluorophosphate, Preferably, the triarylsulfonium salt of phosphoric acid is one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide-bishexafluorophosphate, or triphenylsulfonium hexafluorophosphate, Preferably, the triarylsulfonium salt of antimonate is one or more selected from the group consisting of bis(4-t-butylphenyl)iodonium hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, or diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate, and the cationic photocurable composition according to any one of claims 1 to 4 is characterized in that.

6. The cationic photocurable composition further contains component D: a sensitizer. Preferably, the component D is 0.1 to 5% by mass based on the cationic photocurable composition. Preferably, the component D is one or more selected from the group consisting of thioxanthone compounds, xanthone compounds, acridine compounds, anthracene compounds, or coumarin compounds, more preferably the anthracene compounds and / or the thioxanthone compounds. More preferably, the anthracene compounds are one or more selected from the group consisting of PSS303, PSS306, PSS510, PSS513, or PSS515. More preferably, the thioxanthone compound is one or more selected from the group consisting of JRCure-1105 (ITX) or JRCure-1106 (DETX), and the cationic photocurable composition according to any one of claims 1 to 5.

7. The cationic photocurable composition further contains component E: a colorant. Preferably, the component E is 2 to 20% by mass based on the photocurable resin composition. Preferably, the colorant is selected from inorganic pigments and / or organic pigments. More preferably, the organic pigment is one or more selected from the group consisting of perylene, phthalocyanine dye, cyanine pigment, naphthalocyanine pigment, nitroso pigment, azo pigment, diazo pigment, diazo condensation pigment, basic dye pigment, alkaline blue pigment, indigo pigment, phloxine pigment, quinacridone pigment, isoindolinone pigment, dioxazine pigment, carbazole dioxazine violet pigment, alizarin lake pigment, phthalamide pigment, carmine lake pigment, tetrachloroisoindolinone pigment, perinone pigment, anthraquinone pigment, or quinophthalone pigment. More preferably, the inorganic pigment is one or more selected from the group consisting of metal oxides, silicon oxides, carbon black pigments, metal sulfides, or metal chlorides, and the cationic photocurable composition according to any one of claims 1 to 6.

8. A paint comprising the cationic photocurable composition according to any one of claims 1 to 6.

9. A product comprising a base material layer and a photocurable coating layer, wherein the photocurable coating layer has a photocurable coating layer coated on at least a part of the region of the base material layer. The photocurable coating layer is obtained by radiation-curing the cationic photocurable composition according to any one of claims 1 to 6, and the product.

10. The base material layer is a metal base material layer or a plastic base material layer. Preferably, the plastic substrate layer is a propylene film, a polyethylene film, or a polyester film, Preferably, the metal substrate layer is a brass or an aluminum plate, and the product having the photocurable coating layer according to claim 9.

11. The radiation curing is performed under a radiation source. Preferably, the radiation source is one or more selected from the group consisting of ultraviolet rays, visible light, infrared rays, electron beams, and lasers. More preferably, the radiation source is a mercury lamp ultraviolet lamp or a UV-LED lamp having a wavelength range of 200 to 500 nm. Even more preferably, the irradiation energy of the radiation source is 20 to 1000 mj / cm ２ and the product having the photocurable coating layer according to claim 9 or 10.

12. An ink comprising the cationic photocurable composition according to claim 7.

13. Use of the ink according to claim 12 for gravure printing.

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