Recording method, and method of producing printed matter

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 a printed matter, and more particularly to a recording method characterized by improving the adhesion between a plurality of curable compositions to suppress interlayer peeling. [Background technology]

[0002] Conventionally, photolithography and screen printing 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 for printed circuit boards, and it has already been proposed that after applying inkjet ink, preliminary curing with light (hereinafter also referred to as "temporary curing") is performed, and then main curing with heat is performed to form a cured layer. Furthermore, additional printing indicating the type, date, etc. may be added to the cured layer. In such cases, the adhesion or bonding strength between the cured layer and the additional printing may be insufficient, causing problems such as the additional printing peeling off from the cured layer or bleeding onto the cured layer.

[0003] For example, Patent Document 1 discloses a method of forming a cured layer by inkjet printing a UV free radical curable inkjet ink onto a support, temporarily curing the ink with light, and then fully curing the ink with heat; however, the adhesion between the substrate and the interface of the cured layer is insufficient.

[0004] Furthermore, Patent Document 2 discloses a method in which a curable composition is applied, and then provisionally cured by light to form a laminate having a high precision and thickness, and then main curing by heat to form a cured layer. However, there is no description regarding the adhesiveness between different curable compositions, and the problem of interlayer delamination remains.

[0005] Patent Document 3 discloses a method for forming a cured layer that is less likely to cause delamination, in which a photocurable liquid thin film material is applied onto a substrate to form a liquid film, and the liquid film is pre-cured by irradiating it with pre-curing light, repeating this procedure while gradually increasing the light intensity to form a laminate, and then the liquid film is fully cured by irradiating it with full curing light, thereby curing the deeper parts of the cured layer. However, this method also does not describe the adhesion between different curable compositions, and the problem of delamination remains.

[0006] Patent Document 4 discloses a method for forming a thin film in which a first thin film material is applied and semi-cured, then a second thin film material is applied and semi-cured, and then fully cured with light, thereby sufficiently curing the deeper portions and making peeling less likely to occur. However, this method also makes no mention of the adhesiveness between different inks, and there is a problem with interlayer peeling. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2018-529220 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-089540 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-236169 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-233704 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in consideration of the above problems and circumstances, and an object of the present invention is to provide a recording method that can improve the adhesion between multiple curable compositions and suppress interlayer delamination, and a method for producing a printed matter using the recording method. [Means for solving the problem]

[0009] In order to solve the above-mentioned problems, the present inventors have investigated the causes of the above-mentioned problems, and as a result have found that when applying a plurality of curable compositions in stages on a recording medium, the above-mentioned problems can be solved by applying a different curable composition on top of an uncured curable composition, and then performing main curing, thereby arriving at the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.

[0010] 1. A recording method using a curable composition, applying a first curable composition to a recording medium in the form of a thin film; applying a second curable composition onto the applied first curable composition; a step of curing the first and second curable compositions by at least heat or light, applying the second curable composition without subjecting the first curable composition to a heat or light curing treatment; and The first and second curable compositions are at least a heat-curable composition or a photo-curable composition. A recording method characterized by:

[0011] 2. The first curable composition contains a polymerization inhibitor, The polymerization inhibitor contains any one of an N-oxyl-based polymerization inhibitor, a phenol-based polymerization inhibitor containing an ot-butyl group, and a polymerization inhibitor having two or more aromatic rings. 2. The recording method according to claim 1,

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

[0013] 4. Both the first curable composition and the second curable composition contain a multifunctional polymerizable compound. 4. The recording method according to any one of items 1 to 3, wherein:

[0014] 5. After the step of applying the second curable composition, a step of photocuring is performed before the step of thermally curing the first and second curable compositions. 5. The recording method according to any one of items 1 to 4, wherein:

[0015] 6. The first curable composition contains a photopolymerization initiator in which the content of the hydrogen abstraction type radical polymerization initiator is greater than the content of the α-cleavage type radical polymerization initiator. 6. The recording method according to any one of items 1 to 5,

[0016] 7. The first curable composition contains a gelling agent. 7. The recording method according to any one of items 1 to 6,

[0017] 8. The recording method using the curable composition is an inkjet recording method. 8. The recording method according to any one of items 1 to 7, wherein:

[0018] 9. A printed matter is produced using the recording method described in any one of items 1 to 8. A method for producing a printed matter. [Effects of the Invention]

[0019] The above-described means of the present invention can provide a recording method that can improve the adhesion between a plurality of curable compositions and suppress interlayer delamination, and a method for producing a printed matter using the recording method. The mechanism by which the effects of the present invention are manifested or the mechanism of action is not clear, but is speculated as follows.

[0020] In the present invention, after applying a first curable composition onto a recording medium, the second curable composition is applied while the first curable composition is still in an uncured state. This presumably causes some mixing of the components of each composition at and near the interface between the first and second layers, promoting the polymerization reaction and thereby improving the adhesion between the first and second layers.

[0021] Furthermore, it has been found that when the first curable composition contains at least one polymerization inhibitor selected from the group consisting of an N-oxyl-based polymerization inhibitor, a phenol-based polymerization inhibitor containing an ot-butyl group, and a polymerization inhibitor having two or more aromatic rings, inhibition of polymerization at the interface between the two layers can be suppressed, interlayer adhesion can be further improved, and storage stability can also be improved. Moreover, compared to when other polymerization inhibitors are used, polymerization inhibition is reduced, and therefore polymerization at the interface between the two layers is carried out efficiently, resulting in stronger interlayer adhesion.

[0022] Furthermore, when 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 the use of a highly reactive polyfunctional monomer increases the number of bonds that connect the two layers. Furthermore, since the interlayer adhesion is improved, the pencil hardness can also be improved at the same time.

[0023] Furthermore, by including a photo-curing step after the step of applying the second curable composition and before the step of thermally curing the first and second curable compositions, the monomer component of the first curable composition can be cured, further improving adhesion to the recording medium (substrate), and improving thin line formation of the second curable composition. Furthermore, the interlayer adhesion can be maintained at a high level.

[0024] Furthermore, when the first curable composition contains a larger amount of hydrogen abstraction radical polymerization initiator than α-cleavage radical polymerization initiator as the photopolymerization initiator, crosslinking and gelling of the coating film proceeds due to the hydrogen abstraction effect, and the crosslinking density of the coating film is further improved, thereby improving adhesion to the recording medium (substrate).

[0025] Furthermore, when the first curable composition contains a gelling agent, the formation of fine lines is further improved while maintaining interlayer adhesion. That is, by increasing the viscosity on the recording medium (substrate) with the gelling agent, bleeding of the second curable composition into the first curable composition can be significantly improved, and fine line formation can be further improved. Furthermore, at the interface with the first curable composition, the two layers are mixed together, so good interlayer adhesion can be maintained. [Brief explanation of the drawings]

[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 device [Figure 3A] Schematic diagram of an inkjet device with a reverse printing feature [Figure 3B] Schematic diagram of a multi-carriage inkjet device [Figure 3C] Schematic diagram of a multi-carriage (with tandem transport) inkjet device [Figure 4] Schematic diagram of a recording device that rotates between each process DETAILED DESCRIPTION OF THE INVENTION

[0027] The recording method of the present invention is a recording method using a curable composition, and includes the steps of applying a first curable composition in the form of a thin film onto a recording medium, applying a second curable composition onto the applied first curable composition, and thermally curing the first and second curable compositions, wherein the second curable composition is applied without applying a heat or light curing treatment to the first curable composition, and the first and second curable compositions are at least a heat-curable composition or a light-curable composition. This feature is a technical feature common to or corresponding to each of the following embodiments (configurations).

[0028] As an embodiment of the present invention, it is preferable that the first curable composition contains a polymerization inhibitor from the viewpoint of improving adhesion between a plurality of curable compositions. From the viewpoint of improving interlayer adhesion, it is more preferable that the polymerization inhibitor contains at least one of an N-oxyl-based polymerization inhibitor, a phenol-based polymerization inhibitor containing an ot-butyl group, and a polymerization inhibitor having two or more aromatic rings.

[0029] The first curable composition preferably contains an epoxy resin as a heat curing agent from the viewpoints of substrate adhesion and pencil hardness. Furthermore, it is more preferable that the first curable composition contains a blocked isocyanate compound as a heat curing agent, from the viewpoints of substrate adhesion and pencil hardness.

[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 one embodiment, it is preferable from the viewpoint of interlayer adhesion to include 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 content of the hydrogen abstraction radical polymerization initiator as the photopolymerization initiator contained in the first curable composition is greater than that of the α-cleavage radical polymerization initiator, in that crosslinking and gelation of the coating film proceeds due to the hydrogen abstraction effect, and the crosslinking density of the coating film is further improved, thereby improving the adhesion to the substrate.

[0033] Furthermore, the first curable composition preferably contains a gelling agent, which significantly reduces bleeding of the second curable composition into the first curable composition, further improving fine line formation and maintaining interlayer adhesion.

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

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

[0036] [Outline of the recording method of the present invention] The recording method of the present invention is a recording method using a curable composition, and includes a step of applying a first curable composition in the form of a thin film onto a recording medium (hereinafter referred to as "Step 1"), a step of applying a second curable composition onto the applied first curable composition (hereinafter referred to as "Step 2"), and a step of curing the first and second curable compositions by heat or light (hereinafter referred to as "Step 3"), characterized in that 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 heat-curable compositions or light-curable compositions. FIG. 1 shows a schematic diagram of the process flow of the present invention.

[0037] Here, the "uncured state of the first curable composition" in the present invention refers to the state before and after the first curable composition applied to a recording medium is subjected to a curing treatment such as irradiation with actinic rays to cure it, heating, or removal of the solvent, and refers to the state before polymerization or crosslinking reaction between the components of the curable composition has partially progressed to some extent, or before the solvent contained in the curable composition has been removed by drying or the like, causing the curable composition to become highly viscous and lose fluidity, and before the composition as a whole finally becomes completely solid.

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

[0039] The above-mentioned "uncured state" refers to the degree of progress of the polymerization reaction of the polymerizable compound contained in the first curable composition, i.e., the rate of polymerization (also referred to as "conversion rate"), and when the rate of polymerization at the time of complete solidification is taken as 100, the rate of polymerization in the uncured state is lower than 100 and varies depending on the chemical structure and performance of the constituent components, but in the present invention, it is preferable to apply the second curable compound under conditions where the rate of polymerization is maintained within a range of 90 or less.

[0040] The degree of polymerization can be measured by measuring the change over time of a specific peak attributed to a specific structure of the polymerizable compound using an infrared spectrophotometer, for example, by the method described in JP-A-2006-76122.

[0041] In the present invention, an additional step of irradiating, heating, or drying the first curable composition with actinic rays to an extent that the first curable composition does not become completely solid may be provided between Step 1 and Step 2, as long as the first curable composition is kept in an uncured state.

[0042] The phrase "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 any of three types of curable compositions: a thermosetting composition, a photocurable composition, or a composition having both thermosetting and photocurable properties.

[0043] 1. Recording method (1.1) Recording medium The recording medium used in the present invention is not particularly limited, but examples thereof include copper-clad laminates of all grades (FR-4, etc.) made of materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits made of fluorine-polyethylene-PPO-cyanate ester, etc., as well as polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, stainless steel plates, copper plates, etc.

[0044] (1.2) Step 1 and Step 2 Step 1 is a step of applying a first curable composition to a recording medium in the form of a thin film. Step 2 is a step of applying a second curable composition onto the first curable composition that 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 be carried out using various conventionally known application methods and printing methods. For example, coater application, offset printing, screen printing, gravure printing, flexographic printing, ink jet recording, etc. can be used. The coating methods used in steps 1 and 2 may be the same or different.

[0045] (1.3) Process 3 The curing step in step 3 is a step of applying sufficient actinic ray and / or heat energy to the layer of the curable composition to completely cure the curable composition. As the curing method, any conventionally known method can be used as appropriate.

[0046] The actinic ray can be selected from, for example, electron beams, ultraviolet rays, α rays, γ rays, and X-rays, and is preferably ultraviolet rays. The ultraviolet light can be irradiated 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 prevent poor curing of the curable composition due to melting of the curable composition caused by radiant heat from the light source.

[0047] For the irradiation of ultraviolet light, ultraviolet light having a wavelength in the range of 340 to 410 nm is used, and the peak irradiance on the surface of the curable composition is preferably 0.05 to 10 W / cm. 2 within the range of 0.1 to 5 W / cm 2 The measurement should be carried out so that it is within the range of From the viewpoint of suppressing the irradiation of the curable composition with radiant heat, the amount of light to be irradiated is set to 1500 mJ / cm 2 It is preferable that it is less than 10 ...

[0048] The irradiation with actinic rays is preferably carried out within 0.001 to 300 seconds after application of the curable composition, and more preferably within 0.001 to 60 seconds in order to form a highly precise resist film.

[0049] After the first and second curable compositions are irradiated with light, they are heated to be completely cured.

[0050] The heating method is preferably, for example, placing the product in an oven set at a temperature in the range of 110 to 180° C. for 10 to 120 minutes.

[0051] (1.4) Additional process As described above, a step of irradiating the first curable composition with actinic rays or heat, or drying the first curable composition, to an extent that the first curable composition is kept in an uncured state, can be added between Step 1 and Step 2, but not to an extent that the first curable composition becomes completely solid. The first curable composition after step 1 can be irradiated with actinic rays. In this case, it is preferable to select the same means as the actinic rays used in step 3. In order to irradiate the first curable composition with actinic rays while keeping the composition uncured, the amount of light irradiated is preferably less than that used 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 an inkjet recording method. By using the inkjet recording method, it becomes easy to apply the curable composition only to the required area, which is particularly advantageous when applying a resist pattern or letters. The inkjet method is a method in which inkjet ink is ejected from a nozzle and landed on a recording medium. For example, in step 1, droplets of the first curable composition according to the present invention are ejected from an inkjet head and landed on a substrate, which is a recording medium, such as a printed circuit board, at positions corresponding to the resist film to be formed, thereby forming a pattern.

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

[0054] The ejection method from the inkjet head may be either an on-demand method or a continuous method. The on-demand inkjet head may be of any of the following types: electro-mechanical conversion type, such as single cavity type, double cavity type, bender type, piston type, shear mode type, and shared wall type; and electro-thermal conversion type, such as thermal inkjet type and Bubble Jet (registered trademark) type (Bubble Jet is a registered trademark of Canon Inc.).

[0055] By ejecting droplets of the first curable composition from an inkjet head in a heated state, ejection stability can be improved. The temperature of the first curable composition when it is discharged is preferably within a range of 40 to 100°C, and more preferably within a range of 40 to 90°C in order to further improve discharge stability. In particular, it is preferable to perform the ejection 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 a sol-gel phase transition ink containing a gelling agent is used as the first and / or second curable composition, the temperature of the ink when filled into the inkjet head is preferably set to (gelation temperature + 10)°C to (gelation temperature + 30)°C of the ink, in order to improve the ejection properties of the ink from the inkjet head. When the temperature of the ink inside the inkjet head is (gelling temperature + 10)°C or higher, it is possible to prevent the ink from gelling inside the inkjet head or on the nozzle surface, which would otherwise cause a decrease in the ink ejection properties. On the other hand, if the temperature of the ink inside the inkjet head is lowered to (gelation temperature + 30)° C. or lower, the ejection stability of the ink deteriorates.

[0057] The method for heating the first and / or second curable composition is not particularly limited. For example, at least one of the ink supply system such as the ink tank, supply pipe, and front chamber ink tank immediately before the head that make up the head carriage, the piping with filter, and the piezo head can be heated by a panel heater, ribbon heater, or warm water.

[0058] The droplet volume of the first and / or second curable composition when ejected is preferably within the range of 2 to 20 pL in terms of recording speed and image quality. As the inkjet coating device, a device such as that shown in FIG. 2 can be used. Figure 2A shows a scan-type device in which the print head unit HU moves back and forth perpendicular to the substrate transport direction Q to perform printing, while Figure 2B shows a single-pass type device in which the print head unit is fixed to the substrate transport direction Q to perform printing. In applying the first curable composition and applying the second curable composition, the combination of FIG. 2A and FIG. 2B can be freely selected. In FIG. 2, the print head unit HU is shown to have a plurality of heads H, but the number of heads H may be one. Mounting a plurality of heads H is preferable in that it allows for faster printing speed and improves 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 device, several effective configurations can be proposed for the timing of transporting the substrate P and inkjet printing, some of which are shown in Figure 3.

[0060] Figure 3A shows a configuration in which the substrate is transported in a turn after the first curable composition has been applied, and the second curable composition can be applied during this turn, or the substrate can be returned to its initial position and then transported again (upward) to apply the second curable composition. This method has the advantage that it is not necessary to change the substrate.

[0061] FIG. 3B shows a configuration in which a plurality of 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 the application of the first curable composition and the application of the second curable composition to be carried out consecutively while the substrate P is being transported in one direction, thereby enabling efficient processing. This is particularly advantageous when, after the application of the first curable composition, the second curable composition is applied while the composition is still uncured.

[0062] FIG. 3C is a modification of the device in FIG. 3B, and has a configuration in which a plurality of substrates P (two in the figure) are transported in parallel. This allows for simultaneous treatment of multiple substrates, making it even more efficient. Each print head unit HU in FIG. 3 can be of either the scan type shown in FIG. 2A or the single pass type shown in FIG. 2B, as appropriate. 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 this.

[0064] The apparatus for carrying out the present invention may perform steps 1, 2, 3, and the additional step in an independent apparatus, or may perform several steps in a combined apparatus.Furthermore, the apparatus may be provided with functions for performing processes other than these steps.

[0065] When each process is performed in an independent apparatus, an automatic transfer function such as conveyor movement or robot transfer can be provided to move the substrate to be processed between the independent apparatuses. In the case of an apparatus in which multiple steps are combined within the same apparatus, the arrangement of the steps can take various forms. It is possible to adopt various configurations as appropriate, such as a conveyor system or slider system with a linear transport path, a turntable system in which the substrate and processed material move relatively by rotating between processes, or a system in which multiple processes are arranged one above the other. Performing a series of processes within one device reduces the handling work involved in transferring the substrate, resulting in increased productivity.

[0066] As an example of an apparatus for carrying out the present invention, a schematic diagram of an apparatus configured to move in a rotary manner between each process is shown in FIG. FIG. 4 is a schematic diagram of only the substrate conveying table, and S in FIG. 4 indicates the rotation direction of the conveying table. The numbers (1) to (6) in FIG. 4 are 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 a conveying table (1), and a first curable composition is applied in the form of a thin film at the position (2) (step 1). Thereafter, if necessary, at position (3), the first curable composition is irradiated with actinic rays or heat, or dried, to an extent that the first curable composition does not become completely solid (an additional step), and at position (4), a second curable composition is applied onto the uncured first curable composition (step 2), and at position (5), the layer of curable composition is cured by being given sufficient actinic rays and / or heat energy to completely cure the curable composition (step 3). When the transfer table reaches position (6), the substrate is removed and each process is completed.

[0068] In FIG. 4, each process is installed in one stage, but it is also possible to configure the process to be installed across multiple stages in order to adjust the processing time at each stage.

[0069] 3. Component compounds constituting the first and second curable compositions Hereinafter, component compounds constituting the curable composition that can be suitably used in the recording method of the present invention will be described. The first curable composition and the second curable composition according to the present invention are different compositions, but the same compounds can be used.

[0070] (3.1)Thermopolymerizable compounds As component compounds constituting the first and second curable compositions according to the present invention, the following compounds can be used as "thermally polymerizable compounds" or "thermosetting agents". The thermally polymerizable compound according to the present invention also includes a compound that also has the ability to undergo a polymerization reaction by light depending on the reaction conditions.

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

[0072] In the present invention, the thermally polymerizable compound as a "thermosetting agent" is preferably contained in an amount within a range of 1 to 15% by mass, more preferably within a range of 2 to 10% by mass, based on the total mass of the curable composition.

[0073] (3.1.1) Cyclic ether group-containing thermally polymerizable compound The cyclic ether group-containing thermally polymerizable compound may have a plurality of cyclic ether groups in the molecule, and is preferably a compound having an epoxy group or an oxetanyl group.

[0074] (compounds having epoxy groups) Examples of compounds having an epoxy group 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, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, hydrogenated phthalic acid diglycidyl ester, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol glycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol glycidyl ether, and cresol novolac 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'-cyclohexydienebisphenol 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 hydrocarbons. The epoxy resin may include one or more selected from the group consisting of novolac-type epoxy resins such as novolac-type epoxy resins having a basic structure; biphenyl-type epoxy resins; aralkyl-type epoxy resins such as xylylene-type epoxy resins and biphenylaralkyl-type epoxy resins; epoxy resins having a naphthalene skeleton such as naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins, difunctional to tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, and naphthalenearalkyl-type epoxy resins; anthracene-type epoxy resins; phenoxy-type epoxy resins; dicyclopentadiene-type epoxy resins; norbornene-type epoxy resins; adamantane-type epoxy resins; and fluorene-type epoxy resins.

[0076] (Compounds containing an oxetanyl group) Examples of the compound having an oxetanyl group include polyfunctional oxetanes such as 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 oligomers or copolymers thereof, 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 thermally polymerizable compound The isocyanate group-containing thermally polymerizable compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule, and specific examples thereof include aromatic isocyanates 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), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), and 1,5-naphthalene diisocyanate (NDI). aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, and norbornane diisocyanatomethyl (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 biuret, isocyanurate, and carbodiimide-modified products thereof.

[0078] (Blocked isocyanate compounds) Among the above-mentioned isocyanate group-containing thermally polymerizable compounds, blocked isocyanate compounds, which are polyfunctional isocyanates having isocyanate groups protected by a thermally dissociable blocking agent, are particularly preferred from the viewpoints of adhesion to a recording medium and surface hardness of a coating film, because the thermal curing reaction proceeds as a result of thermal dissociation of the isocyanate groups protected by the blocking agent.

[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 stability and thermal dissociability of the curable composition.

[0080] In the case of the double cure method, when 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 because it has heat-melting properties, it functions as a dissolving aid for the thermosetting agent during thermal polymerization, thereby accelerating the thermosetting reaction.

[0081] Furthermore, when the first curable composition according to the present invention contains a gelling agent, the effect is even more pronounced due to the high compatibility between the isocyanate and the gelling agent. Among these, the solubility is further increased in the case of an aliphatic polyisocyanate type, and as a result, higher adhesion to the recording medium can be obtained. Furthermore, the heat curing agent becomes uniform throughout the coating film during thermal polymerization, improving surface hardness.

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

[0083] Examples of pyrazole-based blocking agents include pyrazole-based compounds such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

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

[0085] (Examples of blocked isocyanate compounds) Examples of the polyfunctional isocyanate compound having an isocyanate group protected with a 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] 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), Coronate 2554 (manufactured by Tosoh Corporation), VESTANAT B 1358 A (manufactured by Evonik), and VESTANAT B 1186 A (manufactured by Evonik).

[0087] (3.1.3) Maleimide group-containing thermally polymerizable compound Examples of the maleimide group-containing thermally polymerizable compound 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, and 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, bismaleimidomethane, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, bismaleimidododecane, N,N '-m-phenylene dimaleimide, N,N'-p-phenylene dimaleimide, 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-tolylene dimaleimide, N,N'-2,6-tolylene dimaleimide, N,N'-m-xylylene dimaleimide, bisphenol A diphenyl ether bismaleimide, and the like. Of these, bismaleimide is preferred.

[0088] Commercially available thermally polymerizable compounds include 4-hydroxybutyl acrylate glycidyl ether 4HBAGE (manufactured by Mitsubishi Chemical Corporation), 4,4'-diphenylmethane bismaleimide BMI-1000 (manufactured by Daiwa Chemical Industry Co., Ltd.), bisphenol A epoxy resin YD-127 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 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 may be any compound that undergoes a polymerization or crosslinking reaction upon irradiation with actinic rays, thereby polymerizing or crosslinking and curing the composition. The photopolymerizable compound according to the present invention also includes a compound that also has the ability to undergo a polymerization reaction when heated, depending on the reaction conditions.

[0090] Examples of the photopolymerizable compound include a radically polymerizable compound and a cationically polymerizable compound. The photopolymerizable compound may be any of a monomer, a polymerizable oligomer, a prepolymer, or a mixture thereof. The curable composition may contain only one type of photopolymerizable compound, or may contain two or more types of photopolymerizable compounds.

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

[0092] (3.2.1) Radical polymerizable compound The radically polymerizable compound is preferably, for example, a compound having a radically polymerizable ethylenically unsaturated bond, and any compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule may be used, including compounds having chemical forms such as a monomer, oligomer, or polymer.

[0093] The radical polymerizable compound may be used alone, or two or more kinds may be used in any ratio in combination to improve the desired properties.

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

[0095] (Examples of (meth)acrylates) Examples of (meth)acrylates include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomylstyryl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalate, 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 cumylphenoxylethyl acrylate. , tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, and t-butylcyclohexyl (meth)acrylate, as well as monofunctional acrylates such 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,Examples of the acrylate include bifunctional 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, hydroxypivalic acid neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and tricyclodecane dimethanol diacrylate, as well as multifunctional 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 ethoxy tetra(meth)acrylate.

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

[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] The (meth)acrylate may be a modified product. Examples of modified (meth)acrylates include ethylene oxide-modified (meth)acrylates such as ethylene oxide-modified trimethylolpropane tri(meth)acrylate and ethylene oxide-modified pentaerythritol tetraacrylate, caprolactone-modified (meth)acrylates such as caprolactone-modified trimethylolpropane tri(meth)acrylate, and caprolactam-modified (meth)acrylates such as caprolactam-modified dipentaerythritol hexa(meth)acrylate.

[0099] The (meth)acrylate may be a polymerizable oligomer. Examples of the polymerizable oligomer (meth)acrylate 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 The cationically polymerizable compound may be an epoxy compound, a vinyl ether compound, an oxetane compound, or the like. The curable composition may contain only one type of cationically polymerizable compound, or may contain two or more types of cationically polymerizable compounds.

[0101] (3.2.3) Photopolymerization initiator 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 cationically polymerizable compound, it is preferable to use a photoacid generator. The curable composition according to the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators.

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

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

[0104] When the photopolymerization initiator contained in the first curable composition according to the present invention is a hydrogen abstraction radical polymerization initiator in a larger amount than an α-cleavage radical polymerization initiator, crosslinking and gelation of the coating film proceeds due to the hydrogen abstraction effect, and the crosslinking density of the coating film is further improved, thereby improving the adhesion to the recording medium (substrate).

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

[0106] The α-cleavage type radical polymerization initiator is an initiator that cleaves after photoexcitation to directly give an initiating radical. A hydrogen abstraction type radical polymerization initiator is a photopolymerization initiator that is activated by actinic rays (e.g., ultraviolet rays) and generates free radicals by abstracting hydrogen from a second compound, and the second compound becomes the actual initiating free radical. This second compound is called a polymerization synergist or coinitiator. Both Type I and Type II photoinitiators can be used in the present invention, either alone or in combination.

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

[0108] Examples of acetophenone-based initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenyl 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 the acylphosphine oxide initiator include 2,4,6-trimethylbenzoindiphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0110] Examples of the hydrogen abstraction type radical initiator include benzophenone-based initiators, thioxanthone-based initiators, aminobenzophenone-based initiators, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone. Examples of benzophenone-based initiators include benzophenone, o-benzoylmethylbenzoate-4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated 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 the compounds described in Organic Electronics Materials Research Group, "Imaging Organic Materials," Bunshin Publishing (1993), pp. 187-192. The content of the photopolymerization initiator may be in any range that allows the curable composition to be sufficiently cured, and may be, for example, 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) (manufactured by BASF), Irgacure 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) (manufactured by BASF), Irgacure 379 (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone) (manufactured by BASF), Irgacure 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one), Speedcure DETX (2,4-diethylthioxanthone), Speedcure ITX (2-isopropylthioxanthone) (all manufactured by Lambson), Genocure ITX (manufactured by Rahn AG), and Genocure EPD (manufactured by Rahn AG). AG) and others.

[0113] The curable composition according to the present invention may further contain a photopolymerization initiator aid, a polymerization inhibitor, and the like, as needed. The photoinitiator coagent may be a tertiary amine compound, preferably an aromatic tertiary amine compound.

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

[0115] The amount of photopolymerization initiator added is preferably small so that the curing by light is appropriately suppressed and the thermosetting reaction is promoted. The content is preferably in the range of 0.2 to 10% by mass, more preferably in the range of 0.5 to 5% by mass, based on the total mass of the curable composition.

[0116] (3.3) Polymerization inhibitor It is preferable that the first curable composition according to the present invention contains a polymerization inhibitor, from the viewpoint of improving the adhesiveness between a plurality of curable compositions. Here, the term "polymerization inhibitor" generally includes all compounds that are added to inhibit polymerization reactions during the preparation of a curable composition containing a polymerizable compound or during storage after preparation.

[0117] In the present invention, various conventionally known polymerization inhibitors can be used. However, from the viewpoint of exerting the effect, it is more preferable that the polymerization inhibitor contains any one of an N-oxyl-based polymerization inhibitor, a phenol-based polymerization inhibitor containing an ot-butyl group, and a polymerization inhibitor having two or more aromatic rings.

[0118] Among these, it is more preferable to contain an N-oxyl-based polymerization inhibitor from the viewpoint of interlayer adhesion. Similarly, for the second curable composition, an N-oxyl-based polymerization inhibitor is preferred. The content of the polymerization inhibitor is preferably within a 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 the N-oxyl polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, and Irgastab UV10 (manufactured by BASF).

[0120] (3.3.2) Phenol-based polymerization inhibitors Examples of the phenolic polymerization inhibitor 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 polymerization inhibitors Examples of the quinone polymerization inhibitor include hydroquinone, methoxyhydroquinone, benzoquinone, 1,4-naphthoquinone, and p-tert-butylcatechol.

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

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

[0124] These may be used alone or in combination of two or more. Among these, N-oxyl and quinone 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 naphthoquinone, etc., as a polymerization inhibitor having two or more aromatic rings, are preferably used.

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

[0126] The polyfunctional radically polymerizable compound preferably has two or more radically polymerizable functional groups. Examples of the polyfunctional radically polymerizable compound include polyfunctional (meth)acrylates, polyfunctional urethane acrylates, and epoxy-modified polyfunctional acrylates. The radical polymerizable compound may be one kind or more kinds.

[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 by turning it 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 to an uncured or insufficiently cured state, the first and second curable compositions mix at their interface, improving interlayer adhesion while preventing bleeding.

[0128] The gelling agent preferably crystallizes at a temperature equal to or lower than the gelling temperature of the curable composition. The gelling temperature refers to the temperature at which, when a curable composition that has been converted into a sol or liquid by heating is cooled, the gelling agent undergoes a phase transition from sol to gel, causing a sudden change in viscosity of the curable composition. Specifically, the solated or liquefied curable composition is cooled while measuring its viscosity using a viscoelasticity measuring device (e.g., MCR300, manufactured by Anton Paar), and the temperature at which the viscosity suddenly increases can be determined 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 formed by the gelling agent crystallized into a plate shape, a so-called house-of-cards structure.

[0130] To form a house-of-cards structure, it is preferable that the photopolymerizable compound and the gelling agent dissolved in the curable composition are compatible with each other.

[0131] Examples of gelling agents suitable for forming house-of-card structures include aliphatic ketones, aliphatic esters, petroleum waxes, vegetable 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 acid and dimer diol.

[0132] Among these, from the viewpoint of further enhancing pinning properties, aliphatic ketones, aliphatic esters, higher fatty acids, and higher alcohols having a hydrocarbon group with 9 to 25 carbon atoms are preferred. The curable composition may contain only one type of gelling agent, or may contain two or more types of gelling agents.

[0133] (3.5.1) Aliphatic ketones Examples of aliphatic ketones include dilignoceryl ketone, dibehenyl ketone, distearyl ketone, dieicosyl ketone, dipalmityl ketone, dilauryl ketone, dimyristyl ketone, myristyl palmityl ketone, and palmityl stearyl ketone.

[0134] (3.5.2) Aliphatic esters Examples of the fatty esters include fatty acid esters of monoalcohols such as behenyl behenate, eicosanoic acid icosyl, and oleyl palmitate; and fatty acid esters of polyhydric alcohols such as glycerin 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 products of the above aliphatic esters include the EMALEX series manufactured by Nippon Emulsion Co., Ltd. ("EMALEX" is a registered trademark of the company), and the Rikemal series and Poem series manufactured by Riken Vitamin Co., Ltd. ("Rikemal" 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 Among them, in the present invention, the gelling agent is particularly preferably an aliphatic ketone represented by the following general formula (G1) or an aliphatic ester represented by the following general formula (G2).

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

[0140] (In general formula (G1), R1 and R2 each independently represent an alkyl group having 12 to 26 carbon atoms, which includes a linear portion and may include a branch. 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 having 12 to 26 carbon atoms, which includes a linear portion and may include a branch. R3 and R4 may be the same or different.)

[0143] In general formulas (G1) and (G2), the linear or branched hydrocarbon group has 12 or more carbon atoms, which increases the crystallinity of the aliphatic ketone represented by general formula (G1) and the aliphatic ester represented by general formula (G2), and creates more space in the house-of-card structure. Therefore, the photopolymerizable compound can be easily and sufficiently enclosed within the spaces, and the pinning ability of the curable composition can be improved. Since the number of carbon atoms in the linear or branched hydrocarbon group is 26 or less, the melting points of the aliphatic ketone represented by general formula (G1) and the aliphatic ester represented by general formula (G2) do not become excessively high, and there is no need to excessively heat the curable composition when ejecting it.

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

[0145] Commercially available examples of the aliphatic ketone represented by general formula (G1) include 18-Pentatriacontanone manufactured by Alfa Aeser, Hentriacontan-16-one manufactured by Alfa Aeser, and Kaowax T-1 manufactured by Kao Corporation.

[0146] Examples of the aliphatic ester represented by general formula (G2) include behenyl behenate (number of carbon atoms: 21, 22), icosanoic acid icosyl (number of carbon atoms: 19, 20), stearyl stearate (number of carbon atoms: 17, 18), palmityl stearate (number of carbon atoms: 16, 17), lauryl stearate (number of carbon atoms: 12, 17), cetyl palmitate (number of carbon atoms: 6, 15), stearyl palmitate (number of carbon atoms: 15, 18), myristoyl stearate (number of carbon atoms: 16, 17), Myristate (C13,14), cetyl myristate (C13,16), octyldodecyl myristate (C13,20), stearyl oleate (C17,18), stearyl erucate (C18,21), stearyl linoleate (C17,18), behenyl oleate (C18,22), and arachidyl linoleate (C17,20). The carbon numbers in parentheses indicate the number of carbons in each of the two hydrocarbon groups separated by the ester group.

[0147] Commercially available examples of 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), Exepar SS and Exepar MY-M, manufactured by Kao Corporation ("Exepar" 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 Amuleps PC, manufactured by Kokyu Alcohol Kogyo Co., Ltd. ("Amuleps" is a registered trademark of the company).

[0148] (3.5.6) Gelling agent content The content of the gelling agent is preferably within a 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, alkyl naphthalene 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 colorant, if necessary. The colorant may be a pigment or a dye, but a pigment is preferred because it has good dispersibility in the components of the curable composition and excellent weather resistance. The pigment is not particularly limited, but examples thereof include organic pigments or inorganic pigments having the following numbers listed in the Color Index.

[0151] The curable composition of the present invention may contain one or more colorants to obtain a desired color. The content of the colorant is preferably within a range of 0.1 to 20% by mass, more preferably within a range of 0.2 to 10% by mass, based on 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, and Pigment Orange. 13, 16, 20, 36 or a mixture thereof.

[0153] Blue or cyan pigment Examples of blue or cyan pigments include pigments 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, or mixtures thereof.

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

[0155] Yellow pigment Examples of yellow pigments include pigments 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, or mixtures thereof.

[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 (manufactured by 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, Chrome Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chrome Fine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770, Seikafast Red 8040, C405(F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seikafast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seikafast Bordeaux 10B-430, Seikalite Rose R40, Seikalite Violet B800, 7805, Seikafast Maroon 460N, Seikafast Orange 900, 2900, Seikalite Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (all manufactured by Dainichiseika Color & Chemicals Mfg. 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 Dye 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, Hostapearm Blue B2G (all manufactured by Hoechst Industries); Novoperm P-HG, Hostaperm Pink E, Hostaperm Blue 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, and CF9 (all manufactured by Mitsubishi Chemical Corporation) are examples.

[0158] Pigment Dispersion The pigment can be dispersed using, for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker, or the like.

[0159] The pigment is preferably dispersed so that the volume average particle size of the pigment particles is preferably within a range of 0.08 to 0.5 μm, and the maximum particle size is preferably within a range of 0.3 to 10 μm, more preferably within a range of 0.3 to 3 μm. The dispersion of the pigment is adjusted by selecting the pigment, dispersant, and dispersion medium, and 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 carboxylic acid esters having a hydroxy group, 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, polymeric copolymers, modified polyurethanes, modified polyacrylates, polyether ester-type anionic surfactants, naphthalenesulfonic 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 the Solsperse series from Avecia and the PB series from Ajinomoto Fine-Techno Co., Ltd.

[0161] <Dispersion aid> The curable composition according to the present invention may further contain a dispersing aid, if necessary. The dispersing aid may be selected depending on the pigment, and the total amount of the dispersing agent and dispersing aid is preferably within 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 contain a dispersion medium for dispersing the pigment, if necessary. A solvent may be contained in the curable composition as a dispersion medium. However, in order to suppress the solvent from remaining in the formed image, it is preferable to use a photopolymerizable compound (particularly a monomer having low viscosity) as described above as a dispersion medium.

[0163] (3.6.3) Other additives In the present invention, curing accelerators, coupling agents, ion trapping agents, solvents, etc. may be used as needed.

[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 4 A viscosity within the range of Pa·s is preferred in that the curable composition is sufficiently gelled when cooled to room temperature after application, and the pinning properties are good. Furthermore, from the viewpoint of further improving the ejection properties from an inkjet head, the viscosity of the curable composition according to the present invention at 80°C is preferably within the range of 3 to 20 mPa·s, and more preferably within 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 point within the range of 40 to 100°C. When the phase transition point is 40° C. or higher, the curable composition quickly gels after being applied to a recording medium, resulting in higher pinning properties. Furthermore, when the phase transition point is lower than 100°C, the handleability of the curable composition is improved and the injection stability is increased. From the viewpoint of enabling the curable composition to be discharged at a lower temperature and reducing the load on the image forming apparatus, the phase transition point of the curable composition according to the present invention is more preferably within the range of 40 to 60°C.

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

[0167] In the present invention, these viscosities and phase transition points are values ​​obtained by the following methods. 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 temperature curve of viscosity.

[0168] The viscosity at 80°C and the viscosity at 25°C can be determined by reading the viscosity at 80°C and the viscosity at 25°C on a temperature change curve of viscosity. The phase transition point can be determined as the temperature at which the viscosity reaches 200 mPa·s on the viscosity temperature curve. [Example]

[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, operations were carried out at room temperature (25°C). Unless otherwise specified, "%" and "parts" mean "mass %" and "parts" respectively. It means "parts by mass."

[0170] <Preparation of Yellow Pigment Dispersion A> Dispersant 1 and Dispersant 2 shown below and the dispersion medium were placed in a stainless steel beaker, heated on a hot plate at 65°C for 1 hour while stirring and dissolving, and then cooled to room temperature. The pigment shown below was added to this, and the mixture was placed in a glass bottle together with 200 g of zirconia beads with a diameter of 0.5 mm and sealed. This was dispersed in a paint shaker until the desired particle size was reached, and then the zirconia beads were removed.

[0171] Dispersant 1: PX4701 (manufactured by BASF) 6.0 parts by mass Dispersant 2: Solsperse 22000 (manufactured by Lubrizol Japan) 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 Cyan Pigment Dispersion B> Dispersion A was prepared in the same manner as Dispersion A, except that the dispersant, dispersion medium, and pigment used in the preparation of the yellow pigment dispersion 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 (Dainichi Seika Chemicals, Chromofine Blue 6332JC) 23 parts by mass

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

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

[0176] In this experiment, the following compounds were used as a polymerizable compound, a polymerization inhibitor, a heat curing agent, a photopolymerization initiator, a dispersant, and a gelling agent. Details of the polymerizable compound, polymerization inhibitor, heat curing agent, photopolymerization initiator, dispersant and gelling agent are given below.

[0177] <Polymerizable compound> 2-(1,2-Cyclohexanedicarboximide)ethyl acrylate M140 (Toagosei Co., Ltd., molecular weight 251) Dipropylene glycol diacrylate SR508NS (Sartomer, molecular weight 242) Diethylene glycol diacrylate SR259 (Sartomer, molecular weight 302) Dioxane glycol diacrylate A-DOG (Shin-Nakamura Chemical Co., Ltd., molecular weight 326) 3PO-modified trimethylolpropane triacrylate M360 (Miwon, molecular weight 471) Bisphenol A 4EO modified diacrylate M240 (Miwon, molecular weight 512) Cyclic trimethylolpropane formacrylate M1110 (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] <Thermal curing agent> 4-Hydroxybutyl acrylate glycidyl ether 4HBAGE (Mitsubishi Chemical Corporation) 4,4'-Diphenylmethane bismaleimide BMI-1000 (Manufactured by Daiwa Chemical Industry Co., Ltd.) Bisphenol A epoxy resin YD-127 (Manufactured by Nippon Steel & Sumikin 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; Norrish Type I (referred to as "Type I") (Manufactured by BASF) Irgacure819; Norrish Type I (referred to as "Type I") (Manufactured by BASF) Irgacure907; Norrish Type I (referred to as "Type I") (Manufactured by BASF) Speedcure ITX; Norish Type II (referred to as "Type II") (Lambson)

[0181] The Norrish type I described above means an α-cleavage type radical polymerization initiator. The Norrish II type described above means a hydrogen abstraction type radical polymerization initiator.

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

[0183] <Gelling agent> Stearyl stearate Dibehenyl ketone

[0184] <Preparation of Curable Composition> In this experiment, curable compositions 1 to 35 using two types of polymerizable compounds, a polymerization inhibitor, a heat curing agent, two types of photopolymerization initiators, and two types of dispersants are shown in the following Tables I to IV.

[0185] [Table 1]

[0186] [Table 2]

[0187] [Table 3]

[0188] [Table 4]

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

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

[0191] The viscosity at 25°C of each of the curable compositions 21 to 27 containing a gelling agent is 1 to 1 × 10 4 In contrast, the viscosities of curable compositions 1 to 20 and curable compositions 28 to 35, which did not contain a gelling agent, were all less than 1 Pa·s. 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 to 39)> [Example 1] (Process 1) The prepared curable composition 1 was loaded as a first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this device, a pattern was formed by applying the above curable composition 1 in the form of a thin film onto a copper-clad laminate for printed wiring boards (FR-4, thickness 1.6 mm, size 150 mm×95 mm) which was a recording medium.

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

[0194] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern 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 step 1, the applied curable composition was not subjected to a curing treatment using heat or light.

[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 device, the second curable composition was applied onto the uncured first curable composition that had been applied in the above (Step 1).

[0196] As in step 1, 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, and the ink temperature inside the recording head was heated to 45°C. The piezo head had a nozzle diameter of 22 μm and a nozzle resolution of 360 dpi, which was arranged in a staggered pattern to form a nozzle row of 720 dpi.

[0197] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern 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 the above (Step 2), the composition was placed in an oven set at 150° C. for 60 minutes for full curing, and a print sample was obtained.

[0199] [Examples 2 to 6] In (Step 2) of Example 1, a print sample was obtained in the same manner as in Example 1, except that the curable composition charged into the inkjet recording apparatus as the second curable composition was changed as shown in Table V.

[0200] [Examples 7 to 20] A print 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 apparatus as the first curable composition was changed as shown in Table V.

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

[0202] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. The ink is heated to 80°C from the ink tank to the head. A heater was also built into the piezo head, and the ink temperature inside the recording head was heated to 80°C.

[0203] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern 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 step 1, the applied curable composition was not subjected to a curing treatment using heat or light.

[0204] (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 device, the second curable composition was applied onto the uncured first curable composition that had been applied in a thin film form onto the copper-clad laminate for printed wiring boards in the above (Step 1).

[0205] 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, and the ink temperature inside the recording head was heated to 45°C. The piezo head had a nozzle diameter of 22 μm and a nozzle resolution of 360 dpi, which was arranged in a staggered pattern to form a nozzle row of 720 dpi.

[0206] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm.

[0207] (Step 3) After the above (Step 2), a Phoseon Technology LED lamp, FireJet™ FJ100 (395 nm, 8 W / cm 2 ) at 2W / cm 2 , 500mJ / cm 2 The layer of the curable composition was cured by irradiation so as to obtain a value of 1000 nm. Thereafter, the coating was placed in an oven set at 150°C for 60 minutes for full curing, and a print sample was obtained.

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

[0209] [Examples 25 to 28] In the above (Step 1), a print sample was obtained in the same manner as in Example 1, except that the curable composition charged into the inkjet recording device as the first curable composition was changed as shown in Table VI.

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

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

[0212] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm.

[0213] (Additional Step: Step of Curing the First Curable Composition by Irradiation with Light) After the above (Step 1), a Phoseon Technology LED lamp, FireJet™ FJ100 (395 nm, 8 W / cm 2 ) to 0.1W / cm 2 , 50 mJ / cm 2 The first curable composition applied in a thin film form on the copper clad laminate for printed wiring board was cured to the extent that it remained in an uncured state without reaching full curing.

[0214] (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 device, the second curable composition was applied onto the uncured first curable composition that had been applied in a thin film form onto the copper-clad laminate for printed wiring boards in the above (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, and the ink temperature inside the recording head was heated to 45°C. The piezo head had a nozzle diameter of 22 μm and a nozzle resolution of 360 dpi, which was arranged in a staggered pattern to form a nozzle row of 720 dpi.

[0216] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern and a comb-shaped pattern with lines and spaces of 100 μm were printed on the substrate, each with a thickness of 20 μm.

[0217] (Step 3) After the above (Step 2), the composition was placed in an oven set at 150° C. for 60 minutes for full curing, and a print sample was obtained.

[0218] [Example 30] The same procedure as in Example 29 was carried out except that in step 3 of Example 29, a full curing step using light and heat was carried out. The light irradiation conditions were the same as those in Example 21 (step 3).

[0219] [Example 31] In (Step 1) of Example 1, the curable composition to be loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 20 which did not contain a thermosetting agent but used an N-oxyl-based polymerization inhibitor as a polymerization inhibitor. Other than that, a print sample was obtained in the same manner as in Example 1.

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

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

[0222] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern 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: Step of Curing the First Curable Composition by Irradiation with Light) After the above (Step 1), a Phoseon Technology LED lamp, FireJet™ FJ100 (395 nm, 8 W / cm 2 ) to 0.1W / cm 2 ,50mJ / cm 2 The first curable composition applied in a thin film form on the copper clad laminate for printed wiring board was cured to the 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 device, the second curable composition was applied onto the uncured first curable composition that had been applied in a thin film form onto the copper-clad laminate for printed wiring boards in the above (Step 1).

[0225] 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, and the ink temperature inside the recording head was heated to 45°C. The piezo head had a nozzle diameter of 22 μm and a nozzle resolution of 360 dpi, which was arranged in a staggered pattern to form a nozzle row of 720 dpi.

[0226] Using this inkjet device, a voltage was applied to print dots with a droplet volume of 6.0 pL, and a 20 mm x 50 mm solid pattern 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 LED lamp, FireJet™ FJ100 (395 nm, 8 W / cm 2 ) at 2W / cm 2 , 500mJ / cm 2 The layer of the curable composition was cured by irradiation so as to obtain a value of 1000 nm. Thereafter, the coating was placed in an oven set at 150°C for 60 minutes for full curing, and a print sample was obtained.

[0228] [Examples 33 to 37] In (Step 1) of Example 1, the curable composition to be loaded into the inkjet recording apparatus as the first curable composition was changed as shown in Table VII. Other than that, a print sample was obtained in the same manner as in Example 1.

[0229] [Example 38] In (Step 1) of Example 21, the curable composition charged into the inkjet recording apparatus as the first curable composition was changed to Curable Composition 23. Other than that, a print sample was obtained in the same manner as in Example 21.

[0230] [Example 39] A print 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 print sample was obtained in the same manner as in Example 29, except that in (Step 1) of Example 29, the curable composition loaded into the inkjet recording device as the first curable composition was changed to Curable Composition 23.

[0232] After the additional process (light irradiation), the first curable composition applied in a thin film form to the copper-clad laminate for printed wiring boards remained in an uncured state, not fully cured, and still had tackiness.

[0233] [Example 41] A print 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. After the additional process (light irradiation), the first curable composition applied in a thin film form to the copper-clad laminate for printed wiring boards remained in an uncured state, not fully cured, and still had 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 did not contain a thermosetting agent but contained a gelling agent. A print sample was obtained in the same manner as in Example 1 except for this.

[0235] <Pattern formation by inkjet recording method (Comparative Examples 1 and 2)> [Comparative Example 1] In (Step 1) of Example 40, the curable composition charged into the inkjet recording apparatus as the first curable composition was changed to Curable Composition 2. In addition, in an additional step after the step 1, an LED lamp FireJet™ FJ100 (395 nm, 8 W / cm) manufactured by Phoseon Technology was used. 2 ) at 2W / cm 2 , 500mJ / cm 2 A print 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 the layer with light so that the light intensity became 100 .mu.m.

[0236] Comparative Example 2 In (Step 1) of Example 41, the curable composition charged into the inkjet recording apparatus as the first curable composition was changed to Curable Composition 21. In addition, in an additional step after the step 1, an LED lamp FireJet™ FJ100 (395 nm, 8 W / cm) manufactured by Phoseon Technology was used. 2 ) at 2W / cm 2, 500mJ / cm 2 A print 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 the layer with light so that the light intensity became 100 .mu.m.

[0237] [evaluation] Tables V to VII show the cured states of the curable compositions in (Step 1) to (Step 3) and the evaluation results after (Step 3) for Examples 1 to 42 and Comparative Examples 1 and 2. Examples 29, 30, 32, 40, and 41 are reference examples. The evaluation was carried out with respect to interlayer adhesion, storage stability, adhesion to substrate, pencil hardness and bleeding. The evaluation methods and standards were as follows:

[0238] <Interlayer adhesion> For a print sample of a solid pattern of the second curable composition on the first curable composition, checkerboard cuts were made in the cured film according to the cross-cut method of JIS K5600, adhesive tape was applied and peeled off, and the peeling state of the cured film was observed. The residual adhesion rate was determined by the method described below and evaluated according to the criteria described below. Here, the residual adhesion rate is calculated by taking the number of squares created by cutting as the denominator and the number of squares remaining after tape peeling as the numerator.

[0239] (standard) ◎: Adhesion remaining rate 100% ○: Adhesion residual rate 90% or more but less than 100% △: Adhesion remaining rate is 70% or more but less than 90% ×: Adhesion remaining rate less than 70%

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

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

[0242] <Substrate adhesion> For a solid pattern print sample of the first curable composition, checkerboard cuts were made in the cured film in accordance with the cross-cut method of JIS K5600, adhesive tape was attached to the cured film, and the tape was peeled off to observe the peeling state of the cured film. The residual adhesion rate was determined by the method described below and evaluated according to the criteria described below. Here, the residual adhesion rate is calculated by taking the number of squares created by cutting as the denominator and the number of squares remaining after tape peeling as the numerator.

[0243] (standard) ◎: Adhesion remaining rate 100% ○: Adhesion residual rate 90% or more but less than 100% △: Adhesion remaining rate is 70% or more but less than 90% ×: Adhesion remaining rate less than 70%

[0244] <Pencil hardness> For a sample in which a solid pattern of the second curable composition was printed on the first curable composition, the pencil hardness of the surface was measured according to the method described in "JIS Standard K-5400." The evaluation was carried out according to the following criteria.

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

[0246] <Bleeding> The bleeding was evaluated according to the following method and criteria. That is, the print samples printed under the above conditions were visually inspected for bleeding and graininess. The presence or absence of bleeding was determined visually according to the following criteria.

[0247] (standard) ○: Little bleeding and low graininess. ×: Blurring and high graininess.

[0248] [Table 5]

[0249] [Table 6]

[0250] [Table 7]

[0251] A comparison of Examples 1 to 6 reveals that the pencil hardness is improved when an N-oxyl-based polymerization inhibitor is used as the polymerization inhibitor in the second curable composition. That is, 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 one of the following polymerization inhibitors in the second curable composition: an N-oxyl-based polymerization inhibitor (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Irgastab UV-10), a phenol-based 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, it can be seen that Examples 5 and 6, which use curable compositions 5 and 6 that use an N-oxyl-based polymerization inhibitor among the above polymerization inhibitors, have improved pencil hardness compared to Examples 3 and 4.

[0252] A comparison of Examples 7 to 16 reveals that the pencil hardness is improved when a bisphenol A epoxy resin or a blocked isocyanate compound is used as the heat curing agent for the first curable composition. In particular, it is preferable to use a blocked isocyanate compound.

[0253] That is, a comparison between Examples 7 to 11 and Examples 11 to 16 and Example 32 reveals that the pencil hardness is improved when a bisphenol A epoxy resin or a blocked isocyanate compound is used as the heat curing agent for the first curable composition. Furthermore, it can be seen that Examples 14 to 16 and Example 32, which use curable compositions 9, 10, 11 and 28 that use blocked isocyanate compounds among the above-mentioned heat curing agents, have improved substrate adhesion compared to Example 13.

[0254] Furthermore, a comparison of Examples 7 to 11 reveals that the use of an N-oxyl-based polymerization inhibitor as the polymerization inhibitor in the first curable composition improves interlayer adhesion and storage stability.

[0255] That is, a comparison between Example 7 and Examples 8 to 11 shows that the interlayer adhesion and storage stability are improved by including any one of the following polymerization inhibitors in the first curable composition: an N-oxyl-based polymerization inhibitor (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Irgastab UV-10), a phenol-based 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, it can be seen that Examples 10 and 11, which use curable compositions 5 and 6 that employ an N-oxyl-based polymerization inhibitor among the above polymerization inhibitors, have improved interlayer adhesion and storage stability compared to Examples 8 and 9.

[0257] A comparison of Examples 11 to 16 and Example 32 reveals that the use of a blocked isocyanate compound as the heat curing agent of the first curable composition improves the substrate adhesion.

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

[0259] A comparison between Example 10 and Examples 17 to 20 shows that the interlayer adhesion and substrate adhesion are improved by including a polyfunctional polymerizable compound formed using a monomer having an alicyclic structure, a monomer having a trifunctional polymerizable group, or a monomer having an aromatic ring as the first curable composition.

[0260] A comparison of Examples 12 to 15 and Examples 21 to 24 shows that by curing the first curable composition and the second curable composition by light irradiation after application and before thermal curing, the thermal curing can be more reliably achieved, and the pencil hardness is further improved.

[0261] From Example 25, it can be seen that the effect of the present invention is exhibited even when the type of initiator is changed. A comparison between Example 25 and Example 26 shows that the effects of the present invention are exhibited even when the type of photopolymerization initiator is changed.

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

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

[0264] In both Examples 29 and 30, after the additional process (light irradiation), the first curable composition applied in a thin film form to a copper-clad laminate for printed wiring boards remained in an uncured state, not fully cured, and still had tackiness. The difference between Examples 29 and 30 is that in Example 30, a curing treatment by light irradiation is carried out in step 3, and as a result, it can be seen that the pencil hardness of Example 30 is further improved. Furthermore, it can be seen that Examples 29 and 30 have poorer interlayer adhesion than Example 10, which also uses Curable Composition 5 as the first curable composition.

[0265] Examples 33 to 41 are examples in which the first curable composition containing a gelling agent was used, and comparison with the various examples above shows that bleeding was improved.

[0266] Examples 31 and 42 are examples in which the first curable composition containing no thermal curing agent was used. Comparing Examples 20 and 31 and Examples 37 and 42, it can be seen that Examples 31 and 42, which do not contain a heat curing agent, have an overall performance that does not pose a practical problem, but Examples 20 and 37, which contain a heat curing agent, have improved substrate adhesion and pencil hardness compared to Examples 31 and 42.

[0267] In Example 32, neither the first curable composition nor the second curable composition contained a polyfunctional polymerizable compound, and therefore the evaluations of interlayer adhesion and pencil hardness were poor. This shows that the inclusion of a polyfunctional polymerizable compound in the first curable composition and the second curable composition improves interlayer adhesion and pencil hardness.

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

[0269] Comparing Example 7 with Comparative Example 1 and Example 33 with Comparative Example 2, it can be seen 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, taking into consideration the evaluation results of Examples 29 and 30, it can be seen that the timing for applying the second curable composition is the time (period) when the first curable composition is in an uncured state and has not been subjected to any curing treatment.

[0271] It is possible to provide a recording method that can improve the adhesion between a plurality of curable compositions and suppress interlayer delamination, and a method for producing a printed matter using the recording method. [Explanation of symbols]

[0272] P Substrate, base material H Head HU head unit HU1 Head Unit 1 HU2 Head Unit 2 Q Board transport direction R Head carriage transport direction L Transport rail

Claims

1. A recording method using a curable composition, comprising: applying a first curable composition to a recording medium in the form of a thin film; applying a second curable composition onto the applied first curable composition; a step of curing the first and second curable compositions by at least heat or light, applying the second curable composition without subjecting the first curable composition to a heat or light curing treatment; and A recording method, wherein the first and second curable compositions are at least a heat-curable composition or a photo-curable composition.

2. the first curable composition contains a polymerization inhibitor, The polymerization inhibitor contains any one of an N-oxyl-based polymerization inhibitor, a phenol-based polymerization inhibitor containing an o-t-butyl group, and a polymerization inhibitor having two or more aromatic rings.

2. The recording method according to claim 1.

3. The first curable composition contains at least one of an epoxy resin and a blocked isocyanate compound as a heat curing agent.

3. The recording method according to claim 1 or 2.

4. Both the first curable composition and the second curable composition contain a multifunctional polymerizable compound.

4. The recording method according to claim 1, wherein the recording medium is a recording medium having a recording capacity of 1000 sq ft.

5. 5. The recording method according to claim 1, further comprising a photo-curing step after the step of applying the second curable composition and before the step of thermally curing the first and second curable compositions.

6. The first curable composition contains a photopolymerization initiator in which the content of the hydrogen abstraction type radical polymerization initiator is greater than the content of the α-cleavage type radical polymerization initiator.

6. The recording method according to claim 1, wherein the recording medium is a recording medium having a recording capacity of 1000 sq ft.

7. The first curable composition contains a gelling agent.

7. The recording method according to claim 1, wherein the recording medium is a recording medium having a recording capacity of 1000 kJ / s.

8. The recording method using the curable composition is an inkjet recording method.

8. The recording method according to claim 1, wherein the recording medium is a recording medium having a recording capacity of 1000 kJ / s.

9. A method for producing a printed matter, comprising producing a printed matter using the recording method according to any one of claims 1 to 8.

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