Recording method and method for producing printed materials

Abstract

To provide a recording method capable of suppressing delamination by improving adhesiveness between a plurality of curable compositions, and a method of producing a printed matter using the recording method.SOLUTION: A recording method using curable compositions includes: a process of applying a first curable composition to a recording medium in a thin film manner; a process of applying a second curable composition to the applied first curable composition; and a process of curing the first and second curable compositions by at least heat or light, where the second curable composition is applied before curing the first curable composition by heat or light, and the first and second curable compositions are at least heat-curable compositions, or light-curable compositions.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a recording method and a method for producing printed materials. More specifically, it relates to a recording method characterized by improving the adhesion between multiple curable compositions and suppressing delamination between layers. [Background technology]

[0002] Traditionally, photolithography and screen printing methods have been used to form etching resists, solder resists, and markings on printed circuit boards. For example, an inkjet method is used to form solder resist on printed circuit boards, and it has already been proposed that after applying inkjet ink, preliminary curing with light (hereinafter also referred to as "preliminary curing") is performed, followed by final curing with heat to form a hardened layer. Furthermore, sometimes additional printing indicating the type or date is added to the cured layer. However, in such cases, the adhesion and bonding between the cured layer and the additional printing are insufficient, leading to problems such as the additional printing peeling off the cured layer or bleeding on the cured layer.

[0003] For example, Patent Document 1 discloses a method for forming a cured layer by inkjet printing a UV free radical curable inkjet ink onto a support, performing a preliminary curing with light, and then performing a final curing with heat. However, the substrate adhesion between the substrate and the cured layer interface was not sufficient.

[0004] Furthermore, Patent Document 2 discloses a method for forming a hardened layer by applying a curable composition, performing a preliminary curing with light to form a high-precision, thick laminate, and then performing a final curing with heat. However, there is no description regarding the adhesion between different curable compositions, leaving the problem of delamination between layers unresolved.

[0005] Patent Document 3 discloses a method for forming a cured layer that is less prone to delamination. This method involves applying a photocurable liquid thin film material onto a substrate to form a liquid film, then irradiating it with light for pre-curing to pre-cur it, repeating this process while gradually increasing the light intensity to form a laminate, and then irradiating it with light for final curing to cure the deep layers of the cured layer. However, this method also lacks any description regarding the adhesion between different curable compositions, leaving the problem of delamination unresolved.

[0006] Patent Document 4 discloses a method for forming a thin film that is less prone to peeling by applying a first thin film material, partially curing it, then applying a second thin film material, partially curing it, and then fully curing it with light, thereby ensuring sufficient hardening in the deeper layers. However, this method also lacks any description regarding the adhesion between different inks, resulting in the problem of interlayer delamination. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Special Publication No. 2018-529220 [Patent Document 2] Japanese Patent Publication No. 2015-089540 [Patent Document 3] Japanese Patent Publication No. 2014-236169 [Patent Document 4] Japanese Patent Publication No. 2014-233704 [Overview of the project] [Problems that the invention aims to solve]

[0008] This invention has been made in view of the above-mentioned problems and circumstances, and its objective is to provide a recording method that can improve the adhesion between multiple curable compositions and suppress delamination, and a method for producing printed materials using this recording method. [Means for solving the problem]

[0009] In order to solve the above problems, the inventor of the present invention studied the causes of the above problems and found that when applying a plurality of curable compositions stepwise on a recording medium, the above problems can be solved by applying a different curable composition on top of the uncured curable composition and then subjecting it to final curing, thus arriving at the present invention. That is, the above problems according to the present invention are solved by the following means.

[0010] 1. A recording method using a curable composition, comprising: a step of applying a first curable composition in a thin film form on a recording medium; a step of applying a second curable composition on top of the applied first curable composition; a step of curing at least the first and second curable compositions by heat or light; applying the second curable composition without subjecting the first curable composition to curing measures by heat or light; 、 before wherein the first and second curable compositions are at least thermosetting compositions or photocurable compositions; the law of nature, The process includes a step of photocuring after the step of applying the second curable composition and before the step of thermal curing the first and second curable compositions. A recording method characterized by the above.

[0011] 2. The first curable composition contains a polymerization inhibitor, wherein the polymerization inhibitor contains any one of an N-oxyl-based polymerization inhibitor, a phenolic polymerization inhibitor containing an o-t-butyl group, or a polymerization inhibitor having two or more aromatic rings; The recording method according to claim 1, characterized by the above.

[0012] 3. The first curable composition contains at least one of an epoxy resin or a blocked isocyanate compound as a thermosetting agent; The recording method according to claim 1 or 2, characterized by the above.

[0013] 4. Both the first curable composition and the second curable composition contain a polyfunctional polymerizable compound. A recording method according to any one of paragraphs 1 to 3, characterized by the above.

[0015] 5 The first curable composition contains a photopolymerization initiator with a higher content of hydrogen abstraction-type radical polymerization initiator than an α-cleavage-type radical polymerization initiator. The first to the second paragraphs characterized by... 4 The recording method described in any one of the items up to item number.

[0016] 6 The first curable composition contains a gelling agent. The first to the second paragraphs characterized by... 5 The recording method described in any one of the items up to item number.

[0017] 7 The recording method using the curable composition is an inkjet recording method. The first to the second paragraphs characterized by... 6 The recording method described in any one of the items up to item number.

[0018] 8 Articles 1 through 1 7 Printed materials shall be prepared using the recording method described in any one of the items up to item [number]. A method for producing printed materials characterized by the following features. [Effects of the Invention]

[0019] The present invention provides a recording method that can improve the adhesion between multiple curable compositions and suppress delamination, as well as a method for producing printed materials using this recording method. Although the mechanism by which the effects of this invention manifest or the mechanism of action are not yet clear, we speculate as follows.

[0020] In this invention, it is presumed that by applying a first curable composition onto a recording medium, and then applying a second curable composition while the first curable composition is still uncured, the components of each composition mix to some extent at and near the interface between the first and second layers, promoting the polymerization reaction, and thus improving the adhesion between the first and second layers.

[0021] Furthermore, it was found that by including at least one polymerization inhibitor among N-oxyl polymerization inhibitors, phenol polymerization inhibitors containing ot-butyl groups, or polymerization inhibitors having two or more aromatic rings, the polymerization inhibition at the two-layer interface can be suppressed, interlayer adhesion can be further improved, and storage properties can be good. Furthermore, compared to when other polymerization inhibitors are used, polymerization inhibition is reduced, which may explain why polymerization at the two-layer interface is carried out more efficiently, resulting in improved interlayer adhesion.

[0022] Furthermore, if both the first curable composition and the second curable composition contain a polyfunctional polymerizable compound, the interlayer adhesion and pencil hardness are further improved. This is because using highly reactive polyfunctional monomers increases the number of bonds that connect the two layers. Furthermore, because the interlayer adhesion is improved, the pencil hardness can also be improved at the same time.

[0023] Furthermore, by including a photocuring step after the step of applying the second curable composition and before the step of thermal curing the first and second curable compositions, the monomer components of the first curable composition can be cured, further improving adhesion to the recording medium (substrate), and the formation of fine lines of the second curable composition can be improved. Furthermore, it is possible to maintain a high level of interlayer adhesion.

[0024] Furthermore, by using a higher proportion of hydrogen abstraction-type radical polymerization initiators than α-cleavage-type radical polymerization initiators as photopolymerization initiators in the first curable composition, crosslinking gelation of the coating film due to the hydrogen abstraction effect progresses, further improving the crosslinking density of the coating film and thus improving adhesion to the recording medium (substrate).

[0025] Furthermore, the inclusion of a gelling agent in the first curable composition further improves the formation of fine lines while maintaining interlayer adhesion. In other words, by increasing the viscosity on the recording medium (substrate) with a gelling agent, the bleeding of the second curable composition into the first curable composition can be greatly improved, further enhancing the formation of fine lines. Furthermore, since the two layers are mixed together at the interface with the first curable composition, good interlayer adhesion can be maintained. [Brief explanation of the drawing]

[0026] [Figure 1] Basic process flow of the present invention [Figure 2A] Schematic diagram of a scan-type inkjet coating device [Figure 2B] Schematic diagram of a single-pass inkjet printer [Figure 3A] Schematic diagram of an inkjet device with the characteristic of reverse printing. [Figure 3B] Schematic diagram of a multi-carriage inkjet printer [Figure 3C] Schematic diagram of a multi-carriage (tandem transport) inkjet printer. [Figure 4] Schematic diagram of a recording device configured to move rotatably between each process. [Modes for carrying out the invention]

[0027] The present invention relates to a recording method using a curable composition, comprising the steps of: applying a first curable composition in the form of a thin film onto a recording medium; applying a second curable composition on top of the applied first curable composition; and thermally curing the first and second curable compositions, wherein the second curable composition is applied without curing the first curable composition with heat or light, and the first and second curable compositions are at least thermosetting compositions or photocurable compositions. This feature is a technical feature common to or corresponding to each of the embodiments (forms) described below.

[0028] In embodiments of the present invention, it is preferable that the first curable composition contains a polymerization inhibitor from the viewpoint of improving the adhesion between multiple curable compositions. Furthermore, from the viewpoint of improving interlayer adhesion, it is more preferable that the polymerization inhibitor contains at least one of the following polymerization inhibitors: an N-oxyl polymerization inhibitor, a phenol polymerization inhibitor containing an ot-butyl group, or a polymerization inhibitor having two or more aromatic rings.

[0029] From the viewpoint of substrate adhesion and pencil hardness, it is preferable that the first curable composition contains an epoxy resin as a thermosetting agent. Furthermore, it is even more preferable, from the viewpoint of substrate adhesion and pencil hardness, that the first curable composition contains a blocked isocyanate compound as a thermosetting agent.

[0030] Furthermore, it is preferable that both the first curable composition and the second curable composition contain a polyfunctional polymerizable compound, from the viewpoint of improving the interlayer adhesion and pencil hardness of the first and second curable compositions.

[0031] In an embodiment, it is preferable from the viewpoint of interlayer adhesion to have a photocuring step between the step of applying the second curable composition and the step of thermally curing the first and second curable compositions.

[0032] Furthermore, it is preferable that the first curable composition contains a higher content of hydrogen abstraction-type radical polymerization initiator than α-cleavage-type radical polymerization initiator as a photopolymerization initiator, as this promotes crosslinking gelation of the coating film due to the hydrogen abstraction effect, further improving the crosslinking density of the coating film and thus improving adhesion to the substrate.

[0033] Furthermore, the inclusion of a gelling agent in the first curable composition is preferable because it significantly improves the bleeding of the second curable composition into the first curable composition, further enhancing fine line formation and maintaining interlayer adhesion.

[0034] The recording method using the curable composition is preferably an inkjet recording method. Furthermore, the recording method of the present invention can be suitably used as a method for producing printed materials.

[0035] The present invention, its components, and embodiments and models for carrying out the present invention will be described in detail below. In this application, "~" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0036] [Summary of the recording method of the present invention] The present invention relates to a recording method using a curable composition, comprising the steps of: applying a first curable composition in the form of a thin film onto a recording medium (hereinafter referred to as "step 1"); applying a second curable composition on top of the applied first curable composition (hereinafter referred to as "step 2"); and curing the first and second curable compositions by heat or light (hereinafter referred to as "step 3"), wherein the second curable composition is applied while the first curable composition is in an uncured state, and the first and second curable compositions are at least thermosetting compositions or photocurable compositions. Figure 1 schematically shows the process flow of the present invention.

[0037] Here, in the present invention, "the state in which the first curable composition is uncured" refers to the state before and after curing measures such as irradiation with curing active light, heating, and removal of solvent are applied to the first curable composition coated on the recording medium, in which polymerization and crosslinking reactions between the constituent components of the curable composition have partially progressed, or the solvent contained in the curable composition has been removed by drying or the like, causing the curable composition to have high viscosity and lose fluidity, and furthermore, before the composition as a whole becomes completely solid.

[0038] Therefore, based on the above definition, a state in which a curable composition has adhesive properties (also called "tackiness") is included in the uncured state. In this specification, the state in which the entire composition becomes completely solid will be referred to as the "fully cured state."

[0039] The above-mentioned "uncured state" refers to the degree of polymerization of the polymerizable compound contained in the first curable composition, i.e., the degree of polymerization (also called the "conversion rate"). When the degree of polymerization at the time of complete solidification is set to 100, the degree of polymerization in the uncured state is lower than 100 and varies depending on the chemical structure and performance of the constituent components. However, in the present invention, it is preferable to apply the second curable compound under conditions that maintain the degree of polymerization within the range of 90 or less.

[0040] The degree of polymerization can be measured by measuring the time-dependent changes in specific peaks attributed to specific structures of the polymerizable compound using an infrared spectrophotometer, for example, by the method described in Japanese Patent Application Publication No. 2006-76122.

[0041] In the present invention, an additional step may be provided between step 1 and step 2, such as irradiation with active light, heating, or drying, within the range that the first curable composition remains in an uncured state, so as not to cause the first curable composition to become completely solid.

[0042] "The first and second curable compositions are at least a thermosetting composition or a photocurable composition" means that the first and second curable compositions are curable compositions of one of three types: a thermosetting composition, a photocurable composition, or a composition that possesses both thermosetting and photocurable properties.

[0043] 1. Recording Method (1.1) Recording media The recording medium used in the present invention is not particularly limited, but preferably it is made of materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluorine, polyethylene, PPO, cyanate ester, etc., and preferably all grades (FR-4, etc.) of copper-clad laminates, as well as polyimide film, PET film, glass substrate, ceramic substrate, wafer plate, stainless steel plate, copper plate, etc.

[0044] (1.2) Steps 1 and 2 Step 1 is the step of coating a first curable composition in the form of a thin film onto a recording medium. Step 2 is the step of applying a second curable composition onto the first curable composition, which has been applied and is in an uncured state. The application of the first curable composition in step 1 and the application of the second curable composition in step 2 can each be carried out using various conventionally known application and printing methods. For example, coating, offset printing, screen printing, gravure printing, flexographic printing, and inkjet recording methods can be used. The coating methods used in Step 1 and Step 2 may be the same or different.

[0045] (1.3) Process 3 The curing step in step 3 is a step of applying sufficient active light and / or thermal energy to the layer of the curable composition to completely cure the composition. These curing methods can be conventionally known methods as appropriate.

[0046] The active light can be selected from, for example, electron beams, ultraviolet rays, alpha rays, gamma rays, and X-rays, but ultraviolet rays are preferred. Ultraviolet irradiation can be performed using, for example, a water-cooled LED manufactured by Phoseon Technology, under conditions of a wavelength of 395 nm. By using an LED as the light source, it is possible to suppress curing defects in the curable composition caused by the melting of the curable composition due to the radiant heat of the light source.

[0047] The ultraviolet irradiation uses ultraviolet light with a wavelength in the range of 340 to 410 nm, and the peak illuminance on the surface of the curable composition is preferably 0.05 to 10 W / cm². 2 Within the range of 0.1 to 5 W / cm², more preferably 0.1 to 5 W / cm². 2 It should be done within the specified range. From the viewpoint of suppressing the irradiation of radiant heat onto the curable composition, the amount of light irradiated should be 1500 mJ / cm². 2 It is preferable that it be less than [a certain value].

[0048] Irradiation with active light is preferably performed between 0.001 and 300 seconds after application of the curable composition, and more preferably between 0.001 and 60 seconds in order to form a high-resolution resist film.

[0049] The first and second curable compositions are irradiated with light and then heated to cure them completely.

[0050] The preferred heating method is, for example, to place the food in an oven set to a temperature within the range of 110 to 180°C for 10 to 120 minutes.

[0051] (1.4) Additional steps As described above, within the scope of keeping the first curable composition in an uncured state, a step can be added between step 1 and step 2, such as irradiation with active light or heat or drying, to the extent that the first curable composition does not become a completely solid. The first curable composition after step 1 can be irradiated with active light. In that case, it is preferable to select from the same methods as those used for the activated light in step 3. For irradiation with active light while keeping the first curable composition uncured, it is preferable that the amount of light irradiated is less than that irradiated in step 3.

[0052] (Inkjet recording method) The application of the first and second curable compositions in steps 1 and 2 can be carried out by inkjet recording. By using the inkjet recording method, it becomes easy to apply the curable composition only to the necessary areas, which is particularly advantageous when applying resist patterns or characters. The inkjet method is a method of ejecting inkjet ink from nozzles and depositing it onto a recording medium. For example, in step 1, droplets of the first curable composition according to the present invention can be ejected from an inkjet head and landed on a substrate, such as a printed circuit board, which is a recording medium, at a position corresponding to the resist film to be formed, thereby enabling patterning.

[0053] In step 2, droplets of the second curable composition are ejected from the inkjet head onto the first curable composition, which is in an uncured state, and applied onto the first curable composition which has been applied to a substrate, such as a printed circuit board, which is a recording medium, at a position corresponding to the resist film to be formed, and then patterned.

[0054] The inkjet head can use either an on-demand or continuous ejection method. The on-demand inkjet head may be any of the following: electromechanical conversion methods such as single-cavity type, double-cavity type, bender type, piston type, shear-mode type, and shared-wall type, as well as electro-thermal conversion methods such as thermal inkjet type and bubble jet (registered trademark) (bubble jet is a registered trademark of Canon Inc.).

[0055] By ejecting droplets of the first curable composition from the inkjet head while heated, ejection stability can be improved. The temperature of the first curable composition when it is dispensed is preferably in the range of 40 to 100°C, and more preferably in the range of 40 to 90°C to further improve the dispensing stability. In particular, it is preferable to perform injection at an ink temperature such that the viscosity of the first curable composition is in the range of 7 to 15 mPa·s, more preferably in the range of 8 to 13 mPa·s.

[0056] When using a sol-gel phase transition type ink containing a gelling agent as the first and / or second curable composition, it is preferable that the temperature of the ink when it is filled into the inkjet head be set to (gelling temperature + 10)°C to (gelling temperature + 30)°C in order to improve the ejection of the ink from the inkjet head. If the ink temperature inside the inkjet head is (gelling temperature + 10)°C or higher, it is possible to suppress the gelling of the ink inside the inkjet head or on the nozzle surface, which can reduce the ink ejection performance. On the other hand, if the ink temperature inside the inkjet head falls below (gelling temperature + 30)°C, the ink ejection stability deteriorates.

[0057] The heating method for the first and / or second curable composition is not particularly limited. For example, at least one of the components of the head carriage, such as the ink supply system including the ink tank, supply pipe, and pre-chamber ink tank directly in front of the head, filtered piping, and piezo head, can be heated by a panel heater, ribbon heater, or warm water.

[0058] The amount of droplets of the first and / or second curable composition being ejected is preferably in the range of 2 to 20 pL, from the viewpoint of recording speed and image quality. As an inkjet coating apparatus, an apparatus like the one shown in Figure 2 can be used. Figure 2A shows a scan-type device in which the print head unit HU reciprocates perpendicularly to the transport direction Q of the substrate to perform printing, while Figure 2B shows a single-pass type device in which the print head unit is fixed relative to the transport direction Q of the substrate to perform printing. The combination of applying the first curable composition and applying the second curable composition as shown in Figures 2A and 2B can be freely selected. In Figure 2, multiple heads H are shown in the print head unit HU, but there may be only one head H. Using multiple print heads H is preferable because it allows for faster printing speeds and thus increases production efficiency.

[0059] When the application of the first curable composition and the application of the second curable composition are performed consecutively within the same apparatus, several configurations that are effective for substrate P transport and inkjet printing timing can be proposed, some of which are shown in Figure 3.

[0060] Figure 3A shows a configuration in which the substrate is folded and transported after the application of the first curable composition, and it is possible to apply the second curable composition during this folded transport, or to return the substrate to its initial position and then transport it again (upward) to apply the second curable composition. This method has the advantage of not requiring the replacement of the circuit board.

[0061] Figure 3B shows a configuration in which multiple print head units HU (two in the figure) are provided, and the application of the first curable composition and the application of the second curable composition are performed by different print head units HU. This method allows for efficient processing because the application of the first curable composition and the application of the second curable composition can be carried out continuously while the substrate P is being transported in one direction. This is particularly advantageous when the second curable composition is applied while the first curable composition is still uncured after application.

[0062] Figure 3C shows a variation of the apparatus in Figure 3B, configured to transport multiple substrates P (two in the figure) in parallel. This allows for simultaneous processing of multiple substrates, making it even more efficient. Each print head unit HU in Figure 3 can be appropriately adopted as either the scan type shown in Figure 2A or the single-pass type shown in Figure 2B. Furthermore, the drive timing of each print head unit HU may be individual or synchronized.

[0063] 2. Recording device (Device configuration) The recording method of the present invention can be carried out using an apparatus having the following configuration, but is not limited to these.

[0064] The apparatus for carrying out the present invention may perform steps 1, 2, 3, and additional steps in separate, independent devices, or it may perform them in a device that combines several of the steps. Furthermore, the apparatus may be equipped with functions to perform processes other than those listed above.

[0065] When each process is carried out by independent equipment, automated transport functions such as conveyor belts and robotic transfers can be provided to move the processing substrates between these independent devices. In the case of equipment where multiple processes are combined within the same device, the arrangement of each process can take various forms. It is possible to adopt various configurations as appropriate, such as a conveyor system, a slider system with a linear transport path, a turntable system where the substrate and the processed material move relative to each other by rotating between processes, and a configuration where multiple processes are arranged vertically. Performing a series of processes within a single device reduces handling work associated with substrate transfer, resulting in increased productivity.

[0066] Figure 4 shows an example of a schematic diagram of an apparatus for implementing the present invention, which has a configuration that moves rotatably between each process. Figure 4 is a schematic diagram of the substrate transport table only, where S represents the rotation direction of the transport table. In Figure 4, the numbers (1) to (6) represent the numbers of the transport tables on which the substrates are placed.

[0067] For example, a substrate P, which is a recording medium, is placed at the position of the transport table (1), and the first curable composition is applied in a thin film at position (2) (step 1). Subsequently, if necessary, the first curable composition is irradiated with active light or heat or dried at position (3) to the extent that it does not become completely solid (additional step), the second curable composition is applied on top of the uncured first curable composition at position (4) (step 2), and the layer of curable composition is cured at position (5) by being exposed to sufficient active light and / or heat energy to completely cure the curable composition (step 3). When the transport table reaches position (6), the circuit board is removed, and each process is completed.

[0068] In Figure 4, each process is shown as a separate stage; however, it is also possible to configure the processes to span multiple stages in order to adjust the processing time at each stage.

[0069] 3. Component compounds constituting the first and second curable compositions The following describes the component compounds that constitute the curable composition suitable for use in the recording method of the present invention. Although the first curable composition and the second curable composition according to the present invention are different compositions, the same compound can be used.

[0070] (3.1)Thermopolymerizable compounds The following compounds can be used as "thermally polymerizable compounds" or "thermosetting agents" as component compounds constituting the first and second curable compositions according to the present invention. Furthermore, the thermopolymerizable compounds according to the present invention also include compounds that, depending on the reaction conditions, possess the property of undergoing polymerization reactions in response to light.

[0071] The thermally polymerizable compound is preferably at least one selected from cyclic ether group-containing thermally polymerizable compounds, isocyanate group-containing thermally polymerizable compounds, and maleimide group-containing thermally polymerizable compounds. In particular, 4-hydroxybutyl acrylate glycidyl ether, 4,4′-diphenylmethane bismaleimide, bisphenol A type epoxy resin, and blocked isocyanates are preferred. Bisphenol A type epoxy resin is more preferred, and blocked isocyanate is even more preferred.

[0072] In the present invention, it is preferable to include a thermopolymerizable compound as a "thermosetting agent" in an amount of 1 to 15% by mass, more preferably 2 to 10%, based on the total mass of the curable composition.

[0073] (3.1.1) Cyclic ether group-containing thermopolymerizable compounds The cyclic ether group-containing thermopolymerizable compound may have multiple cyclic ether groups in its molecule, and compounds having epoxy groups or oxetanyl groups are preferred.

[0074] (Compounds containing epoxy groups) Examples of compounds having epoxy groups include 4-hydroxybutyl acrylate glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, terephthalate diglycidyl ester, phthalate diglycidyl ester, hydrogenated phthalate diglycidyl ester, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol glycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol glycidyl ether, and cresol novolac type epoxy emulsion.

[0075] Examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4′-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4′-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), and bisphenol Z type epoxy resin (4,4′-cyclohexydiene bisphenol type epoxy resin); phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, and condensed ring aromatic carbonized water. This may include one or more of the following: novolac epoxy resins having an elementary structure; biphenyl epoxy resins; xylylene epoxy resins, biphenylaralkyl epoxy resins, and other aralkyl epoxy resins; epoxy resins having a naphthalene skeleton, such as naphthylene ether epoxy resins, naphthol epoxy resins, naphthalenediol epoxy resins, bifunctional or tetrafunctional epoxy naphthalene resins, binaphthyl epoxy resins, and naphthalenearalkyl epoxy resins; anthracene epoxy resins; phenoxy epoxy resins; dicyclopentadiene epoxy resins; norbornene epoxy resins; adamantane epoxy resins; and fluorene epoxy resins.

[0076] (Compounds containing an oxetanyl group) Examples of compounds having an oxetanyl group include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate and polyfunctional oxetanes such as their oligomers or copolymers, as well as oxetane alcohols and novolac resins. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

[0077] (4.1.2) Isocyanate group-containing thermopolymerizable compounds The isocyanate group-containing thermopolymerizable compounds are not particularly limited as long as they have two or more isocyanate groups in their molecule, and specifically include aromatic compounds such as 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), and 1,5-naphthalene diisocyanate (NDI). Examples include aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, and norbornane diisocyanate methyl (NBDI); alicyclic polyisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6XDI (hydrogenated XDI), H12MDI (hydrogenated MDI), and H6TDI (hydrogenated TDI); polyisocyanates such as polymethylene polyphenylene polyisocyanate; and their bilets, isocyanurates, and carbodiimide modified products.

[0078] (Blocked isocyanate compounds) Among the above-mentioned isocyanate group-containing thermopolymerizable compounds, blocked isocyanate compounds, which are polyfunctional isocyanates having isocyanate groups protected by a thermally dissociable blocking agent, are preferable in terms of adhesion to recording media and surface hardness of the coating film because the thermosetting reaction proceeds as the isocyanate groups protected by the blocking agent undergo thermal dissociation.

[0079] The thermally dissociable blocking agent is preferably at least one compound selected from the group consisting of oxime compounds, pyrazole compounds, and active ethylene compounds, in terms of the storage capacity and thermal dissociation properties of the curable composition.

[0080] In the case of the double-cure method, if the first curable composition according to the present invention contains a gelling agent, the gelling agent is not incorporated into the monomer polymerization during UV irradiation and is meltable upon heating, so it can function as a dissolving aid for the thermosetting agent during thermal polymerization and can promote the thermosetting reaction.

[0081] Furthermore, when the first curable composition according to the present invention contains a gelling agent, the effect becomes even more pronounced due to the high compatibility between the isocyanate and the gelling agent. In particular, aliphatic polyisocyanate types exhibit even greater solubility, resulting in higher adhesion to recording media. Furthermore, since the thermosetting agent becomes uniform throughout the coating during thermal polymerization, the surface hardness is also improved.

[0082] Examples of oxime-based blocking agents include formamide oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketone oxime, and cyclohexanone oxime.

[0083] Examples of pyrazole-based blocking agents include pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole, among others.

[0084] Examples of active ethylene-based blocking agents include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone.

[0085] (Examples of blocked isocyanate compounds) Examples of polyfunctional isocyanate compounds having isocyanate groups protected by the blocking agent include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, 2-[(3-butylidene)aminooxycarbonylamino]ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl acrylate, and 2-[(3-butylidene)aminooxycarbonylamino]ethyl acrylate.

[0086] Examples of commercially available products include trixeneBI7982 (manufactured by LANXESS), trixeneBI7961 (manufactured by LANXESS), Blonate1601V (manufactured by Daiei Sangyo Co., Ltd.), PU5208 (manufactured by Lesson Polyurethanes), PU5364 (manufactured by Lesson Polyurethanes), Coronate2554 (manufactured by Tosoh Corporation), Vestanat B 1358 A (manufactured by Evonik), Vestanat B 1186 A (manufactured by Evonik), and others.

[0087] (3.1.3) Maleimide group-containing thermally polymerizable compound Examples of maleimide group-containing thermopolymerizable compounds include N-methylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-propylmaleimide, N-butylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, Np-carboxyphenylmaleimide, Np-hydroxyphenylmaleimide, Np-chlorophenylmaleimide, Np-tolylmaleimide, Np- Xylylmaleimide, No-chlorophenylmaleimide, No-tolylmaleimide, N-benzylmaleimide, N-2,5-diethylphenylmaleimide, N-2,5-dimethylphenylmaleimide, Nm-tolylmaleimide, N-α-naphthylmaleimide, No-xylylmaleimide, Nm-xylylmaleimide, bismaleimimomethane, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, bismaleimidodecane, N,N Examples include '-m-phenylenedimaleimide, N,N'-p-phenylenedimaleimide, 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide-di(3-methylphenyl)methane, 4,4'-bismaleimide-di(3-ethylphenyl)methane, 4,4'-bismaleimide-di(3-methyl-5-ethyl-phenyl)methane, N,N'-(2,2-bis-(4-phenoxyphenyl)propane)dimaleimide, N,N'-2,4-tolylenedimaleimide, N,N'-2,6-tolylenedimaleimide, N,N'-m-xylylenedimaleimide, and bisphenol A diphenyl ether bismaleimide. Among these, bismaleimide is preferred.

[0088] Examples of commercially available thermopolymerizable compounds include 4-hydroxybutyl acrylate glycidyl ether 4HBAGE (manufactured by Mitsubishi Chemical Corporation), 4,4′-diphenylmethane bismaleimide BMI-1000 (manufactured by Yamato Chemical Industries Co., Ltd.), bisphenol A type epoxy resin YD-127 (manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation), blocked isocyanate trixeneBI7982 (manufactured by LANXESS), blocked isocyanate trixeneBI7961 (manufactured by LANXESS), and blocked isocyanate Blonate 1601 V (manufactured by Daiei Sangyo Co., Ltd.).

[0089] (3.2) Photopolymerizable compound The photocurable composition according to the present invention contains a photopolymerizable compound. The photopolymerizable compound can be any compound that undergoes polymerization or crosslinking reactions upon irradiation with active light, thereby curing the composition. Furthermore, the photopolymerizable compounds according to the present invention also include compounds that, depending on the reaction conditions, possess the property of undergoing a polymerization reaction upon heating.

[0090] Examples of photopolymerizable compounds include radical polymerizable compounds and cationic polymerizable compounds. The photopolymerizable compound may be a monomer, a polymerizable oligomer, a prepolymer, or a mixture thereof. The photopolymerizable compound may be present in the curable composition as one type only, or as two or more types.

[0091] The content of the photopolymerizable compound can be, for example, in the range of 1 to 97% by mass, preferably in the range of 60 to 90%, based on the total mass of the curable composition.

[0092] (3.2.1) Radical polymerizable compounds The radical polymerizable compound is preferably a compound having a radically polymerizable ethylenically unsaturated bond, and any compound having at least one radically polymerizable ethylenically unsaturated bond in its molecule is acceptable, including those in chemical forms such as monomers, oligomers, and polymers.

[0093] Only one type of radical polymerizable compound may be used, or two or more types may be used in any ratio to improve the desired properties.

[0094] The radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth)acrylate. In this invention, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl group" means acryloyl group or methacryloyl group, and "(meth)acrylic" means acrylic or methacrylic.

[0095] (Example of (meth)acrylate) Examples of (meth)acrylates include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomirsutyl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and cumylphenoxyethyl acrylate. Monofunctional acrylates including tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid, and t-butylcyclohexyl (meth)acrylate, as well as triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,This includes difunctional acrylates such as 9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A PO adduct di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and tricyclodecane dimethanol diacrylate, as well as polyfunctional acrylates including trifunctional or more acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, and pentaerythritol ethoxytetra(meth)acrylate.

[0096] Of the above (meth)acrylates, phenoxyethyl (meth)acrylate, o-phenylphenol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and cumylphenoxyethyl acrylate are preferred from the viewpoint of curing shrinkage and other factors.

[0097] From the viewpoint of curability, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, bisphenol A PO adduct di(meth)acrylate, and hydroxypivalic acid neopentyl glycol di(meth)acrylate are preferred.

[0098] Furthermore, (meth)acrylate may be a modified form. Examples of modified (meth)acrylates include ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetraacrylate, and other ethylene oxide-modified (meth)acrylates; caprolactone-modified (meth)acrylates, including caprolactone-modified trimethylolpropane tri(meth)acrylate; and caprolactam-modified (meth)acrylates, including caprolactam-modified dipentaerythritol hexa(meth)acrylate.

[0099] The (meth)acrylate may also be a polymerizable oligomer. Examples of polymerizable oligomers (meth)acrylates include epoxy (meth)acrylate oligomers, aliphatic urethane (meth)acrylate oligomers, aromatic urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and linear (meth)acrylic oligomers.

[0100] (3.2.2) Cationic polymerizable compounds Cationic polymerizable compounds can include epoxy compounds, vinyl ether compounds, and oxetane compounds. The curable composition may contain only one cationic polymerizable compound, or it may contain two or more types.

[0101] (3.2.3) Photopolymerization initiators When the photopolymerizable compound is a radical polymerizable compound, it is preferable to use a photoradical initiator as the photopolymerization initiator, and when the photopolymerizable compound is a cationic polymerizable compound, it is preferable to use a photoacid generator. The photopolymerization initiator may be one type or two or more types in the curable composition according to the present invention.

[0102] The photopolymerization initiator may be a combination of both a photoradical initiator and a photoacid generator.

[0103] (Photoradical initiator) Photo-radical initiators include α-cleavage type radical polymerization initiators (also known as Norrish type I polymerization initiators) and hydrogen abstraction type radical polymerization initiators (also known as Norrish type II polymerization initiators).

[0104] In the first curable composition according to the present invention, the amount of hydrogen abstraction-type radical polymerization initiator is greater than that of α-cleavage-type radical polymerization initiator. This promotes crosslinking and gelling of the coating film due to the hydrogen abstraction effect, further improving the crosslinking density of the coating film and thus improving adhesion to the recording medium (substrate).

[0105] The content of the hydrogen abstraction type radical polymerization initiator is preferably in the range of 4 to 10% by mass relative to the mass of the curable composition. The content of the α-cleavage type radical polymerization initiator is preferably in the range of 0.3 to 3% by mass relative to the mass of the curable composition.

[0106] α-cleavage type radical polymerization initiators are initiators that cleave after photoexcitation and directly provide an initiation radical. Hydrogen abstraction radical polymerization initiators are photopolymerization initiators that are activated by active light (e.g., ultraviolet light) and generate free radicals by abstracting hydrogen from a second compound, with the second compound becoming the actual initiating free radical. This second compound is called a polymerization synergist or co-initiator. Both type I and type II photopolymerization initiators can be used individually or in combination in the present invention.

[0107] Examples of cleavage-type radical polymerization initiators include acetophenone-based initiators, benzoin-based initiators, acylphosphine oxide-based initiators, benzyl, and methylphenylglyoxyesters.

[0108] Examples of acetophenone initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

[0109] Examples of benzoin-based initiators include benzoin, benzoin methyl ether, and benzoin isopropyl ether. Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoindiphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0110] Examples of hydrogen abstraction radical initiators include benzophenone-based initiators, thioxanthone-based initiators, aminobenzophenone-based initiators, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone. Examples of benzophenone initiators include benzophenone, o-benzoylmethyl-4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylic benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3′-dimethyl-4-methoxybenzophenone. Examples of thioxanthone initiators include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. Examples of aminobenzophenone initiators include Michler's ketone and 4,4′-diethylaminobenzophenone.

[0111] (Photoacid generator) Examples of photoacid generators include compounds listed on pages 187-192 of "Organic Materials for Imaging," edited by the Organic Electronic Materials Research Group, Bunshin Publishing (1993). The amount of photopolymerization initiator should be within a range that allows the curable composition to cure sufficiently, for example, it can be in the range of 0.01 to 10% by mass relative to the total mass of the curable composition according to the present invention.

[0112] Examples of commercially available photopolymerization initiators include DAROCURE TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) (BASF), Irgacure 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) (BASF), Irgacure 379 (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone) (BASF), Irgacure 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one), Speedcure DETX (2,4-diethylthioxanthone), Speedcure ITX (2-isopropylthioxanthone) (both Lambson), Genocure ITX (Rahn AG), and Genocure EPD (Rahn AG). This includes products manufactured by AG Corporation, etc.

[0113] The curable composition according to the present invention may further contain, if necessary, photopolymerization initiators, polymerization inhibitors, and the like. The photopolymerization initiator aid may be a tertiary amine compound, and an aromatic tertiary amine compound is preferred.

[0114] Examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-methylamino-p-benzoate ethyl ester, N,N-dimethylamino-p-benzoate isoamyl ethyl ester, N,N-dihydroxyethylaniline, triethylamine, and N,N-dimethylhexylamine. Among these, N,N-dimethylamino-p-benzoate ethyl ester and N,N-dimethylamino-p-benzoate isoamyl ethyl ester are preferred. These compounds may be used individually or in combination of two or more.

[0115] Regarding the amount of photopolymerization initiator added, it is better to add a small amount in order to promote the thermosetting reaction by moderately suppressing the curing by light. The amount of the curable composition is preferably in the range of 0.2 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, relative to the total mass of the curable composition.

[0116] (3.3) Polymerization inhibitors From the viewpoint of improving the adhesion between multiple curable compositions, it is preferable that the first curable composition according to the present invention contains a polymerization inhibitor. Here, "polymerization inhibitor" generally includes all compounds added to suppress polymerization reactions during the preparation or storage of curable compositions containing polymerizable compounds.

[0117] In the present invention, various conventionally known polymerization inhibitors can be used, but from the viewpoint of effectiveness, it is more preferable to include a polymerization inhibitor that is one of the following: an N-oxyl polymerization inhibitor, a phenol polymerization inhibitor containing an ot-butyl group, or a polymerization inhibitor having two or more aromatic rings.

[0118] Furthermore, from the viewpoint of interlayer adhesion, it is even more preferable to include an N-oxyl polymerization inhibitor among these. Similarly, for the second curable composition, an N-oxyl polymerization inhibitor is preferred. The polymerization inhibitor content is preferably in the range of 0.05 to 0.5% by mass relative to the mass of the curable composition.

[0119] (3.3.1) N-oxyl polymerization inhibitors Examples of N-oxyl polymerization inhibitors include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and Irgastab UV10 (manufactured by BASF).

[0120] (3.3.2) Phenolic polymerization inhibitors Examples of phenolic polymerization inhibitors include 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT), 4-methoxyphenol, and 2-methoxy-4-methylphenol.

[0121] (3.3.3) Quinone-based polymerization inhibitors Examples of quinone polymerization inhibitors include hydroquinone, methoxyhydroquinone, benzoquinone, 1,4-naphthoquinone, and p-tert-butylcatechol.

[0122] (3.3.4) Amine-based polymerization inhibitors Examples of amine-based polymerization inhibitors include alkylated diphenylamine, N,N′-diphenyl-p-phenylenediamine, and phenothiazine.

[0123] (3.3.5) Other polymerization inhibitors Other examples include copper dithiocarbamate-based polymerization inhibitors such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate.

[0124] These can be used individually, or two or more can be used in combination. Among these, N-oxyl and quinone-based polymerization inhibitors are preferred, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT), 2,4-di-tert-butylphenol, and, as polymerization inhibitors having two or more aromatic rings, naphthoquinone and the like are suitably used.

[0125] (3.4) Multifunctional polymerizable compound From the viewpoint of improving interlayer adhesion between the first and second curable compositions, it is preferable that both the first and second curable compositions according to the present invention contain a polyfunctional polymerizable compound. Examples of polyfunctional polymerizable compounds include polyfunctional radical polymerizable compounds having multiple radical polymerizable functional groups.

[0126] Polyfunctional radical polymerizable compounds preferably have two or more radical polymerizable functional groups. Examples of such polyfunctional radical polymerizable compounds include polyfunctional (meth)acrylates and polyfunctional urethane acrylates, epoxy-modified polyfunctional acrylates, and the like. The above-mentioned radical polymerizable compounds may be one or more.

[0127] (3.5) Gelling agent The first curable composition according to the present invention preferably contains a gelling agent. The gelling agent has the function of temporarily fixing (pinning) the curable composition applied to the recording medium into a gel state. When a curable composition containing a gelling agent is pinned in a gel state, the wetting and spreading of the curable composition is suppressed. When the second curable composition is applied while the first curable composition is uncured or insufficiently cured, the two layers mix at the interface between the first and second curable compositions, thereby improving interlayer adhesion while preventing bleeding.

[0128] It is preferable that the gelling agent crystallizes at a temperature below the gelation temperature of the curable composition. The gelation temperature is the temperature at which, when a curable composition that has been sol-like or liquefied by heating is cooled, the gelling agent undergoes a phase transition from sol to gel, causing a rapid change in the viscosity of the curable composition. Specifically, a sol- or liquefied curable composition can be cooled while its viscosity is measured using a viscoelasticity measuring device (e.g., MCR300, manufactured by Anton Paar), and the temperature at which the viscosity rapidly increases can be defined as the gelation temperature of the curable composition.

[0129] When the gelling agent crystallizes in the curable composition, a structure is formed in which the photopolymerizable compound is encapsulated in a three-dimensional space created by the plate-like crystallized gelling agent, a structure known as a cardhouse structure.

[0130] To form a cardhouse structure, it is preferable that the photopolymerizable compound dissolved in the curable composition and the gelling agent are compatible.

[0131] Examples of gelling agents suitable for forming cardhouse structures include aliphatic ketones, aliphatic esters, petroleum waxes, plant waxes, animal waxes, mineral waxes, hydrogenated castor oil, modified waxes, higher fatty acids, higher alcohols, hydroxystearic acid, fatty acid amides including N-substituted fatty acid amides and special fatty acid amides, higher amines, esters of sucrose fatty acids, synthetic waxes, dibenzylidene sorbitol, dimer acids, and dimer ols.

[0132] In particular, from the viewpoint of further enhancing pinning properties, aliphatic ketones, aliphatic esters, higher fatty acids, and higher alcohols having hydrocarbon groups in the range of 9 to 25 carbon atoms are preferred. The gelling agent may be present in the curable composition as one type only, or as two or more types.

[0133] (3.5.1) Faliphatic ketones Examples of aliphatic ketones include dilignoseryl ketone, dibehenyl ketone, distearyl ketone, dieicosyl ketone, dipalmityl ketone, dilauryl ketone, dimyristyl ketone, myristylpalmityl ketone, and palmitylstearyl ketone.

[0134] (3.5.2) Aliphatic esters Examples of aliphatic esters include fatty acid esters of monoalcohols such as behenyl behenate, eicosyl eicosanoate, and oleyl palmitate; and fatty acid esters of polyhydric alcohols such as glycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, ethylene glycol fatty acid esters, and polyoxyethylene fatty acid esters.

[0135] Examples of commercially available aliphatic esters include the EMALEX series, manufactured by Nippon Emulsion Co., Ltd. ("EMALEX" is a registered trademark of the company), the Rikemar series and Poem series, manufactured by Riken Vitamin Co., Ltd. ("Rikemar" and "Poem" are both registered trademarks of the company).

[0136] (3.5.3) Higher fatty acids Examples of higher fatty acids include behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid.

[0137] (3.5.4) Higher alcohols Examples of higher alcohols include stearyl alcohol and behenyl alcohol.

[0138] (3.5.5) Particularly preferred gelling agents In particular, in the present invention, an aliphatic ketone represented by the following general formula (G1) or an aliphatic ester represented by the following general formula (G2) is especially preferred as a gelling agent.

[0139] General formula (G1): R1-CO-R2

[0140] (In general formula (G1), R1 and R2 each independently represent an alkyl group containing a straight chain portion with 12 to 26 carbon atoms, and which may also contain branching. R1 and R2 may be the same or different.)

[0141] General formula (G2): R3-COO-R4

[0142] (In general formula (G2), R3 and R4 each independently represent an alkyl group containing a linear portion with 12 to 26 carbon atoms, and which may also contain branching. R3 and R4 may be the same or different.)

[0143] In general formulas (G1) and (G2), the number of carbon atoms in the linear or branched hydrocarbon group is 12 or more, which increases the crystallinity of the aliphatic ketone represented by general formula (G1) and the aliphatic ester represented by general formula (G2), and also creates more space in the cardhouse structure described above. Therefore, the photopolymerizable compound is more easily encapsulated within the above-mentioned space, and the pinning properties of the curable composition are further enhanced. Because the number of carbon atoms in the linear or branched hydrocarbon groups is 26 or less, the melting points of the aliphatic ketones represented by general formula (G1) and the aliphatic esters represented by general formula (G2) do not rise excessively, and there is no need to excessively heat the curable composition when injecting it.

[0144] Examples of aliphatic ketones represented by general formula (G1) include dilignoseryl ketone (23,24 carbon atoms), dibehenyl ketone (21,22 carbon atoms), distearyl ketone (17,18 carbon atoms), dieicosyl ketone (19,20 carbon atoms), dipalmityl ketone (15,16 carbon atoms), dimyristyl ketone (13,14 carbon atoms), dilauryl ketone (11,12 carbon atoms), and lauryl myristyl ketone (carbon atoms) This includes carbon 11, 14), lauryl palmityl ketone (carbon number: 11, 16), myristyl palmityl ketone (carbon number: 13, 16), myristyl stearyl ketone (carbon number: 13, 18), myristyl behenyl ketone (carbon number: 13, 22), palmityl stearyl ketone (carbon number: 15, 18), palmityl behenyl ketone (carbon number: 15, 22), and stearyl behenyl ketone (carbon number: 17, 22). The carbon numbers in parentheses represent the number of carbon atoms in each of the two hydrocarbon groups separated by the carbonyl group.

[0145] Examples of commercially available aliphatic ketones represented by general formula (G1) include 18-Pentatriacontanon, manufactured by Alfa Aeser; Hentriacontan-16-on, manufactured by Alfa Aeser; and Kao Wax T-1, manufactured by Kao Corporation.

[0146] Examples of aliphatic esters represented by general formula (G2) include behenyl behenate (21,22 carbon atoms), eicosyl eicosanoate (19,20 carbon atoms), stearyl stearate (17,18 carbon atoms), palmityl stearate (16,17 carbon atoms), lauryl stearate (12,17 carbon atoms), cetyl palmitate (6,15 carbon atoms), stearyl palmitate (15,18 carbon atoms), and myris. This includes myristyl tinate (13,14 carbon atoms), cetyl myristate (13,16 carbon atoms), octyldodecyl myristate (13,20 carbon atoms), stearyl oleate (17,18 carbon atoms), stearyl erucate (18,21 carbon atoms), stearyl linoleate (17,18 carbon atoms), behenyl oleate (18,22 carbon atoms), and arachidyl linoleate (17,20 carbon atoms). The carbon numbers in parentheses represent the number of carbon atoms in each of the two hydrocarbon groups separated by the ester group.

[0147] Examples of commercially available aliphatic esters represented by general formula (G2) include Unistar M-2222SL and Sperm Acetate, manufactured by NOF Corporation ("Unistar" is a registered trademark of the company), Excepearl SS and Excepearl MY-M, manufactured by Kao Corporation ("Excepearl" is a registered trademark of the company), EMALEX CC-18 and EMALEX CC-10, manufactured by Nippon Emulsion Co., Ltd. ("EMALEX" is a registered trademark of the company), and Amlepus PC, manufactured by Higher Alcohol Industry Co., Ltd. ("Amlepus" is a registered trademark of the company).

[0148] (3.5.6) Content of gelling agent The gelling agent content is preferably in the range of 1.0 to 10.0% by mass relative to the total mass of the curable composition.

[0149] (3.6) Other ingredients (3.6.1) Surfactants A surfactant may be added to the curable composition according to the present invention, depending on the purpose. Examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene-polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and silicone-based and fluorine-based surfactants.

[0150] (3.6.2) Colorants The curable composition according to the present invention may further contain a coloring agent if necessary. The coloring agent may be a pigment or a dye, but a pigment is preferred because it has good dispersibility with the components of the curable composition and excellent weather resistance. The pigments are not particularly limited, but examples include organic or inorganic pigments with the following numbers listed in the color index.

[0151] The coloring agent may be included in the curable composition according to the present invention, one or more types, and may be toned to a desired color. The colorant content is preferably in the range of 0.1 to 20% by mass, and more preferably in the range of 0.2 to 10% by mass, relative to the total amount of the curable composition.

[0152] (Pigment) Red or magenta pigment Examples of red or magenta pigments include: Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257; Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88; Pigment Orange It includes pigments or mixtures thereof selected from 13, 16, 20, and 36.

[0153] Blue or cyan pigment Examples of blue or cyan pigments include pigments or mixtures thereof selected from Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, and 60.

[0154] Green pigment Examples of green pigments include pigments or mixtures thereof selected from Pigment Green 7, 26, 36, and 50.

[0155] Yellow pigment Examples of yellow pigments include pigments or mixtures thereof selected from Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, and 193.

[0156] Black pigment Examples of black pigments include pigments selected from Pigment Black 7, 28, and 26, or mixtures thereof.

[0157] Examples of commercially available pigments Examples of commercially available pigments include Black Pigment (Mikuni), Chromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromofine Orange 3700L, 6730, Chromofine Scarlet 6750, Chromofine Magenta 6880, 6886, 6891N, 6790, 6887, Chromofine Violet RE, Chromofine Red 6820, 6830, Chromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromofine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromofine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770, Seika Fast Red 8040, C405(F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seika Light Rose R40, Seika Light Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 900, 2900, Seika Light Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (all manufactured by Dainichi Seika Kogyo Co., Ltd.); KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (manufactured by DIC);Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T-13, T-05, Pigment Yellow1705, Colortex Orange 202, Colortex Red101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon601, Colortex BrownB610N, Colortex Violet600, Pigment Red 122, Colortex Blue516, 517, 518, 519, A818, P-908, 510, Colortex Green 402, 403, Colortex Black 702, U905 (all manufactured by Sanyo Pigment Co., Ltd.); Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (all manufactured by Toyo Ink Co., Ltd.), Toner Magenta E02, Permanent Rubin F6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapean Blue B2G (all manufactured by Hoechst Industries Co., Ltd.); Novoperm P-HG, Hostapean Pink E, Hostapean Blue Examples include B2G (all manufactured by Clariant); Carbon Black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, CF9 (all manufactured by Mitsubishi Chemical), etc.

[0158] Pigment dispersion Pigment dispersion can be performed using, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, and paint shaker.

[0159] The pigment dispersion is preferably carried out such that the volume-average particle size of the pigment particles is preferably in the range of 0.08 to 0.5 μm, the maximum particle size is preferably in the range of 0.3 to 10 μm, and more preferably in the range of 0.3 to 3 μm. The dispersion of pigments is controlled by selecting the pigment, dispersant, and dispersion medium, as well as by adjusting the dispersion conditions and filtration conditions.

[0160] Dispersant The curable composition according to the present invention may further contain a dispersant to enhance the dispersibility of the pigment. Examples of dispersants include hydroxyl group-containing carboxylic acid esters, salts of long-chain polyaminoamides and high molecular weight acid esters, salts of high molecular weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, high molecular weight unsaturated acid esters, polymer copolymers, modified polyurethanes, modified polyacrylates, polyether ester-type anionic surfactants, naphthalene sulfonic acid formalin condensate salts, aromatic sulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, polyoxyethylene nonylphenyl ether, and stearylamine acetate. Examples of commercially available dispersants include Avecia's Solsperse series and Ajinomoto Fine Techno's PB series.

[0161] Dispersing agent The curable composition according to the present invention may further contain a dispersion aid as needed. The dispersing agent should be selected according to the pigment. The total amount of the dispersant and dispersing agent is preferably in the range of 1 to 50% by mass relative to the pigment.

[0162] 《Dispersion medium》 The curable composition according to the present invention may further include a dispersion medium for dispersing pigments, if necessary. While a solvent may be included in the curable composition as a dispersion medium, it is preferable to use a photopolymerizable compound (particularly a low-viscosity monomer) as a dispersion medium in order to suppress solvent residue in the formed image.

[0163] (3.6.3) Other coatings In the present invention, curing accelerators, coupling agents, ion scavenging agents, solvents, etc., can be used as appropriate, if necessary.

[0164] (3.7) Physical properties (3.7.1) Viscosity The viscosity of the curable composition according to the present invention at 25°C is 1 to 1 × 10⁻⁶. 4 A Pa·s range is preferable because it allows the curable composition to gel sufficiently when applied and cooled to room temperature, resulting in good pinning properties. Furthermore, from the viewpoint of further improving ejection performance from the inkjet head, the viscosity of the curable composition according to the present invention at 80°C is preferably in the range of 3 to 20 mPa·s, and more preferably in the range of 7 to 9 mPa·s.

[0165] (3.7.2) Phase transition point The curable composition according to the present invention preferably has a phase transition temperature in the range of 40 to 100°C. If the phase transition temperature is 40°C or higher, the curable composition gels rapidly after being applied to the recording medium, resulting in improved pinning properties. Furthermore, if the phase transition temperature is below 100°C, the handling properties of the curable composition improve, and injection stability increases. From the viewpoint of enabling the curable composition to be dispensed at a lower temperature and reducing the load on the image forming apparatus, it is more preferable that the phase transition point of the curable composition according to the present invention be in the range of 40 to 60°C.

[0166] (3.7.3) Methods for measuring and determining viscosity and phase transition point The viscosity at 80°C, viscosity at 25°C, and phase transition point of the curable composition according to the present invention can be determined by measuring the temperature dependence of the dynamic viscoelasticity of the curable composition using a rheometer.

[0167] In the present invention, these viscosity and phase transition point values ​​were obtained by the following method. The curable composition according to the present invention is heated to 100°C, and while measuring the viscosity using a stress-controlled rheometer Physica MCR301 (cone plate diameter: 75 mm, cone angle: 1.0°), manufactured by Anton Paar, the curable composition is cooled to 20°C under conditions of a shear rate of 11.7 (1 / s) and a cooling rate of 0.1°C / s to obtain a viscosity temperature dependence curve.

[0168] The viscosity at 80°C and 25°C can be determined by reading the viscosity values ​​at 80°C and 25°C, respectively, from the viscosity temperature dependence curve. The phase transition point can be determined as the temperature at which the viscosity becomes 200 mPa·s in the viscosity temperature dependence curve. [Examples]

[0169] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the operations were performed at room temperature (25°C). Furthermore, unless otherwise specified, "%" and "parts" refer to "mass%" and "parts," respectively. It means "mass part".

[0170] <Preparation of yellow pigment dispersion A> Dispersant 1 and Dispersant 2, along with the dispersion medium, were placed in a stainless steel beaker and heated on a 65°C hot plate for 1 hour while stirring until dissolved. After cooling to room temperature, the pigments listed below were added, and the mixture was placed in a glass bottle with 200g of 0.5mm diameter zirconia beads and sealed tightly. This was dispersed using a paint shaker until the desired particle size was achieved, after which the zirconia beads were removed.

[0171] Dispersant 1: PX4701 (BASF) 6.0 parts by mass Dispersant 2: Solsperse 22000 (manufactured by Lubrizol Japan Co., Ltd.) 0.3 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 61.5 parts by mass Pigment: PY185 (BASF, Paliotol Yellow D1155) 10.2 parts by mass

[0172] <Preparation of cyanide pigment dispersion B> The yellow pigment dispersion was prepared in the same manner as dispersion A, except that the dispersant, dispersion medium, and pigment were changed as shown below.

[0173] Dispersant: PX4701 (BASF) 7.0 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 70 parts by mass Pigment: PB15:4 (manufactured by Dainichi Seika, Chromofine Blue 6332JC) 23 parts by mass

[0174] <Preparation of White Pigment Dispersion C> The yellow pigment dispersion was prepared in the same manner as dispersion A, except that the dispersant, dispersion medium, and pigment were changed as shown below.

[0175] Dispersant: PB824 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 9 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 71 parts by mass Pigment: Titanium dioxide (manufactured by Sakai Chemical Industry Co., Ltd., TCR-52) 60 parts by mass

[0176] In this experiment, the following compounds were used as polymerizable compounds, polymerization inhibitors, thermosetting agents, photopolymerization initiators, dispersions, and gelling agents. Details regarding polymerizable compounds, polymerization inhibitors, thermosetting agents, photopolymerization initiators, dispersions, and gelling agents are provided below.

[0177] <Polymerizable compound> 2-(1,2-cyclohexanedicarboximide)ethyl acrylate M140 (Manufactured by Toagosei Co., Ltd., molecular weight 251) Dipropylene glycol diacrylate SR508NS (Manufactured by Sartomer, molecular weight 242) Diethylene glycol diacrylate SR259 (Manufactured by Sartomer, molecular weight 302) Dioxaneglycol diacrylate A-DOG (Manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) 3PO-modified trimethylolpropane triacrylate M360 (Manufactured by Miwon, molecular weight 471) Bisphenol A type 4EO-modified diacrylate M240 (Manufactured by Miwon, molecular weight 512) Cyclic trimethylolpropaneformacrylate M1110 (Manufactured by Miwon, molecular weight 200)

[0178] <Polymerization inhibitor> 4-Methoxyphenol Hydroquinone 2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT) Naphthoquinone 2,2,6,6-Tetramethylpiperidine-N-oxyl (TEMPO) Irgastab UV-10

[0179] <Thermosetting agent> 4-Hydroxybutyl acrylate glycidyl ether 4HBAGE (Manufactured by Mitsubishi Chemical Corporation) 4,4′-Diphenylmethanebismaleimide BMI-1000 (Manufactured by Yamato Chemical Industries Co., Ltd.) Bisphenol A type epoxy resin YD-127 (Manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) Blocked isocyanate trixeneBI7982 (Manufactured by LANXESS) Blocked isocyanate trixeneBI7961 (Manufactured by LANXESS) Blocked isocyanate Blonate1601V (Manufactured by Daiei Sangyo Co., Ltd.)

[0180] <Photopolymerization initiator> DAROCURE TPO; Norish Type I (referred to as "Type I"). (Manufactured by BASF) Irgacure819; Norish Type I (referred to as "Type I"). (Manufactured by BASF) Irgacure907; Norish Type I (referred to as "Type I"). (Manufactured by BASF) Speedcure ITX; Norish Type II (referred to as "Type II"). (Made by Lambson)

[0181] Note that the Nourish Type I mentioned above refers to an α-cleavage type radical polymerization initiator. Furthermore, the Nourish Type II mentioned above refers to a hydrogen abstraction type radical polymerization initiator.

[0182] <Dispersion> Dispersion A (Yellow pigment dispersion A) Dispersion B (Cyanide pigment dispersion B) Dispersion C (White pigment dispersion C)

[0183] <Gelling agent> Stearyl stearate Dibehenyl ketones

[0184] <Preparation of curable composition> In this experiment, curable compositions 1 to 35 using two kinds of polymerizable compounds, a polymerization inhibitor, a thermosetting agent, two kinds of photoinitiators, and two kinds of dispersions are shown in Tables I to IV below.

[0185]

Table 1

[0186]

Table 2

[0187]

Table 3

[0188]

Table 4

[0189] Each curable composition (hereinafter also referred to as "ink") described in Tables I to IV above was prepared and filtered through a 3 μm membrane filter made of Teflon (registered trademark) manufactured by ADVATEC. Using a viscoelasticity measuring device MCR300 manufactured by Physica at a shear rate of 1000 (1 / s), the viscosity at 80°C and the gel phase transition temperature of each ink were measured.

[0190] Here, the gel phase transition temperature represents the temperature at which the complex viscosity becomes 1 Pa or more in the viscoelasticity curve obtained by changing the temperature at a temperature decrease rate of 0.1°C / s, a strain of 5%, an angular frequency of 10 radian / s, and a temperature decrease rate of 0.1°C / s.

[0191] The viscosities at 25°C of curable compositions 21 to 27 containing a gelling agent were all 1 to 1×10 4 Pa·s, while the viscosities of curable compositions 1 to 20 and curable compositions 28 to 35 not containing a gelling agent were all less than 1 Pa·s. [[ID=四十九]] Furthermore, the gel phase transition temperatures of the curable compositions according to the present invention were all within the range of 40 to 100°C.

[0192] <Pattern formation by inkjet recording method (Examples 1-39)> [Example 1] (Process 1) The prepared curable composition 1 was loaded as the first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, a pattern was formed by applying the above-mentioned curable composition 1 in a thin film onto a copper-clad laminate for printed circuit boards (FR-4, 1.6 mm thick, 150 mm x 95 mm in size), which was used as a recording medium.

[0193] The ink supply system consists of an ink tank, an ink channel, and an inkjet head. The ink was heated to 80°C from the ink tank to the print head. A heater was also incorporated into the piezo head to heat the ink temperature inside the recording head to 80°C.

[0194] Using this inkjet device, a voltage was applied to create dots with a droplet volume of 6.0 pl, and a solid pattern measuring 20 mm x 50 mm and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm. In addition, no heat or light curing treatment was applied to the coated curable composition in step 1.

[0195] (Process 2) The prepared curable composition 29 was loaded as a second curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied onto the first curable composition, which was in an uncured state and applied in step 1.

[0196] Similar to step 1, the ink supply system consists of an ink tank, an ink channel, and an inkjet head. A heater was also incorporated into the piezo head to heat the ink temperature inside the recording head to 45°C. The piezo head had a nozzle diameter of 22 μm, and the nozzle resolution was 360 dpi, with the heads arranged in a staggered pattern to form a nozzle row with a resolution of 720 dpi.

[0197] Using this inkjet device, a voltage was applied to create dots with a droplet volume of 6.0 pl, and a solid pattern measuring 20 mm x 50 mm and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm.

[0198] (Step 3) After step 2, the material was placed in an oven set to 150°C for 60 minutes to fully cure, and a printed sample was obtained.

[0199] [Examples 2-6] A printed sample was obtained in the same manner as in Example 1, except that the curable composition to be loaded into the inkjet recording device as the second curable composition in (Step 2) was changed as shown in Table V.

[0200] [Examples 7-20] A printed sample was obtained in the same manner as in Example 1, except that the curable composition to be loaded into the inkjet recording device as the first curable composition in (Step 1) was changed as shown in Table V.

[0201] [Example 21] (Process 1) The prepared curable composition 7 was loaded as the first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, a pattern was formed by applying the above-mentioned curable composition 7 in a thin film onto a copper-clad laminate for printed circuit boards (FR-4, 1.6 mm thick, 150 mm x 95 mm in size), which was used as a recording medium.

[0202] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. Heat the ink from the ink tank to 80 °C up to the head part. Also incorporate a heater in the piezo head and heat the ink temperature inside the recording head to 80 °C.

[0203] Using this inkjet device, apply a voltage so that dots with a droplet volume of 6.0 pl are formed, and print a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm on the substrate to a thickness of 20 μm each. Note that no curing measures by heat or light were applied to the applied curable composition in Step 1.

[0204] (Step 2) Loaded the prepared curable composition 29 as the second curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo type inkjet nozzle. Using this apparatus, apply the second curable composition onto the uncured first curable composition applied in a thin film state on a copper-clad laminate for a printed wiring board in the above (Step 1).

[0205] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. Also incorporate a heater in the piezo head and heat the ink temperature inside the recording head to 45 °C. The piezo head has nozzles with a diameter of 22 μm, and the heads with a nozzle resolution of 360 dpi are arranged staggeredly to form a nozzle row with a resolution of 720 dpi.

[0206] Using this inkjet device, apply a voltage so that dots with a droplet volume of 6.0 pl are formed, and print a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm on the substrate to a thickness of 20 μm each.

[0207] (Step 3) After the above (step 2), a Phoseon Technology FireJet™ FJ100 LED lamp (395nm, 8W / cm²) is used. 2 ) 2W / cm 2 500 mJ / cm² 2 The layer of the curable composition was cured by irradiating it to achieve the desired result. The material was then placed in an oven set to 150°C for 60 minutes to fully harden, and a printed sample was obtained.

[0208] [Examples 22-24] A printed sample was obtained in the same manner as in Example 21, except that the curable composition to be loaded into the inkjet recording device as the first curable composition was changed as shown in Table VI in (Step 1) of Example 21.

[0209] [Examples 25-28] A printed sample was obtained in the same manner as in Example 1, except that the curable composition to be loaded into the inkjet recording device as the first curable composition in the above-mentioned (Step 1) was changed as shown in Table VI.

[0210] [Example 29] (Process 1) A curable composition 5, prepared in the same manner as in Example 10, was loaded as the first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, a pattern was formed by applying the above-mentioned curable composition 5 in a thin film onto a copper-clad laminate for printed circuit boards (FR-4, 1.6 mm thick, 150 mm x 95 mm in size), which was used as a recording medium.

[0211] The ink supply system consists of an ink tank, an ink channel, and an inkjet head. The ink is heated to 80°C from the ink tank to the print head. A heater was also incorporated into the piezo head to heat the ink temperature inside the recording head to 80°C.

[0212] Using this inkjet device, a voltage was applied so that dots with a droplet volume of 6.0 pl were formed, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed on the substrate to a thickness of 20 μm each.

[0213] (Additional step: a step of curing the first curable composition by light irradiation) After the said (Step 1), a Phoseon Technology LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) was irradiated at 0.1 W / cm 2 , 50 mJ / cm 2 so that the first curable composition applied in a thin film on a copper-clad laminate for printed wiring boards was cured within the extent of maintaining an uncured state without reaching full cure.

[0214] (Step 2) The prepared curable composition 29 was loaded as the second curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied on top of the uncured first curable composition applied in a thin film on a copper-clad laminate for printed wiring boards in the said (Step 1).

[0215] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. A heater was also built into the piezo head to heat the ink temperature in the recording head to 45°C. The piezo heads were arranged staggeredly with a nozzle diameter of 22 μm and a nozzle resolution of 360 dpi to form a nozzle array with a resolution of 720 dpi.

[0216] Using this inkjet device, a voltage was applied so that dots with a droplet volume of 6.0 pl were formed, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed on the substrate to a thickness of 20 μm each.

[0217] (Step 3) After step 2, the material was placed in an oven set to 150°C for 60 minutes to fully cure, and a printed sample was obtained.

[0218] [Example 30] The procedure was the same as in Example 29, except that the main curing treatment using light and heat was performed in (Step 3) of Example 29. The light irradiation conditions were the same as those used in (Step 3) of Example 21.

[0219] [Example 31] In step 1 of Example 1, the curable composition to be loaded into the inkjet recording device as the first curable composition was changed to curable composition 20, which does not contain a thermosetting agent but uses an N-oxyl-based polymerization inhibitor as a polymerization inhibitor. Otherwise, printed samples were obtained in the same manner as in Example 1.

[0220] [Example 32] (Process 1) A curable composition 28, prepared in the same manner as in Example 1, was loaded as the first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, a pattern was formed by applying the above-mentioned curable composition 28 in a thin film onto a copper-clad laminate for printed circuit boards (FR-4, 1.6 mm thick, 150 mm x 95 mm in size), which was used as a recording medium.

[0221] The ink supply system consists of an ink tank, an ink channel, and an inkjet head. The ink is heated to 80°C from the ink tank to the print head. A heater was also incorporated into the piezo head to heat the ink temperature inside the recording head to 80°C.

[0222] Using this inkjet device, a voltage was applied to create dots with a droplet volume of 6.0 pl, and a solid pattern measuring 20 mm x 50 mm and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm.

[0223] (Additional step: A step of curing the first curable composition by light irradiation.) After the above (step 1), a Phoseon Technology FireJet™ FJ100 LED lamp (395nm, 8W / cm²) is used. 2 ) 0.1 W / cm² 2 50 mJ / cm² 2 The first curable composition, which was applied as a thin film onto a copper-clad laminate for printed circuit boards, was cured by irradiating it to such an extent that it remained in an uncured state without reaching full curing.

[0224] (Process 2) The prepared curable composition 35 was loaded as a second curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied on top of the first curable composition, which was in an uncured state and had been applied in a thin film on a copper-clad laminate for printed circuit boards in step 1.

[0225] The ink supply system consists of an ink tank, an ink channel, and an inkjet head. A heater was also incorporated into the piezo head to heat the ink temperature inside the recording head to 45°C. The piezo head had a nozzle diameter of 22 μm, and the nozzle resolution was 360 dpi, with the heads arranged in a staggered pattern to form a nozzle row with a resolution of 720 dpi.

[0226] Using this inkjet device, a voltage was applied to create dots with a droplet volume of 6.0 pl, and a solid pattern measuring 20 mm x 50 mm and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm.

[0227] (Step 3) After the above (step 2), a Phoseon Technology FireJet™ FJ100 LED lamp (395nm, 8W / cm²) is used. 2 ) 2W / cm 2 500 mJ / cm² 2 The layer of the curable composition was cured by irradiating it to achieve the desired result. The material was then placed in an oven set to 150°C for 60 minutes to fully harden, and a printed sample was obtained.

[0228] [Examples 33-37] In step 1 of Example 1, the curable composition to be loaded into the inkjet recording device as the first curable composition was changed as shown in Table VII. Otherwise, printed samples were obtained in the same manner as in Example 1.

[0229] [Example 38] In step 1 of the above-mentioned Example 21, the curable composition to be loaded into the inkjet recording device as the first curable composition was changed to curable composition 23. Otherwise, printed samples were obtained in the same manner as in Example 21.

[0230] [Example 39] A printed sample was obtained in the same manner as in Example 1, except that in (Step 1) of Example 1, the curable composition loaded into the inkjet recording device as the first curable composition was changed to curable composition 26.

[0231] [Example 40] A printed sample was obtained in the same manner as in Example 29, except that in (Step 1) of Example 29, the curable composition to be loaded into the inkjet recording device as the first curable composition was changed to curable composition 23.

[0232] Furthermore, after the additional step (light irradiation), the first curable composition, which was applied as a thin film onto the copper-clad laminate for printed circuit boards, remained in an uncured state without reaching full curing and retained its tackiness.

[0233] [Example 41] A printed sample was obtained in the same manner as in Example 30, except that in (Step 1) of Example 30, the curable composition loaded into the inkjet recording device as the first curable composition was changed to curable composition 23. Furthermore, after the additional step (light irradiation), the first curable composition, which was applied as a thin film onto the copper-clad laminate for printed circuit boards, remained in an uncured state without reaching full curing and retained its tackiness.

[0234] [Example 42] In step 1 of Example 1, the curable composition loaded into the inkjet recording device as the first curable composition was changed to curable composition 27, which does not contain a thermosetting agent but contains a gelling agent. Otherwise, a printed sample was obtained in the same manner as in Example 1.

[0235] <Pattern formation by inkjet recording method (Comparative Examples 1 and 2)> [Comparative Example 1] In step 1 of the above-mentioned Example 40, the curable composition to be loaded into the inkjet recording device as the first curable composition was changed to curable composition 2. Furthermore, in an additional step following step 1, a Phoseon Technology FireJet™ FJ100 LED lamp (395nm, 8W / cm²) is used. 2 ) 2W / cm 2 500 mJ / cm² 2 A printed sample was obtained in the same manner as in Example 40, except that the layer of the first curable composition was fully cured by irradiating it to achieve the desired result.

[0236] [Comparative Example 2] In step 1 of the above-mentioned Example 41, the curable composition to be loaded into the inkjet recording device as the first curable composition was changed to curable composition 21. Furthermore, in an additional step following step 1, a Phoseon Technology FireJet™ FJ100 LED lamp (395nm, 8W / cm²) is used. 2 ) 2W / cm 2500 mJ / cm² 2 A printed sample was obtained in the same manner as in Example 41, except that the layer of the first curable composition was fully cured by irradiating it to achieve the desired result.

[0237] [evaluation] Tables V to VII show the curing state of the curable compositions in steps (1) to (3) and the evaluation results after step (3) for Examples 1 to 42, Comparative Example 1, and Comparative Example 2. Examples 29, 30, 32, 40, and 41 are for reference only. The evaluation included assessments of interlayer adhesion, storage stability, substrate adhesion, pencil hardness, and ink bleeding. The evaluation methods and criteria were as follows:

[0238] <Interlayer adhesion> For printed samples of a solid pattern of the second curable composition on the first curable composition, the cured film was cut in a grid pattern according to the JIS K5600 cross-cut method, adhesive tape was applied, and the tape was peeled off to observe the peeling state of the cured film. The adhesion residue rate was determined by the method described below and evaluated according to the criteria below. Here, the adhesion residue rate is calculated using the number of squares created by cutting as the denominator and the number of squares remaining after tape removal as the numerator.

[0239] (standard) ◎: 100% adhesion and residue rate ○: Adhesion and residue rate of 90% or more but less than 100% △: Adhesion / residue rate 70% or more but less than 90% ×: Adhesion residue rate less than 70%

[0240] <Storability> The viscosity of the compositions obtained in each example and comparative example was measured at 80°C using a rotary viscoelasticity measuring device, and then stored for one week under conditions of 85°C. After storage, the viscosity was remeasured at 80°C. The difference in viscosity before and after storage (i.e., viscosity fluctuation) was determined, and storage stability was evaluated based on the viscosity fluctuation according to the following criteria.

[0241] (standard) ◎: Viscosity fluctuation is between 0 cP and less than 0.5 cP ○: Viscosity variation of 0.5 cP or more and less than 1.0 cP △: Viscosity fluctuation of 1.0 cP or more but less than 1.5 cP ×: Viscosity fluctuation of 1.5 cP or more

[0242] <Substrate adhesion> For the solid pattern print samples of the first curable composition, the cured film was cut in a grid pattern according to the JIS K5600 cross-cut method, adhesive tape was applied, and the tape was peeled off to observe the peeling state of the cured film. The adhesion residue rate was determined using the method described below and evaluated according to the criteria below. Here, the adhesion residue rate is calculated using the number of squares created by cutting as the denominator and the number of squares remaining after tape removal as the numerator.

[0243] (standard) ◎: 100% adhesion and residue rate ○: Adhesion and residue rate of 90% or more but less than 100% △: Adhesion / residue rate 70% or more but less than 90% ×: Adhesion residue rate less than 70%

[0244] <Pencil hardness> For printed samples of a solid pattern of the second curable composition on the first curable composition, the pencil hardness of the surface was measured in accordance with the method described in "JIS standard K-5400". The evaluation was conducted according to the following criteria.

[0245] (standard) ◎:Pencil hardness 5H ○: Pencil hardness 4H △:Pencil hardness 3H ×: Pencil hardness 2H or less

[0246] <Bleeding> The following methods and criteria were used to evaluate the degree of bleeding. In other words, the print samples printed under the above conditions were visually inspected for bleeding and granularity. The presence or absence of bleeding was determined by visual inspection according to the following criteria.

[0247] (standard) ○: Less bleeding and low granularity. ×: It has a tendency to bleed and is highly granular.

[0248] [Table 5]

[0249] [Table 6]

[0250] [Table 7]

[0251] A comparison of Examples 1 to 6 shows that using an N-oxyl-based polymerization inhibitor as the polymerization inhibitor in the second curable composition improves pencil hardness, among other things. In other words, a comparison of Examples 1 and 2 with Examples 3 to 6 shows that the interlayer adhesion and pencil hardness are improved by including any of the following polymerization inhibitors as the second curable composition: an N-oxyl polymerization inhibitor (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Irgastab UV-10), a phenol polymerization inhibitor containing an ot-butyl group (2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT)), or a polymerization inhibitor having two or more aromatic rings (naphthoquinone). Furthermore, among the polymerization inhibitors mentioned above, it can be seen that Examples 5 and 6, which use curable compositions 5 and 6 containing an N-oxyl polymerization inhibitor, exhibit improved pencil hardness compared to Examples 3 and 4.

[0252] A comparison of Examples 7 to 16 shows that using a bisphenol A type epoxy resin or a blocked isocyanate compound as the thermosetting agent in the first curable composition improves pencil hardness. In particular, it is preferable to use blocked isocyanate compounds.

[0253] In other words, a comparison between Examples 7 to 11 and each of the examples in Examples 11 to 16 and Example 32 shows that using bisphenol A type epoxy resin or blocked isocyanate compound as the thermosetting agent for the first curable composition improves pencil hardness. Furthermore, among the thermosetting agents mentioned above, it can be seen that Examples 14-16 and Example 32, which use curable compositions 9, 10, 11, and 28 containing blocked isocyanate compounds, exhibit improved substrate adhesion compared to Example 13.

[0254] Furthermore, a comparison of Examples 7 to 11 shows that using an N-oxyl polymerization inhibitor as the polymerization inhibitor for the first curable composition improves interlayer adhesion and shelf life.

[0255] In other words, a comparison of Example 7 with Examples 8 to 11 shows that the interlayer adhesion and shelf life are improved by including one of the following polymerization inhibitors as the first curable composition: an N-oxyl polymerization inhibitor (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Irgastab UV-10), a phenol polymerization inhibitor containing an ot-butyl group (2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT)), or a polymerization inhibitor having two or more aromatic rings (naphthoquinone).

[0256] Furthermore, among the polymerization inhibitors mentioned above, it can be seen that Examples 10 and 11, which use curable compositions 5 and 6 containing N-oxyl polymerization inhibitors, exhibit better interlayer adhesion and storage properties than Examples 8 and 9.

[0257] A comparison of Examples 11-16 and Example 32 shows that using a blocked isocyanate compound as the thermosetting agent in the first curable composition improves substrate adhesion.

[0258] In other words, a comparison of Examples 11 and 12 with Examples 13-16 and 32 shows that the substrate adhesion is improved by including at least one epoxy resin (bisphenol A type epoxy resin YD-127) or blocked isocyanate compounds (blocked isocyanate trixene BI7982, blocked isocyanate trixene BI7961, blocked isocyanate Blonate 1601V) as the first curable composition.

[0259] A comparison of Example 10 with Examples 17-20 shows that the inclusion of a polyfunctional polymerizable compound formed using monomers having an alicyclic structure, monomers having trifunctional polymerizable groups, or monomers having aromatic rings as the first curable composition improves interlayer adhesion and substrate adhesion.

[0260] A comparison of Examples 12-15 and 21-24 shows that curing the first and second curable compositions by light irradiation before heat curing after application allows for more reliable heat curing and improves pencil hardness.

[0261] From Example 25, the effects of the present invention are achieved even when the starting agent is changed. A comparison of Example 25 and Example 26 shows that the effects of the present invention are achieved even when the type of photopolymerization initiator is changed.

[0262] A comparison of Examples 26-28 shows that using a larger amount of hydrogen abstraction-type initiator than α-cleavage-type initiator promotes crosslinking due to gelation of the coating film, thereby improving substrate adhesion.

[0263] Specifically, in Example 26, the curable composition used as the first curable composition is 17, with an α-cleavage type photopolymerization initiator amount of 5.0% by mass and a hydrogen abstraction type initiator amount of 3.0%. In Example 27, curable composition 18 is used as the first curable composition, with an α-cleavage type photopolymerization initiator amount of 2.0% by mass and a hydrogen abstraction type initiator amount of 3.0%. In Example 28, the curable composition used as the first curable composition is 19, with an α-cleavage type photopolymerization initiator amount of 0.5% by mass and a hydrogen abstraction type initiator amount of 3.0%. Therefore, by using a hydrogen abstraction type initiator amount that is a certain percentage higher than the α-cleavage type initiator amount, crosslinking due to gelation of the coating film is promoted, improving substrate adhesion.

[0264] Examples 29 and 30 both show cases where, after an additional step (light irradiation), the first curable composition applied in a thin film onto a copper-clad laminate for printed circuit boards remained in an uncured state without reaching full curing, and retained its tackiness. The difference between Examples 29 and 30 is that in Example 30, a curing treatment by light irradiation was performed in step 3, resulting in a greater improvement in pencil hardness in Example 30. Furthermore, it can be seen that Examples 29 and 30 exhibit inferior interlayer adhesion compared to Example 10, which similarly uses curable composition 5 as the first curable composition.

[0265] Examples 33 to 41 are examples using a first curable composition containing a gelling agent, and by comparing them with the various examples described above, it can be seen that bleeding is improved, etc.

[0266] Examples 31 and 42 are examples using the first curable composition which does not contain a thermosetting agent. A comparison between Examples 20 and 31, and between Examples 37 and 42, shows that while Examples 31 and 42, which do not contain a thermosetting agent, have practically acceptable overall performance, Examples 20 and 37, which contain a thermosetting agent, exhibit improved substrate adhesion and pencil hardness compared to Examples 31 and 42.

[0267] In Example 32, since neither the first nor the second curable composition contained a polyfunctional polymerizable compound, the interlayer adhesion and pencil hardness were poorly evaluated. This indicates that including a polyfunctional polymerizable compound in both the first and second curable compositions improves interlayer adhesion and pencil hardness.

[0268] Comparative Examples 1 and 2 are examples in which the layer of the first curable composition was fully cured by light irradiation under the same conditions as the light irradiation conditions in Step 3, in an additional step after Step 1.

[0269] A comparison between Example 7 and Comparative Example 1, and between Example 33 and Comparative Example 2, reveals that when the first curable composition is fully cured in an additional step, and then the second curable composition is applied, the interlayer adhesion deteriorates.

[0270] Furthermore, considering the evaluation results of Examples 29 and 30, it can be seen that the timing for applying the second curable composition is during the period when the first curable composition is in an uncured state and no curing treatment has been applied.

[0271] This invention provides a recording method that can improve the adhesion between multiple curable compositions and suppress delamination, as well as a method for producing printed materials using this recording method. [Explanation of symbols]

[0272] P Substrate, base material H Head HU Head Unit HU1 Head Unit 1 HU2 Head Unit 2 Q: Transport direction of the substrate R Head carriage transport direction L Transport rail

Claims

1. A recording method using a curable composition, A step of coating a first curable composition in the form of a thin film onto a recording medium, A step of applying a second curable composition on top of the applied first curable composition, The process includes a step of curing the first and second curable compositions by at least heat or light, The second curable composition is applied to the first curable composition without applying any curing treatment with heat or light. The first and second curable compositions are at least a thermosetting composition or a photocurable composition. The process includes a step of photocuring after the step of applying the second curable composition and before the step of thermal curing the first and second curable compositions. A recording method characterized by the following:

2. The first curable composition contains a polymerization inhibitor, The polymerization inhibitor contains one of the following: an N-oxyl polymerization inhibitor, a phenolic polymerization inhibitor containing an o-t-butyl group, or a polymerization inhibitor having two or more aromatic rings. The recording method according to feature 1.

3. The first curable composition contains at least one epoxy resin or blocked isocyanate compound as a thermosetting agent. The recording method according to claim 1 or 2.

4. Both the first curable composition and the second curable composition contain a polyfunctional polymerizable compound. A recording method according to any one of claims 1 to 3.

5. The first curable composition contains a photopolymerization initiator with a higher content of hydrogen abstraction-type radical polymerization initiator than an α-cleavage-type radical polymerization initiator. A recording method according to any one of claims 1 to 4.

6. The first curable composition contains a gelling agent. A recording method according to any one of claims 1 to 5, characterized by the features described herein.

7. The recording method using the curable composition is an inkjet recording method. A recording method according to any one of claims 1 to 6, characterized by the features described above.

8. A method for producing a printed material, characterized by producing a printed material using the recording method described in any one of claims 1 to 7.

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