Recording method and method for producing printed matter

Abstract

The present invention addresses the problem of providing: a recording method capable of improving the adhesiveness between multiple curable compositions and suppressing interlayer separation; and a method for producing a printed article using said recording method.　This recording method uses a curable composition, the method being characterized by comprising: a step for applying a thin layer of a first curable composition on a recording medium; a step for applying a second curable composition on the first curable composition that has been applied; and a step for curing the first and the second curable composition with at least heat or light. The method is also characterized in that: the second curable composition is applied while the first curable composition has not been cured; and the first and the second curable compositions are at least heat-curable compositions or light-curable compositions.

Description

Technical Field

[0001] The present invention relates to a recording method and a method for producing a printed matter. More specifically, the present invention relates to a recording method and the like, characterized by improving the adhesion between a plurality of curable compositions and suppressing delamination between layers.

Background Art

[0002] Conventionally, a photolithography method or a screen printing method has been used for forming an etching resist, a solder resist, and a marking on a printed circuit board. For example, an inkjet method is used for forming a solder resist on a printed circuit board. After applying an inkjet ink and performing preliminary curing by light (hereinafter also referred to as "temporary curing"), a cured layer is formed by main curing by heat, which has already been proposed. Furthermore, printing indicating types, dates, etc. may be additionally applied on the cured layer. In such a case, the adhesion and adhesiveness between the cured layer and the additional printing are not sufficient, and problems such as peeling of the additional printing from the cured layer and bleeding of the additional printing on the cured layer occur.

[0003] For example, Patent Document 1 discloses a method of forming a cured layer by inkjet printing a UV-free radical curable inkjet ink on a support, performing temporary curing by light, and then performing main curing by heat. However, the adhesion of the substrate to the interface of the cured layer was not sufficient.

[0004] In addition, Patent Document 2 discloses a method of forming a cured layer by applying a curable composition, performing temporary curing by light to form a highly accurate thick laminate, and then performing main curing by heat. However, there is no description regarding the adhesion between different curable compositions, and the problem of delamination between layers remains.

[0005] In Patent Document 3, a procedure is disclosed in which a photocurable liquid thin film material is applied onto a substrate to form a liquid film, and the liquid film is temporarily cured by irradiating it with light for temporary curing while gradually increasing the intensity of the light, repeating this to form a laminate, and then irradiating it with light for final curing to perform final curing and cure the deep part of the cured layer, thereby forming a cured layer in which delamination is less likely to occur. However, there is also no description regarding the adhesiveness between different curable compositions, and the problem of delamination remains.

[0006] In Patent Document 4, a method for forming a thin film in which a first thin film material is applied, semi-cured, then a second thin film material is applied, semi-cured, and then final curing is performed by light, thereby sufficiently curing the deep part and making delamination less likely to occur is disclosed. However, there is also no description regarding the adhesiveness between different inks, and the problem of delamination has occurred.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0008] The present invention has been made in view of the above problems and situations, and the problem to be solved is to provide a recording method capable of improving the adhesiveness between a plurality of curable compositions and suppressing delamination, and a method for producing a printed matter using the recording method.

Means for Solving the Problems

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

[0010] 1. A recording method using a curable composition, comprising: a step of applying a first curable composition in a thin film form on a recording medium; a step of applying a second curable composition on top of the applied first curable composition; a step of curing at least the first and the second curable compositions by heat or light; the first curable composition being in an uncured state when the second curable composition is applied; the first and the second curable compositions being at least a thermosetting composition or a photocurable composition; and the first curable composition containing an N - oxyl - type polymerization inhibitor as a polymerization inhibitor and containing at least one of an epoxy resin or a blocked isocyanate compound as a thermosetting agent; at least one of the first curable composition and the second curable composition containing a polyfunctional polymerizable compound A recording method characterized by the above. 。

[0014] 2 . Having a photocuring step after the step of applying the second curable composition and before the step of thermally curing the first and the second curable compositions Characterized by the above as the first in the item The recording method described.

[0015] 3 . The content of the hydrogen - abstraction type radical polymerization initiator is higher than that of the α - cleavage type radical polymerization initiator as the photopolymerization initiator contained in the first curable composition Characterized by the above as item 1or The in item 2 recording method described.

[0016] 4 . The first curable composition contains a gelling agent The recording method according to any one of claims 1 to 3 any one of the claims up to the claim.

[0017] 5 . The recording method using the curable composition is an inkjet recording method The recording method according to any one of claims 1 to 4 any one of the claims up to the claim.

[0018] 6 . A method for producing a printed matter, characterized by producing a printed matter using the recording method according to any one of claims 1 to 5 any one of the claims up to the claim.

Advantages of the Invention

[0019] By the above means of the present invention, it is possible to provide a recording method capable of improving the adhesiveness between a plurality of curable compositions and suppressing delamination, and a method for producing a printed matter using the recording method. Regarding the expression mechanism or action mechanism of the effects of the present invention, it is not clear, but it is speculated as follows.

[0020] In the present invention, after applying the first curable composition on a recording medium, the second curable composition is applied while the first curable composition is in an uncured state, so that the respective composition components at the interface between the first layer and the second layer and in the vicinity thereof are somewhat mixed and the polymerization reaction is promoted. Therefore, it is presumed that the adhesion between the first layer and the second layer could be improved.

[0021] In addition, it has been found that by containing at least one polymerization inhibitor selected from N-oxyl polymerization inhibitors, phenolic polymerization inhibitors containing an o-t-butyl group, or polymerization inhibitors having two or more aromatic rings in the first curable composition, polymerization inhibition at the two-layer interface can be suppressed, the interlayer adhesion can be further improved, and the storage stability is also good. That is, perhaps because the polymerization inhibition is reduced when using polymerization inhibitors other than these, the polymerization at the two-layer interface is efficiently carried out, and the interlayer adhesion can be strengthened.

[0022] Furthermore, when both the first curable composition and the second curable composition contain a polyfunctional polymerizable compound, the interlayer adhesion and the pencil hardness are further improved. This is because the use of a highly reactive polyfunctional monomer increases the number of bonds connecting the two layers. In addition, since the interlayer adhesion is improved, the pencil hardness can be simultaneously improved.

[0023] Also, by having a photocuring 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 components of the first curable composition can be cured, the adhesion to the recording medium (substrate) can be further improved, and the formation of fine lines of the second curable composition is improved. Also, the interlayer adhesion can be maintained at a high level.

[0024] In addition, as the photopolymerization initiator contained in the first curable composition, when there are more hydrogen abstraction type radical polymerization initiators than α-cleavage type radical polymerization initiators, the crosslinking 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).

[0025] Furthermore, by containing a gelling agent in the first curable composition, the formation of fine lines is further improved while maintaining the interlayer adhesion. That is, by thickening on the recording medium (substrate) with the gelling agent, the bleeding of the second curable composition into the first curable composition can be greatly improved, and the formation of fine lines is further improved. Also, at the interface with the first curable composition, since the two layers are intermingled, good interlayer adhesion can be maintained.

Brief Description of the Drawings

[0026]

Figure 1

Figure 2A

Figure 2B

Figure 3A

Figure 3B

Figure 3C

Figure 4

Embodiments for Carrying Out the Invention

[0027] The recording method of the present invention is a recording method using a curable composition, comprising a step of applying a first curable composition in a thin film form on a recording medium, a step of applying a second curable composition on the applied first curable composition, and a step of curing the first and the second curable compositions at least by heat or light. The first curable composition is in an uncured state when the second curable composition is applied, the first and the second curable compositions are at least a thermosetting composition or a photocurable composition, and the first curable composition contains a polymerization inhibitor agent and and contains an N - oxyl - based polymerization inhibitor agent containing and contains at least one of an epoxy resin or a blocked isocyanate compound as a thermosetting agent, and a polyfunctional polymerizable compound is added to at least one of the first curable composition and the second curable composition characterized by containing. This feature is a technical feature common to or corresponding to the following respective embodiments (forms).

[0028] The adhesion between the plurality of curable compositions is improved by the first curable composition containing a polymerization inhibitor. Also, by containing an N-oxyl-based polymerization inhibitor as the polymerization inhibitor, the interlayer adhesion is improved. agent

[0029] As an embodiment of the present invention, the first curable composition contains an epoxy resin as a thermosetting agent. in , substrate adhesion and pencil hardness excellent in . Also, the first curable composition contains a blocked isocyanate compound as a thermosetting agent. in , substrate adhesion and pencil hardness excellent in .

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

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

[0032] Also, as the photopolymerization initiator contained in the first curable composition, it is preferable that the content of the hydrogen abstraction type radical polymerization initiator is larger than that of the α-cleavage type radical polymerization initiator, because the crosslinking gelation of the coating film proceeds due to the hydrogen abstraction effect, and the adhesion to the substrate is improved by further increasing the crosslinking density of the coating film.

[0033] Furthermore, it is preferable that the first curable composition contains a gelling agent, because it can greatly improve the bleeding of the second curable composition into the first curable composition, further improve the formation of fine lines, and maintain the interlayer adhesion.

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

[0035] Hereinafter, the present invention, its components, and embodiments and modes for carrying out the present invention will be described in detail. In the present application, "~" is used to mean including the numerical values described before and after as the lower limit value and the upper limit value.

[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, which includes a step of coating a first curable composition in a thin film on a recording medium, a step of coating a second curable composition on the coated first curable composition, and a step of curing the first and second curable compositions at least by heat or light. The first curable composition is in an uncured state when the second curable composition is coated. The first and second curable compositions are at least a thermosetting composition or a photocurable composition, and the first curable composition contains agent and a polymerization inhibitor, agent an N-oxyl-based polymerization inhibitor and contains at least one of an epoxy resin or a blocked isocyanate compound as a thermosetting agent, and a polyfunctional polymerizable compound is added to at least one of the first curable composition and the second curable composition and is characterized by containing the same. Fig. 1 schematically shows 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 coated on the recording medium is subjected to curing measures such as irradiation with active light rays for curing, heating, and removal of solvents, and in this state, the polymerization and cross-linking reactions between the constituent components of the curable composition proceed partially to some extent, or the solvent contained in the curable composition is removed by drying or the like, and the curable composition has high viscosity and loses fluidity, and further refers to the state before the entire composition finally becomes completely solid.

[0038] Therefore, based on the above definition, the state in which the curable composition has tackiness (also referred to as "tack") is included in the uncured state. In this specification, the state in which the entire composition has become completely solid will be 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, that is, the ratio of the degree of polymerization (also referred to as "conversion rate"). From this perspective, when the ratio of the degree of polymerization at the time of complete solidification is set to 100, the ratio of the degree of polymerization in the uncured state is lower than 100 and varies depending on the chemical structure and performance of the constituent components. However, in the present invention, it is preferable to apply the second curable compound under the condition that the ratio of the degree of polymerization is maintained within the range of 90 or less.

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

[0041] In the present invention, within the range of keeping the first curable composition in the uncured state, an additional step of irradiating, heating, or drying the first curable composition with actinic rays to such an extent that the first curable composition does not completely become solid may be provided between the above-mentioned step 1 and step 2.

[0042] "The first and second curable compositions are at least a thermosetting composition or a photocurable composition." means that the first and second curable compositions are any one of the three types of curable compositions: a thermosetting composition, a photocurable composition, and 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. For example, copper-clad laminates for high-frequency circuits using materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO / cyanate ester, etc., all grades (such as FR-4) of copper-clad laminates, and other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, stainless steel plates, copper plates, etc. are preferable.

[0044] (1.2) Process 1 and Process 2 Process 1 is a process of coating a first curable composition in a thin film form on a recording medium. Process 2 is a process of coating a second curable composition on the first curable composition that has been coated and is in an uncured state. For the coating of the first curable composition in Process 1 and the coating of the second curable composition in Process 2, various known coating methods and printing methods can be used respectively. For example, coater coating, offset printing, screen printing, gravure printing, flexographic printing, inkjet recording method, etc. can be used. The coating methods used in Process 1 and Process 2 may be the same or different.

[0045] (1.3) Process 3 The curing process in Process 3 is a process of applying energy of actinic rays and / or heat sufficient for the curable composition layer to be completely cured to the curable composition layer. For these curing methods, conventionally known methods can be appropriately used.

[0046] The actinic rays can be selected from, for example, electron beams, ultraviolet rays, alpha rays, gamma rays, and X-rays, etc., but ultraviolet rays are preferably used. Irradiation with ultraviolet rays can be performed, for example, using a water-cooled LED manufactured by Phoseon Technology under the condition of a wavelength of 395 nm. By using the LED as a light source, it is possible to suppress the poor curing of the curable composition due to the curable composition melting by the radiant heat of the light source.

[0047] Irradiation with ultraviolet rays uses ultraviolet rays having a wavelength in the range of 340 to 410 nm, and the peak illuminance on the surface of the curable composition is preferably in the range of 0.05 to 10 W / cm 2 and more preferably in the range of 0.1 to 5 W / cm 2 and is performed so as to be within this range. From the viewpoint of suppressing the irradiation of the curable composition with radiant heat, the amount of light irradiated is preferably less than 1500 mJ / cm 2 2.

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

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

[0050] As the heating method, for example, it is preferable to put it into an oven set within the range of 110 to 180 °C for 10 to 120 minutes.

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

[0052] (Inkjet recording method) The application of the first and second curable compositions in the step 1 and the step 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 necessary parts, which is particularly advantageous when applying a resist pattern or characters. The inkjet method is a method of ejecting inkjet ink from a nozzle and landing it 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 at positions corresponding to a resist film to be formed on a substrate as a recording medium, for example, a printed circuit board, and can be patterned.

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

[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 any of electro-mechanical conversion methods such as single cavity type, double cavity type, bender type, piston type, shear mode type, and shared wall type, and electro-thermal conversion methods such as thermal inkjet type and bubble jet (registered trademark) (bubble jet is a registered trademark of Canon Inc.).

[0055] By ejecting the droplets of the first curable composition from the inkjet head in a heated state, the ejection stability can be enhanced. The temperature of the first curable composition at the time of ejection is preferably in the range of 40 to 100°C, and more preferably in the range of 40 to 90°C in order to further enhance the ejection stability. In particular, it is preferable to perform 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 using a sol-gel phase transition type ink containing a gelling agent as the first and / or second curable composition, in order to enhance the ink ejection property from the inkjet head, it is preferable that the temperature of the ink when filled in the inkjet head is set to (gelation temperature + 10)°C to (gelation temperature + 30)°C of the ink. When the temperature of the ink in the inkjet head is (gelation temperature + 10)°C or higher, it is possible to suppress the ink from gelling in the inkjet head or on the nozzle surface and the decrease in the ink ejection property. On the other hand, when the temperature of the ink in the inkjet head is (gelation temperature + 30)°C or lower, the injection stability of the ink deteriorates.

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

[0058] The droplet amount of the first and / or second curable composition when ejected is preferably in the range of 2 to 20 pL in terms of the recording speed and image quality. As the inkjet coating apparatus, an apparatus as shown in FIG. 2 can be used. FIG. 2A is a scan type apparatus in which the printing head unit HU reciprocates vertically to perform printing with respect to the conveyance direction Q of the substrate, and FIG. 2B is a single pass type apparatus in which the printing head unit is fixed with respect to the conveyance direction Q of the substrate to perform printing. In the coating of the first curable composition and the coating of the second curable composition, the combination of FIG. 2A and FIG. 2B can be freely selected. In FIG. 2, a plurality of heads H are shown in the printing head unit HU, but one head H may be sufficient. Placing a plurality of heads H is preferable in terms of increasing the printing speed and enhancing the production efficiency.

[0059] When the application of the first curable composition and the application of the second curable composition are continuously performed in the same apparatus, several effective configurations can be proposed for the conveyance of the substrate P and the timing of inkjet printing, and a part of them is presented in FIG. 3.

[0060] FIG. 3A shows a configuration in which the substrate is conveyed back and forth after the application of the first curable composition, and a method of applying the second curable composition during the back-and-forth conveyance, and a method of once returning the substrate to the initial position and then conveying it again (upward) to apply the second curable composition are possible. This method has the advantage that it is not necessary to transfer the substrate.

[0061] FIG. 3B shows a configuration in which a plurality (two in the figure) of print head units HU 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. In this method, since the application of the first curable composition and the application of the second curable composition can be continuously performed during the conveyance of the substrate P in one direction, the processing can be performed efficiently. In particular, it is advantageous when the second curable composition is applied while the first curable composition is uncured after the application of the first curable composition.

[0062] FIG. 3C is a modification of the apparatus of FIG. 3B, and shows a configuration in which a plurality (two in the figure) of substrates P are conveyed in parallel. Multiple substrate processes can be performed simultaneously, which is more efficient. Each print head unit HU in FIG. 3 can be appropriately adopted whether it is a scan type as shown in FIG. 2A or a single pass type as shown in FIG. 2B. Also, the drive timing of each print head unit HU may be individual or synchronous.

[0063] 2. Recording apparatus (Apparatus configuration) The recording method of the present invention can be implemented by using an apparatus having the following configuration, but is not limited thereto.

[0064] As an apparatus for implementing the present invention, step 1, step 2, step 3, and additional steps may be performed by independent apparatuses respectively, or may be performed by an apparatus combining several steps. Moreover, a function for performing processing other than these steps may be provided.

[0065] When each step is performed by an independent apparatus, in order to move the processing substrate between the independent apparatuses, an automatic conveyance function such as conveyor movement or robot transfer can also be provided. In the case of an apparatus in which a plurality of steps are combined within the same apparatus, the arrangement of each step can take various forms. A configuration having a linear conveyance path such as a conveyor method or a slider method, or a configuration in which the substrate and the processing part move relatively by rotating between steps called a turntable method, and further, a configuration in which a plurality of steps are arranged vertically, etc. can be appropriately adopted. When a series of steps are performed in one apparatus, the handling work associated with the transfer of the base material is reduced, so that an effect of increasing productivity can be obtained.

[0066] As an apparatus for implementing the present invention, an example of a schematic diagram of an apparatus having a configuration in which the steps rotate relative to each other is shown in FIG. 4. FIG. 4 is a schematic diagram of only the substrate transfer table, and S in FIG. 4 represents the rotation direction of the transfer table. Each number (1) to (6) in FIG. 4 is the number of the transfer table on which the substrate is placed.

[0067] For example, a substrate P as a recording medium is loaded at the position of the transfer table (1), and the first curable composition is applied in a thin film state at the position of (2) (step 1). Thereafter, if necessary, irradiation with actinic rays or heat or drying such that the first curable composition does not completely solidify is performed at the position of (3) (additional step), and the second curable composition is applied on the uncured first curable composition at the position of (4) (step 2), and the curable composition layer at the position of (5) is given the energy of actinic rays and / or heat sufficient for the curable composition to completely cure and is cured (step 3). When the transfer table reaches the position of (6), the substrate is taken out and each process is completed.

[0068] In addition, in FIG. 4, each process is installed for each stage, but in order to adjust the processing time at each stage, a configuration in which it is installed over a plurality of stages is also possible.

[0069] 3. Component Compounds Constituting the First and Second Curable Compositions Hereinafter, the component compounds constituting the curable composition that can be preferably 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 Compound As the component compounds constituting the first and second curable compositions according to the present invention, the following compounds can be used as the "thermopolymerizable compound" or "thermosetting agent". In addition, the thermopolymerizable compound according to the present invention includes compounds that also have the performance of causing a polymerization reaction by light depending on the reaction conditions.

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

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

[0073] (3.1.1) Thermopolymerizable compound containing a cyclic ether group The thermopolymerizable compound containing a cyclic ether group may have a plurality of cyclic ether groups in the molecule, and compounds having an epoxy group or an oxetanyl group are preferred.

[0074] (Compound having an epoxy group) Examples of the compound 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 novolak type epoxy emulsion.

[0075] Examples of the epoxy resin include one or more selected from 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-phenylene diisoprene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4′-(1,4-phenylene diisoprene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4′-cyclohexadiene bisphenol type epoxy resin); novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol group ethane type novolak type epoxy resin, novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure; biphenyl type epoxy resin; aralkyl type epoxy resins such as xylylene type epoxy resin, biphenyl aralkyl type epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin; anthracene type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; norbornene type epoxy resin; adamantane type epoxy resin; fluorene type epoxy resin.

[0076] (Compound having 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 their oligomers or copolymers, and also include oxetane alcohol and novolak resin, etc. In addition, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. are also included.

[0077] (4.1.2) Isocyanate group-containing thermopolymerizable compound Examples of the isocyanate group-containing thermopolymerizable compound are not particularly limited as long as the compound has two or more isocyanate groups in the molecule. Specifically, aromatic polyisocyanates 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), 1,5-naphthalene diisocyanate (NDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanatemethyl (NBDI); alicyclic polyisocyanates such as trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6XDI (hydrogenated XDI), H12MDI (hydrogenated MDI), H6TDI (hydrogenated TDI); polyisocyanates such as polymethylene polyphenylene polyisocyanate; their burette bodies, isocyanurate bodies and carbodiimide-modified products; and the like can be mentioned.

[0078] (Blocked isocyanate compound) Among the above isocyanate group-containing thermopolymerizable compounds, the blocked isocyanate compound, which is a polyfunctional isocyanate having an isocyanate group protected by a thermally dissociable blocking agent, is preferable from the viewpoints of adhesion to the recording medium and surface hardness of the coating film because the thermosetting reaction proceeds by thermal dissociation of the isocyanate group protected by the blocking agent.

[0079] The thermally dissociable blocking agent is preferably at least one compound selected from the group consisting of oxime-based compounds, pyrazole-based compounds and active ethylene-based compounds in terms of 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] Examples of commercially available products include trixene BI7982 (manufactured by LANXESS), trixene BI7961 (manufactured by LANXESS), and Blonate 1601V (manufactured by Dainichi 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), VESTANAT B 1186 A (manufactured by Evonik), and the like.

[0087] (3.1.3) Maleimide group-containing thermopolymerizable compound Examples of the maleimide group-containing thermopolymerizable compounds include N-methylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-propylmaleimide, N-butylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-p-carboxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-p-chlorophenylmaleimide, N-p-tolylmaleimide, N-p-xylylmaleimide, N-o-chlorophenylmaleimide, N-o-tolylmaleimide, N-benzylmaleimide, N-2,5-diethylphenylmaleimide, N-2,5-dimethylphenylmaleimide, N-m-tolylmaleimide, N-α-naphthylmaleimide, N-o-xylylmaleimide, N-m-xylylmaleimide, bismaleimidomethane, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, bismaleimidododecane, N,N′-m-phenylenedimaleimide, N,N′-p-phenylenedimaleimide, 4,4′-bismaleimidodiphenyl ether, 4,4′-bismaleimidodiphenylmethane, 4,4′-bismaleimido-di(3-methylphenyl)methane, 4,4′-bismaleimido-di(3-ethylphenyl)methane, 4,4′-bismaleimido-di(3-methyl-5-ethyl-phenyl)methane, N,N′-(2,2-bis-(4-phenoxyphenyl)propane)dimaleimide, N,N′-2,4-tolylenedimaleimide, N,N′-2,6-tolylenedimaleimide, N,N′-m-xylylenedimaleimide, bisphenol A diphenyl ether bismaleimide, and the like. Among these, bismaleimide is preferred.

[0088] Examples of commercially available products of the above heat-polymerizable compounds include 4-hydroxybutyl acrylate glycidyl ether 4HBAGE (manufactured by Mitsubishi Chemical Corporation), 4,4'-diphenylmethane bismaleimide BMI-1000 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), bisphenol A type epoxy resin YD-127 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), blocked isocyanate trixene BI7982 (manufactured by LANXESS), blocked isocyanate trixene BI7961 (manufactured by LANXESS), and blocked isocyanate Blonate 1601V (manufactured by Eisho Sangyo Co., Ltd.), etc.

[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 causes a polymerization or cross-linking reaction upon irradiation with actinic rays to polymerize or cross-link and has the effect of curing the composition. Note that the photopolymerizable compound according to the present invention also includes compounds that have the performance of causing a polymerization reaction by heating depending on the reaction conditions.

[0090] Examples of the photopolymerizable compound include radical polymerizable compounds and cationic polymerizable compounds. The photopolymerizable compound may be any of a monomer, a polymerizable oligomer, a prepolymer, or a mixture thereof. Only one kind of the photopolymerizable compound may be contained in the curable composition, or two or more kinds may be contained.

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

[0092] (3.2.1) Radical polymerizable compound The radical polymerizable compound is preferably a compound having a radically polymerizable ethylenically unsaturated bond, and any compound may be used as long as it has at least one radically polymerizable ethylenically unsaturated bond in the molecule, including those having chemical forms such as monomers, oligomers, and polymers.

[0093] Only one kind of radical polymerizable compound may be used, or two or more kinds may be used in combination at an arbitrary ratio in order to improve the desired properties.

[0094] The radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth)acrylate. In 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 monofunctional acrylates such as isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, cumylphenoxyl ethyl acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and t-butylcyclohexyl (meth)acrylate, and 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,Bifunctional acrylates including 9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, PO adduct of bisphenol A di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and tricyclodecane dimethanol diacrylate, and polyfunctional acrylates including trifunctional or higher acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxylate tri(meth)acrylate, and pentaerythritol ethoxytetra(meth)acrylate are included.,

[0096] Among the above (meth)acrylates, from the viewpoint of curing shrinkage and the like, phenoxyethyl (meth)acrylate, o-phenylphenol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and cumylphenoxyl ethyl acrylate are preferable.

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

[0098] Note that the (meth)acrylate may be a modified product. Examples of the (meth)acrylate which is a modified product 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] (Meth)acrylate may be a polymerizable oligomer. Examples of the (meth)acrylate which is a polymerizable oligomer include epoxy (meth)acrylate oligomer, aliphatic urethane (meth)acrylate oligomer, aromatic urethane (meth)acrylate oligomer, polyester (meth)acrylate oligomer, and linear (meth)acrylic oligomer.

[0100] (3.2.2) Cationically polymerizable compound The cationically polymerizable compound may be an epoxy compound, a vinyl ether compound, an oxetane compound, or the like. Only one kind or two or more kinds of the cationically polymerizable compound may be included in the curable composition.

[0101] (3.2.3) Photoinitiator When the photopolymerizable compound is a radically polymerizable compound, it is preferable to use a photo radical initiator, and when the photopolymerizable compound is a cationically polymerizable compound, it is preferable to use a photoacid generator. Only one kind or two or more kinds of the photoinitiator may be included in the curable composition according to the present invention. The photoinitiator may be a combination of both a photo radical initiator and a photoacid generator.

[0102] (Photo radical initiator) The photoinitiators 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").

[0103] As the photoinitiator contained in the first curable composition according to the present invention, since there are more hydrogen abstraction type radical polymerization initiators than α-cleavage type radical polymerization initiators, crosslinking gelation of the coating film progresses 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).

[0104] The content of the hydrogen abstraction type radical polymerization initiator is preferably in the range of 4 to 10% by mass based on the mass of the curable composition. The content of the α-cleavage type radical polymerization initiator is preferably in the range of 0.3 to 3% by mass based on the mass of the curable composition.

[0105] The α-cleavage type radical polymerization initiator is an initiator that cleaves after photoexcitation and directly provides initiating radicals. The hydrogen abstraction type radical polymerization initiator is a photoinitiator that is activated by actinic rays (for example, ultraviolet rays) and generates free radicals by hydrogen abstraction from a second compound, and the second compound becomes the actual initiating free radical. This second compound is called a polymerization synergist or co-initiator. Both type I and type II photoinitiators can be used alone or in combination in the present invention.

[0106] Examples of the cleavage type radical polymerization initiator include acetophenone-based initiators, benzoin-based initiators, acylphosphine oxide-based initiators, benzyl and methylphenylglyoxylate.

[0107] Examples of acetophenone-based initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and 2-benzyl-2-dimethylamino 1-(4-morpholinophenyl)-butanone.

[0108] Examples of benzoin-based initiators include benzoin, benzoin methyl ether, and benzoin isopropyl ether. Examples of acylphosphine oxide-based initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0109] Examples of hydrogen abstraction type radical initiators include benzophenone-based initiators, thioxanthone-based initiators, aminobenzophenone-based initiators, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone. Examples of benzophenone-based initiators include benzophenone, methyl o-benzoylbenzoate-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-based initiators include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. Examples of aminobenzophenone-based initiators include Michler's ketone and 4,4′-diethylaminobenzophenone.

[0110] (Photoacid generator) Examples of photoacid generators include the compounds described on pages 187 to 192 of "Organic Materials for Imaging" edited by the Research Society of Organic Electronics Materials, published by Bunshin Publishing (1993). The content of the photopolymerization initiator may be within a range where the curable composition can be sufficiently cured. For example, it can be within the range of 0.01 to 10% by mass based on the total mass of the curable composition according to the present invention.

[0111] Examples of commercially available products of photopolymerization initiators include DAROCURE TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) (manufactured by BASF), Irgacure819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) (manufactured by BASF), Irgacure379 (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone) (manufactured by BASF), Irgacure907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one), Speedcure DETX (2,4-diethylthioxanthone), Speedcure ITX (2-isopropylthioxanthone) (manufactured by Lambson), Genocure ITX (manufactured by Rahn A.G.), Genocure EPD (manufactured by Rahn A G.), etc.

[0112] The curable composition according to the present invention may further contain a photopolymerization initiator assistant, a polymerization inhibitor, etc. as necessary. The photopolymerization initiator assistant may be a tertiary amine compound, and an aromatic tertiary amine compound is preferred.

[0113] Examples of the aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-methylaminoethyl p-aminobenzoate, N,N-dimethylamino p-aminobenzoate isoamyl ethyl ester, N,N-dihydroxyethylaniline, triethylamine, N,N-dimethylhexylamine, and the like. Among them, N,N-dimethylaminoethyl p-aminobenzoate and N,N-dimethylamino p-aminobenzoate isoamyl ethyl ester are preferred. These compounds may be used alone or in combination of two or more.

[0114] Regarding the addition amount of the photopolymerization initiator, in order to promote the thermosetting reaction by moderately suppressing the curing by light, the addition amount should be as small as possible. It 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.

[0115] (3.3) Polymerization inhibitor From the viewpoint of improving the adhesion between the plurality of curable compositions, it is preferable that the first curable composition according to the present invention contains a polymerization inhibitor. Here, the "polymerization inhibitor" generally includes all compounds added to suppress the polymerization reaction during the preparation or storage after adjustment of the curable composition containing the polymerizable compound.

[0116] In the present invention, various conventionally known polymerization inhibitors can be used. Among them, it is more preferable from the viewpoint of effect expression to contain any one of N-oxyl-based polymerization inhibitors, phenol-based polymerization inhibitors containing an o-t-butyl group, or polymerization inhibitors having two or more aromatic rings.

[0117] Among these, it is more preferable to contain an N-oxyl-based polymerization inhibitor from the viewpoint of interlayer adhesion. Note that, similarly for the second curable composition, an N-oxyl-based polymerization inhibitor is preferred. The content of the polymerization inhibitor is preferably in the range of 0.05 to 0.5% by mass based on the mass of the curable composition.

[0118] (3.3.1) N-oxyl polymerization inhibitors Examples of N-oxyl polymerization inhibitors include 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-hydroxy-2,2,6,6-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), etc.

[0119] (3.3.2) Phenolic polymerization inhibitors Examples of phenolic polymerization inhibitors include 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT), 4-methoxyphenol, 2-methoxy-4-methylphenol, etc.

[0120] (3.3.3) Quinone polymerization inhibitors Examples of quinone polymerization inhibitors include hydroquinone, methoxyhydroquinone, benzoquinone, 1,4-naphthoquinone, p-tert-butylcatechol, etc.

[0121] (3.3.4) Amine polymerization inhibitors Examples of amine polymerization inhibitors include alkylated diphenylamine, N,N′-diphenyl-p-phenylenediamine, and phenothiazine, etc.

[0122] (3.3.5) Other polymerization inhibitors In addition, copper dithiocarbamate-based polymerization inhibitors such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate can be mentioned.

[0123] These may be used alone or in combination of two or more. Among these, N-oxyl-based and quinone-based polymerization inhibitors are preferred. As the polymerization inhibitors, 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. having two or more aromatic rings are preferably used.

[0124] (3.4) Polyfunctional 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 the interlayer adhesion between the first and second curable compositions. Examples of the polyfunctional polymerizable compound include polyfunctional radically polymerizable compounds having a plurality of radically polymerizable functional groups.

[0125] 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, epoxy-modified polyfunctional acrylates, and the like. The above-mentioned radically polymerizable compound may be one kind or more than one kind.

[0126] (3.5) Gelator It is preferable that the first curable composition according to the present invention contains a gelator. The gelator has a function of gelling the curable composition applied on the recording medium and temporarily fixing (pinning) it. When the curable composition containing the gelator is pinned in a gel state, the wet spreading of the curable composition is suppressed. When the second curable composition is applied in an uncured state or an insufficiently cured state, the two layers are mixed at the interface between the first curable composition and the second curable composition, so that the interlayer adhesion can be improved while preventing bleeding.

[0127] The gelling agent preferably crystallizes at a temperature below the gelling temperature of the curable composition. The gelling temperature refers to the temperature at which the gelling agent undergoes a phase transition from sol to gel and the viscosity of the curable composition changes rapidly when the curable composition solubilized or liquefied by heating is cooled. Specifically, the solubilized or liquefied curable composition can be cooled while measuring the viscosity with a viscoelasticity measuring device (for example, MCR300, manufactured by Anton Paar), and the temperature at which the viscosity rises rapidly can be defined as the gelling temperature of the curable composition.

[0128] When the gelling agent crystallizes in the curable composition, a structure in which the photopolymerizable compound is encapsulated in the three-dimensional space formed by the gelling agent crystallized in a plate shape, so-called card house structure, is formed.

[0129] <JPH In order to form a card house structure, it is preferable that the photopolymerizable compound dissolved in the curable composition and the gelling agent are compatible.

[0130] Examples of gelling agents suitable for forming the card house structure 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 acids and diol dimers.

[0131] Among them, from the viewpoint of further enhancing the pinning property, aliphatic ketones, aliphatic esters, higher fatty acids, and higher alcohols having a hydrocarbon group in the range of 9 to 25 carbon atoms are preferable. The gelling agent may be contained singly or in two or more kinds in the curable composition.

[0132] (3.5.1) Aliphatic ketone Examples of the aliphatic ketone include dilignoceryl ketone, dibehenyl ketone, distearyl ketone, dieicosyl ketone, dipalmitoyl ketone, dilauryl ketone, dimyristyl ketone, myristyl palmitoyl ketone, and palmitoyl stearyl ketone.

[0133] (3.5.2) Aliphatic ester Examples of the aliphatic ester include fatty acid esters of monoalcohols such as behenyl behenate, icosyl icosanoate, and oleyl palmitate; and fatty acid esters of polyhydric alcohols such as glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, and polyoxyethylene fatty acid ester.

[0134] 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 the Poem series, manufactured by Riken Vitamin Co., Ltd. (both 「Rikemal」 and 「Poem」 are registered trademarks of the company).

[0135] (3.5.3) Higher fatty acid Examples of the higher fatty acid include behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid.

[0136] (3.5.4) Higher alcohol Examples of the higher alcohol include stearyl alcohol and behenyl alcohol.

[0137] (3.5.5) Particularly preferred gelling agent Among them, in the present invention, as the gelling agent, an aliphatic ketone represented by the following general formula (G1) or an aliphatic ester represented by the following general formula (G2) is particularly preferred.

[0138] General formula (G1): R1-CO-R2

[0139] (In general formula (G1), R1 and R2 each independently represent an alkyl group containing a linear portion within the range of 12 to 26 carbon atoms and may contain a branch. R1 and R2 may be the same or different.)

[0140] General formula (G2): R3-COO-R4

[0141] (In general formula (G2), R3 and R4 each independently represent an alkyl group containing a linear portion within the range of 12 to 26 carbon atoms and may contain a branch. R3 and R4 may be the same or different.)

[0142] In general formulas (G1) and (G2), since the number of carbon atoms of the linear or branched hydrocarbon group is 12 or more, the crystallinity of the aliphatic ketone represented by general formula (G1) and the aliphatic ester represented by general formula (G2) is further enhanced, and more sufficient space is generated in the above card house structure. Therefore, the photopolymerizable compound is more easily sufficiently encapsulated in the above space, and the pinning property of the curable composition becomes higher. Since the number of carbon atoms of 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 increase excessively, and it is not necessary to heat the curable composition excessively when emitting the curable composition.

[0143] Examples of aliphatic ketones represented by the general formula (G1) include dilignoceryl ketone (number of carbon atoms: 23, 24), dibehenyl ketone (number of carbon atoms: 21, 22), distearyl ketone (number of carbon atoms: 17, 18), dieicosyl ketone (number of carbon atoms: 19, 20), dipalmitoyl ketone (number of carbon atoms: 15, 16), dimyristyl ketone (number of carbon atoms: 13, 14), dilauryl ketone (number of carbon atoms: 11, 12), lauryl myristyl ketone (number of carbon atoms: 11, 14), lauryl palmitoyl ketone (number of carbon atoms: 11, 16), myristyl palmitoyl ketone (number of carbon atoms: 13, 16), myristyl stearyl ketone (number of carbon atoms: 13, 18), myristyl behenyl ketone (number of carbon atoms: 13, 22), palmityl stearyl ketone (number of carbon atoms: 15, 18), palmityl behenyl ketone (number of carbon atoms: 15, 22), and stearyl behenyl ketone (number of carbon atoms: 17, 22). The number of carbon atoms in parentheses represents the number of carbon atoms of each of the two hydrocarbon groups divided by the carbonyl group.

[0144] Examples of commercially available aliphatic ketones represented by the general formula (G1) include 18-Pentatriacontanon, manufactured by Alfa Aeser, Hentriacontan-16-on, manufactured by Alfa Aeser, and Kao Wax T-1, manufactured by Kao Corporation.

[0145] Examples of the aliphatic esters represented by the general formula (G2) include behenyl behenate (carbon numbers: 21, 22), icosyl icosanoate (carbon numbers: 19, 20), stearyl stearate (carbon numbers: 17, 18), palmityl stearate (carbon numbers: 16, 17), lauryl stearate (carbon numbers: 12, 17), cetyl palmitate (carbon numbers: 6, 15), stearyl palmitate (carbon numbers: 15, 18), myristyl myristate (carbon numbers: 13, 14), cetyl myristate (carbon numbers: 13, 16), octyldodecyl myristate (carbon numbers: 13, 20), stearyl oleate (carbon numbers: 17, 18), stearyl erucate (carbon numbers: 18, 21), stearyl linoleate (carbon numbers: 17, 18), behenyl oleate (carbon numbers: 18, 22), and arachidyl linoleate (carbon numbers: 17, 20). The carbon numbers in parentheses represent the carbon numbers of each of the two hydrocarbon groups divided by the ester group.

[0146] Examples of commercially available aliphatic esters represented by the general formula (G2) include Unister M-2222SL and Spam Ace, manufactured by NOF Corporation ("Unister" is a registered trademark of the company), Exceparl SS and Exceparl MY-M, manufactured by Kao Corporation ("Exceparl" 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 Amrepus PC, manufactured by Kao Alcohol Industries Co., Ltd. ("Amrepus" is a registered trademark of the company).

[0147] (3.5.6) Content of the gelling agent The content of the gelling agent is preferably in the range of 1.0 to 10.0% by mass based on the total mass of the curable composition.

[0148] (3.6) Other components (3.6.1) Surfactant A surfactant can be added to the curable composition according to the present invention as needed. Examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, and polyoxyethylene - polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and silicone - based and fluorine - based surfactants.

[0149] (3.6.2) Colorant The curable composition according to the present invention may further contain a colorant as necessary. The colorant can be a pigment or a dye, but a pigment is preferred because it has good dispersibility with respect to the components of the curable composition and excellent weather resistance. The pigment is not particularly limited, and examples include organic pigments or inorganic pigments of the following numbers described in the Color Index.

[0150] The colorant may be included singly or in two or more kinds in the curable composition according to the present invention, and may be adjusted to a desired color. The content of the colorant is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.2 to 10% by mass, based on the total amount of the curable composition.

[0151] (Pigment) 《Red or Magenta Pigment》 Examples of red or magenta pigments include pigments selected from Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, or mixtures thereof, etc.

[0152] 《Blue or Cyan Pigments》 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, 60, or mixtures thereof, etc.

[0153] 《Green Pigments》 Examples of green pigments include pigments selected from Pigment Green 7, 26, 36, 50, or mixtures thereof.

[0154] 《Yellow Pigments》 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, 193, or mixtures thereof, etc.

[0155] 《Black Pigments》 Examples of black pigments include pigments selected from Pigment Black 7, 28, 26, or mixtures thereof, etc.

[0156] 《Examples of Commercially Available Pigments》 Examples of commercially available pigments include Black Pigment (manufactured by Mikuni Corporation), Chromophine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromophine Orange 3700L, 6730, Chromophine Scarlet 6750, Chromophine Magenta 6880, 6886, 6891N, 6790, 6887, Chromophine Violet RE, Chromophine Red 6820, 6830, Chromophine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromophine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromophine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770, Seika Fast Red 8040, C405(F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seika Light Rose R40, Seika Light Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 900, 2900, Seika Light Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (all of the above are manufactured by Dainichi Seika Chemicals 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 (all of the above are manufactured by DIC Corporation);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, ColortexBlue516, 517, 518, 519, A818, P-908, 510, Colortex Green402, 403, Colortex Black 702, U905 (manufactured by Sanyo Pigment Co., Ltd. as above); Lionol Yellow1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (manufactured by Toyo Ink Co., Ltd. as above), Toner Magenta E02, Permanent RubinF6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapeam BlueB2G (manufactured by Hoechst Industries as above); Novoperm P-HG, Hostaperm Pink E, Hostaperm Blue B2G (manufactured by Clariant as above); Carbon Black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, CF9 (manufactured by Mitsubishi Chemical as above), etc. can be mentioned.;

[0157] 《Dispersion of Pigments》 Dispersion of the pigment can be carried out, for example, by 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, etc.

[0158] Dispersion of the pigment is preferably carried out so that the volume average particle diameter of the pigment particles is preferably in the range of 0.08 to 0.5 μm, and the maximum particle diameter is preferably in the range of 0.3 to 10 μm, more preferably in the range of 0.3 to 3 μm. Dispersion of the pigment is adjusted by selection of the pigment, dispersant, and dispersion medium, dispersion conditions, filtration conditions, etc.

[0159] 《Dispersant》 The curable composition according to the present invention may further contain a dispersant in order to enhance the dispersibility of the pigment. Examples of the dispersant 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, high-molecular copolymers, modified polyurethanes, modified polyacrylates, polyether ester type anionic surfactants, naphthalene sulfonic acid formalin condensate salts, aromatic sulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, polyoxyethylene nonylphenyl ethers, and stearylamine acetate, etc. Examples of commercially available products of the dispersant include the Solsperse series of Avecia and the PB series of Ajinomoto Fine-Techno Co., Inc.

[0160] 《Dispersion aid》 The curable composition according to the present invention may further contain a dispersion aid as needed. The dispersion aid may be selected according to the pigment. The total amount of the dispersant and the dispersion aid is preferably in the range of 1 to 50% by mass with respect to the pigment.

[0161] 《Dispersion medium》 The curable composition according to the present invention may further contain a dispersion medium for dispersing a pigment, if necessary. Although a solvent may be included in the curable composition as the dispersion medium, in order to suppress the residue of the solvent in the formed image, it is preferable to use the above-mentioned photopolymerizable compound (especially a monomer with low viscosity) as the dispersion medium.

[0162] (3.6.3) Other additives In the present invention, a curing accelerator, a coupling agent, an ion scavenger, a solvent, etc. can be appropriately used, if necessary.

[0163] (3.7) Physical properties (3.7.1) Viscosity The viscosity of the curable composition according to the present invention at 25°C is preferably in the range of 1 to 1×10 4 Pa·s, because when it is applied and cooled to room temperature, the curable composition can be sufficiently gelled, and the pinning property becomes good. Also, from the viewpoint of further improving the ejection property from the inkjet head, the viscosity of the curable composition according to the present invention at 80°C is preferably in the range of 3 to 20 mPa·s, and more preferably in the range of 7 to 9 mPa·s.

[0164] (3.7.2) Phase transition point The curable composition according to the present invention preferably has a phase transition point in the range of 40 to 100°C. When the phase transition point is 40°C or higher, after being applied to the recording medium, the curable composition gels rapidly, so the pinning property becomes higher. Also, when the phase transition point is less than 100°C, the handleability of the curable composition is good and the ejection stability is high. From the viewpoint of enabling the curable composition to be ejected 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 in the range of 40 to 60°C.

[0165] (2.7.3) Measurement method and determination method of viscosity and phase transition point 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.

[0166] 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 was heated to 100°C, and while measuring the viscosity with a stress-controlled rheometer Physica MCR301 (diameter of the cone plate: 75 mm, cone angle: 1.0°), manufactured by Anton Paar, the curable composition was cooled to 20°C under the conditions of a shear rate of 11.7 (1 / s) and a temperature decrease rate of 0.1°C / s to obtain a temperature change curve of viscosity.

[0167] The viscosity at 80°C and the viscosity at 25°C can be determined by reading the viscosities at 80°C and 25°C, respectively, from the temperature change curve of viscosity. The phase transition point can be determined as the temperature at which the viscosity becomes 200 mPa·s in the temperature change curve of viscosity.

Example

[0168] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, the operations were carried out at room temperature (25°C). Also, unless otherwise specified, “%” and “parts” mean “mass %” and “parts by mass”, respectively.

[0169] <Preparation of Yellow Pigment Dispersion A> The following dispersant 1 and dispersant 2 and a dispersion medium were placed in a stainless steel beaker, heated and stirred for 1 hour while heating on a hot plate at 65°C, cooled to room temperature, and then the following pigment was added thereto, and it was put into a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm and sealed. This was subjected to a dispersion treatment with a paint shaker until a desired particle size was obtained, and then the zirconia beads were removed.

[0170] Dispersant 1: PX4701 (manufactured by BASF) 6.0 parts by mass Dispersant 2: Solsperse22000 (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 (manufactured by BASF, Paliotol Yellow D1155) 10.2 parts by mass

[0171] <Preparation of Cyan Pigment Dispersion B> In the preparation of the yellow pigment dispersion, it was prepared in the same manner as Dispersion A except that the dispersant, dispersion medium, and pigment were changed as shown below.

[0172] Dispersant: PX4701 (manufactured by BASF) 7.0 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 70 parts by mass Pigment: PB15:4 (manufactured by Dainichi Seika, Chromophine Blue 6332JC) 23 parts by mass

[0173] <Preparation of White Pigment Dispersion C> In the preparation of the yellow pigment dispersion, it was prepared in the same manner as Dispersion A except that the dispersant, dispersion medium, and pigment were changed as shown below.

[0174] Dispersant: PB824 (manufactured by Ajinomoto Fine-Techno Co., Inc.) 9 parts by mass Dispersion medium: Dipropylene glycol diacrylate (containing 0.2% UV-10) 71 parts by mass Pigment: Titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., TCR-52) 60 parts by mass

[0175] In this experiment, the following compounds were used as the polymerizable compound, polymerization inhibitor, thermosetting agent, photopolymerization initiator, dispersion, and gelling agent. Details of the polymerizable compound, polymerization inhibitor, thermosetting agent, photoinitiator, dispersion, and gelling agent are shown below.

[0176] <Polymerizable Compound> 2-(1,2-Cyclohexanedicarboximide)ethyl acrylate M140 (Manufactured by Toagosei Co., Ltd., molecular weight 251) Dipropylene glycol diacrylate SR508NS (Manufactured by Sartomer, molecular weight 242) Diethylene glycol diacrylate SR259 (Manufactured by Sartomer, molecular weight 302) Dioxane glycol diacrylate A-DOG (Manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326) 3PO-modified trimethylolpropane triacrylate M360 (Manufactured by Miwon, molecular weight 471) Bisphenol A type 4EO-modified diacrylate M240 (Manufactured by Miwon, molecular weight 512) Cyclic trimethylolpropane formal acrylate M1110 (Manufactured by Miwon, molecular weight 200)

[0177] <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

[0178] <Thermosetting Agent> 4-Hydroxybutyl acrylate glycidyl ether 4HBAGE (Manufactured by Mitsubishi Chemical Corporation) 4,4′-Diphenylmethane bismaleimide BMI-1000 (Manufactured by Daiwa Kasei Kogyo Co., Ltd.) Bisphenol A type epoxy resin YD-127 (Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Blocked isocyanate trixene BI7982 (Manufactured by LANXESS Co., Ltd.) Blocked isocyanate trixene BI7961 (Manufactured by LANXESS Co., Ltd.) Blocked isocyanate Blonate 1601V (Manufactured by Daiei Sangyo Co., Ltd.)

[0179] <Photoinitiator> DAROCURE TPO; Norrish type I (referred to as "Type I"). (Manufactured by BASF SE) Irgacure 819; Norrish type I (referred to as "Type I"). (Manufactured by BASF SE) Irgacure 907; Norrish type I (referred to as "Type I"). (Manufactured by BASF SE) Speedcure ITX; Norrish type II (referred to as "Type II"). (Manufactured by Lambson Ltd.)

[0180] Note that the above-mentioned Norrish type I means an α-cleavage type radical polymerization initiator. Also, the above-mentioned Norrish type II means a hydrogen abstraction type radical polymerization initiator.

[0181] <Dispersion> Dispersion A (Yellow pigment dispersion A) Dispersion B (Cyan pigment dispersion B) Dispersion C (White pigment dispersion C)

[0182] <Gelling agent> Stearyl stearate Dibehenyl ketone

[0183] <Preparation of curable composition> In this experiment, curable compositions 1 to 35 using two kinds of polymerizable compounds, a polymerization inhibitor, a thermosetting agent, two kinds of photopolymerization initiators, and two kinds of dispersions are shown in Tables I to IV below.

[0184]

Table 1

[0185]

Table 2

[0186]

Table 3

[0187]

Table 4

[0188] Each curable composition (hereinafter also referred to as "ink") described in Tables I to IV above was prepared and filtered through a 3 μm Teflon (registered trademark) membrane filter manufactured by ADVATEC. Using a viscoelasticity measuring device MCR300 manufactured by Physica, the viscosity at 80 °C and the gel phase transition temperature of each ink were measured at a shear rate of 1000 (1 / s).

[0189] Here, the gel phase transition temperature represents the temperature at which the complex viscosity becomes 1 Pa or more in the viscoelasticity curve obtained by changing the temperature at a temperature decrease rate of 0.1 °C / s, a strain of 5%, an angular frequency of 10 radian / s, and a temperature decrease rate of 0.1 °C / s.

[0190] The viscosities at 25 °C of curable compositions 21 to 27 containing a gelling agent were all 1 to 1×10 4 Pa·s, whereas the viscosities of curable compositions 1 to 20 and curable compositions 28 to 35 not containing a gelling agent were all less than 1 Pa·s. In addition, the gel phase transition temperatures of the curable compositions according to the present invention were all within the range of 40 to 100°C.

[0191] <Pattern shape by inkjet recording method composition> reference Example 1 (Step 1) The prepared curable composition 1 was loaded as the first curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, pattern formation was performed by applying the above curable composition 1 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) as the recording medium.

[0192] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. The ink was heated to 80°C from the ink tank to the head portion. A heater was also built into the piezo head to heat the ink temperature in the recording head to 80°C.

[0193] Using this inkjet apparatus, a voltage was applied so that dots with a droplet volume of 6.0 pl were formed, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed onto the substrate to a thickness of 20 μm each. Note that no curing measures by heat or light were applied to the applied curable composition in Step 1.

[0194] (Step 2) The prepared curable composition 29 was loaded as the second curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied onto the uncured first curable composition applied in the above (Step 1).

[0195] ​Note that, similar to 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 in the recording head was heated to 45°C. The piezo head had nozzles with a diameter of 22 μm, and the heads with a nozzle resolution of 360 dpi were arranged in a staggered pattern to form a nozzle array with a resolution of 720 dpi.

[0196] Using this inkjet device, a voltage was applied so that the droplet volume became a dot of 6.0 pl, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed on the substrate to a thickness of 20 μm each.

[0197] (Step 3) After the above (Step 2), it was put into an oven set at 150°C for 60 minutes for full curing to obtain a printed sample.

[0198] Reference Examples 2 to 4, Example 5、 6] The above reference In (Step 2) of Example 1, except that the curable composition loaded into the inkjet recording device was changed as shown in Table V as the second curable composition, reference a printed sample was obtained in the same manner as in Example 1.

[0199] Reference Examples 7 to 12, Reference Examples 17 to 20, Example 5、6、13~16 The above reference In (Step 1) of Example 1, except that the curable composition loaded into the inkjet recording device was changed as shown in Table V as the first curable composition, reference a printed sample was obtained in the same manner as in Example 1.

[0200] reference Example 21] (Step 1) The prepared curable composition 7 was loaded as the first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. ​​​​Using this apparatus, pattern formation was carried out by applying the above-mentioned curable composition 7 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 is a recording medium.

[0201] 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 portion. A heater was also built into the piezo head to heat the ink temperature in the recording head to 80°C.

[0202] Using this inkjet apparatus, a voltage was applied so that droplets would form dots with a volume of 6.0 pl, and a solid pattern of 20 mm × 50 mm and a comb-shaped pattern with a line & space of 100 μm were printed onto the substrate to a thickness of 20 μm each. Note that no curing measures by heat or light were applied to the applied curable composition in Step 1.

[0203] (Step 2) The prepared curable composition 29 was loaded as the second curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied onto the uncured first curable composition applied in a thin film form onto the copper-clad laminate for printed wiring boards in the above-mentioned (Step 1).

[0204] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. A heater was also built into the piezo head to heat the ink temperature in the recording head to 45°C. The piezo heads had a nozzle diameter of 22 μm, and heads with a nozzle resolution of 360 dpi were arranged in a staggered pattern to form a nozzle row with a resolution of 720 dpi.

[0205] Using this inkjet device, a voltage was applied so that dots with a droplet volume of 6.0 pl were formed, and a solid pattern of 20 mm × 50 mm and a comb-shaped pattern with a line & space of 100 μm were printed on the substrate to a thickness of 20 μm, respectively.

[0206] (Step 3) After the above (Step 2), an LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) manufactured by Phoseon Technology was irradiated at 2 W / cm 2 to 500 mJ / cm 2 to cure the layer of the curable composition. Thereafter, it was put into an oven set at 150 °C for 60 minutes for final curing to obtain a printed sample.

[0207] reference Example 22 Reference Example 33, 34, 24] The above reference In the (Step 1) of Example 21, a printed sample was obtained in the same manner as in Example 21, except that the curable composition loaded into the inkjet recording device as the first curable composition was changed as shown in Table VI. reference

[0208] reference Examples 25 to 28] In the above (Step 1), a printed sample was obtained in the same manner as in Example 1, except that the curable composition loaded into the inkjet recording device as the first curable composition was changed as shown in Table VI. reference

[0209] reference Example 29] (Step 1) reference A curable composition 5 prepared in the same manner as in Example 10 was loaded as the first curable composition into an inkjet recording device having an inkjet recording head equipped with a piezo-type inkjet nozzle. ​​​Using this apparatus, pattern formation was carried out by applying the above curable composition 5 in a thin film on a copper-clad laminate for printed wiring boards (FR-4 thickness 1.6 mm, size 150 mm × 95 mm) as a recording medium.

[0210] 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 portion. A heater was also built into the piezo head to heat the ink temperature in the recording head to 80 °C.

[0211] Using this inkjet apparatus, a voltage was applied so that the droplet volume would be 6.0 pl dots, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed on the substrate so that each would have a thickness of 20 μm.

[0212] (Additional step: a step of curing the first curable composition by light irradiation) After the above (Step 1), a Phoseon Technology LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) was irradiated at 0.1 W / cm 2 , 50 mJ / cm 2 so that the first curable composition applied in a thin film on the copper-clad laminate for printed wiring boards was cured within the extent of maintaining an uncured state without reaching full curing.

[0213] (Step 2) The prepared curable composition 29 was loaded as the second curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied on the uncured first curable composition applied in a thin film on the copper-clad laminate for printed wiring boards in the above (Step 1).

[0214] 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 in the recording head was heated to 45°C. The piezo head had nozzles with a diameter of 22 μm, and the heads with a nozzle resolution of 360 dpi were arranged in a staggered pattern to form a nozzle row with a resolution of 720 dpi.

[0215] Using this inkjet device, a voltage was applied so that the droplet volume became a dot of 6.0 pl, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed on the substrate to a thickness of 20 μm, respectively.

[0216] (Step 3) After the above (Step 2), it was put into an oven set at 150°C for 60 minutes for full curing to obtain a printed sample.

[0217] reference Example 30 The above reference In the (Step 3) of Example 29, except that measures for full curing by light and heat were taken reference It was carried out in the same manner as Example 29. Note that the conditions for light irradiation were reference The same conditions as the light irradiation in the (Step 3) of Example 21 were used.

[0218] reference Example 31 The above reference In the (Step 1) of Example 1, the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to a curable composition 20 that does not contain a heat curing agent but uses an N-oxyl type polymerization inhibitor as a polymerization inhibitor. Other than that, reference A printed sample was obtained in the same manner as Example 1.

[0219] reference Example 32 (Step 1) reference The curable composition 28 prepared in the same manner as Example 1 was loaded as the first curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo type inkjet nozzle. ​​​Using this apparatus, pattern formation was carried out 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 is a recording medium.

[0220] 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 portion. A heater was also built into the piezo head to heat the ink temperature in the recording head to 80°C.

[0221] Using this inkjet apparatus, a voltage was applied so that droplets would form dots with a volume of 6.0 pl, and a solid pattern of 20 mm × 50 mm and a comb-shaped pattern with a line & space of 100 μm were printed onto the substrate to a thickness of 20 μm each.

[0222] (Additional step: a step of curing the first curable composition by light irradiation) After the above (Step 1), an LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) manufactured by Phoseon Technology was irradiated at 0.1 W / cm 2 , 50 mJ / cm 2 so that the first curable composition applied in a thin film form onto the copper-clad laminate for printed wiring boards was cured within the extent of maintaining an uncured state that did not reach full curing.

[0223] (Step 2) The prepared curable composition 35 was loaded as the second curable composition into an inkjet recording apparatus having an inkjet recording head equipped with a piezo-type inkjet nozzle. Using this apparatus, the second curable composition was applied onto the uncured first curable composition applied in a thin film form onto the copper-clad laminate for printed wiring boards in the above (Step 1).

[0224] The ink supply system consists of an ink tank, an ink flow path, and an inkjet head. A heater was also incorporated into the piezo head, and the ink temperature in the recording head was heated to 45°C. The piezo head had nozzles with a diameter of 22 μm, and the heads with a nozzle resolution of 360 dpi were arranged in a staggered pattern to form a nozzle array with a resolution of 720 dpi.

[0225] Using this inkjet device, a voltage was applied so that the droplet volume became a dot of 6.0 pl, and a solid pattern of 20 mm × 50 mm and a comb pattern with a line & space of 100 μm were printed on the substrate to a thickness of 20 μm, respectively.

[0226] (Step 3) After the above (Step 2), an LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) manufactured by Phoseon Technology was irradiated at 2 W / cm 2 to 500 mJ / cm 2 to cure the layer of the curable composition. Thereafter, it was put into an oven set at 150°C for 60 minutes for final curing to obtain a printed sample.

[0227] Reference Examples 33, 34, Example 3 5、36、 37] In the above reference (Step 1) of Example 1, the curable composition loaded into the inkjet recording device as the first curable composition was changed as shown in Table VII. Otherwise, reference a printed sample was obtained in the same manner as in Example 1.

[0228] [Example 38] In the above reference (Step 1) of Example 21, the curable composition loaded into the inkjet recording device as the first curable composition was changed to curable composition 23. Otherwise, reference a printed sample was obtained in the same manner as in Example 21.

[0229] [Example 39] In the above reference ​In Example 1, in step (1), except that the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 26, reference A printed sample was obtained in the same manner as in Example 1.

[0230] [Example 40] The above reference In Example 29, in step (1), except that the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 23, reference A printed sample was obtained in the same manner as in Example 29. Note that after the additional step (light irradiation), the first curable composition applied in a thin film on the copper-clad laminate for printed wiring boards remained in an uncured state without reaching full cure and had adhesiveness (tack) remaining.

[0231] [Example 41] The above reference In Example 30, in step (1), except that the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 23, reference A printed sample was obtained in the same manner as in Example 30. Note that after the additional step (light irradiation), the first curable composition applied in a thin film on the copper-clad laminate for printed wiring boards remained in an uncured state without reaching full cure and had adhesiveness (tack) remaining.

[0232] reference Example 42] The above reference In Example 1, in step (1), the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 27 which does not contain a thermosetting agent but contains a gelling agent. Otherwise, reference A printed sample was obtained in the same manner as in Example 1.

[0233] [Pattern formation by inkjet recording method (Comparative Examples 1 and 2)] [Comparative Example 1] ​In (Step 1) of Example 40, the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 2. Also, in the additional step after the said (Step 1), Phoseon Technology's LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) was irradiated at 2 W / cm 2 to 500 mJ / cm 2 so that the layer of the first curable composition was fully cured, and a printed sample was obtained in the same manner as in Example 40.

[0234] [Comparative Example 2] In (Step 1) of Example 41, the curable composition loaded into the inkjet recording apparatus as the first curable composition was changed to curable composition 21. Also, in the additional step after the said (Step 1), Phoseon Technology's LED lamp FireJet(TM) FJ100 (395 nm, 8 W / cm 2 ) was irradiated at 2 W / cm 2 to 500 mJ / cm 2 so that the layer of the first curable composition was fully cured, and a printed sample was obtained in the same manner as in Example 41.

[0235] [Evaluation] reference example Example example Comparative of the example The curing state of the curable composition in (Step 1) to (Step 3) and the evaluation results after (Step 3) are shown in Tables V to VII. As for the evaluation, evaluation was performed on interlayer adhesion, storage stability, substrate adhesion, pencil hardness, and bleeding. Regarding each evaluation method and criteria, etc., the following methods and criteria were used.

[0236] [Interlayer Adhesion] Regarding the printing sample of the wet pattern of the second curable composition on the first curable composition, the cured film was cut into a grid pattern according to the cross-cut method of JIS K5600, an adhesive tape was attached, and then peeled off to observe the peeling state of the cured film. The adhesion residue rate was determined by the following method and evaluated according to the following criteria. Here, the adhesion residue rate is calculated with the number of squares created by making cuts as the denominator and the number of squares remaining after tape peeling as the numerator.

[0237] (Criteria) ◎: Adhesion residue rate 100% ○: Adhesion residue rate 90% or more and less than 100% △: Adhesion residue rate 70% or more and less than 90% ×: Adhesion residue rate less than 70%

[0238] <Storage stability> Each reference example For the compositions obtained in each of the Examples and Comparative Examples, the viscosity was measured at 80 °C using a rotational viscoelasticity measuring device, and then stored for 1 week under the condition of 85 °C. After storage, the viscosity was re-measured at 80 °C. The difference in viscosity before and after storage (i.e., viscosity fluctuation) was determined, and based on the following criteria, the storage stability was evaluated by the viscosity fluctuation.

[0239] (Criteria) ◎: 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

[0240] <Substrate adhesion> Regarding the printing sample of the wet pattern of the first curable composition, the cured film was cut into a grid pattern according to the cross-cut method of JIS K5600, an adhesive tape was attached, and then peeled off to observe the peeling state of the cured film. The adhesion residue rate was determined by the following method and evaluated according to the following criteria. Here, the adhesion residue rate is calculated with the number of meshes created by making incisions as the denominator and the number of meshes remaining after tape peeling as the numerator.

[0241] (Standard) ◎: Adhesion residue rate 100% ○: Adhesion residue rate 90% or more and less than 100% △: Adhesion residue rate 70% or more and less than 90% ×: Adhesion residue rate less than 70%

[0242] <Pencil hardness> Regarding the printed sample of the wet pattern of the second curable composition on the first curable composition, the surface pencil hardness was measured according to the description method of "JIS standard K-5400". The evaluation was carried out according to the following criteria.

[0243] (Standard) ◎: Pencil hardness 5H ○: Pencil hardness 4H △: Pencil hardness 3H ×: Pencil hardness 2H or less

[0244] <Bleeding> Regarding the evaluation of bleeding, it was carried out according to the following method and criteria. That is, for the printed sample printed under the above conditions, bleeding and granularity were visually confirmed. The presence or absence of bleeding was determined visually according to the following criteria.

[0245] (Standard) ○: Little bleeding and low granularity. ×: Bleeding present and high granularity.

[0246]

Table 1

[0247]

Table 2

[0248]

Table 3

[0249] Reference Examples 1 to 4 Examples 5、 From the comparison in Example 6, it can be seen that using an N-oxyl polymerization inhibitor as the polymerization inhibitor for the second curable composition improves the pencil hardness and so on. That is, reference Examples 1 and 2 and Reference Examples 3, 4 Examples 5、 From the comparison with Example 6, as the second curable composition, by containing any one of an N-oxyl polymerization inhibitor (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Irgastab UV-10), a phenolic polymerization inhibitor containing an o-t-butyl group (2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT)), or a polymerization inhibitor having two or more aromatic rings (naphthoquinone), it can be seen that the interlayer adhesion and pencil hardness are improved. Also, among the above polymerization inhibitors, Examples 5 and 6 in which Curable Compositions 5 and 6 using an N-oxyl polymerization inhibitor are used reference are found to have improved pencil hardness compared to Examples 3 and 4.

[0250] Reference Examples 7 to 12 Examples 13 From the comparison of Examples 1 to 16, it can be seen that using a bisphenol A type epoxy resin or a blocked isocyanate compound as the thermosetting agent for the first curable composition improves the pencil hardness. In particular, it is preferable to use a blocked isocyanate compound.

[0251] That is, reference Examples 7 to reference Examples 11 and Reference Example 12 Example 1 3 to 16 and reference each in Example 32 ratio ofFrom the comparison, it can be seen that using bisphenol A type epoxy resin or blocked isocyanate compound as the heat curing agent of the first curable composition improves the pencil hardness. Also, among the above heat curing agents, Examples 14 to 16 and reference Example 32 in which curable compositions 9, 10, 11 and 28 using a blocked isocyanate compound are used show better substrate adhesion than Example 13.

[0252] Furthermore, reference From the comparison of Examples 7 to 11, it can be seen that using an N-oxyl type polymerization inhibitor as the polymerization inhibitor of the first curable composition improves the interlayer adhesion and storage stability.

[0253] That is, reference From the comparison between Example 7 and reference Examples 8 to 11, it can be seen that by containing any one of an N-oxyl type polymerization inhibitor (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), Irgastab UV-10), a phenolic polymerization inhibitor containing an o-t-butyl group (2,6-di-t-butyl-p-cresol (butylated hydroxytoluene: BHT)), or a polymerization inhibitor having two or more aromatic rings (naphthoquinone) as the first curable composition, the interlayer adhesion and storage stability are improved.

[0254] Also, among the above polymerization inhibitors, Examples 10 and 11 in which curable compositions 5 and 6 using an N-oxyl type polymerization inhibitor are used reference show better interlayer adhesion and storage stability than reference Examples 8 and 9.

[0255] Reference Examples 11, 12 Example 1 3 ~16 and reference From the comparison of Example 32, it can be seen that using a blocked isocyanate compound as the heat curing agent of the first curable composition improves the substrate adhesion.

[0256] That is,reference Examples 11 and 12, and Examples 13 to 16 and reference From the comparison with Example 32, it can be seen that by containing 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, the substrate adhesion is improved.

[0257] reference Example 10 and reference From the comparison with Examples 17 to 20, it can be seen that by containing a polyfunctional polymerizable compound formed using a monomer having an alicyclic structure, a monomer having a trifunctional polymerizable group, a monomer having an aromatic ring, etc. as the first curable composition, the interlayer adhesion and the substrate adhesion are improved.

[0258] reference Examples 12 to 15 Reference Examples 21, 22 Example 2 3、 From the comparison with Examples 24, it can be seen that by curing the first curable composition and the second curable composition by light irradiation after coating and before heat curing, the heat curing can be more surely cured and the pencil hardness is further improved.

[0259] reference From Example 25, it can be seen that the effects of the present invention are exhibited even when the initiator species is changed. reference Example 25 and reference From the comparison with Example 26, it can be seen that the effects of the present invention are exhibited even when the type of the photopolymerization initiator is changed.

[0260] reference From the comparison of Examples 26 to 28, by using a larger amount of the hydrogen abstraction type initiator than the amount of the α-cleavage type initiator, the crosslinking due to the gelation of the coating film is promoted and the substrate adhesion is improved it can be seen .

[0261] That is, referenceThe curable composition used as the first curable composition in Example 26 is 17, the amount of the α-cleavage type initiator of the photopolymerization initiator is 5.0% by mass, and the amount of the hydrogen abstraction type initiator is 3.0%. reference In Example 27, curable composition 18 is used as the first curable composition, the amount of the α-cleavage type initiator of the photopolymerization initiator is 2.0% by mass, and the amount of the hydrogen abstraction type initiator is 3.0%. reference In Example 28, the curable composition used as the first curable composition is 19. Since the amount of the α-cleavage type initiator of the photopolymerization initiator is 0.5% by mass and the amount of the hydrogen abstraction type initiator is 3.0%, by using the hydrogen abstraction type initiator in a proportion more than a certain ratio than the amount of the α-cleavage type initiator, crosslinking due to gelation of the coating film is promoted and the substrate adhesion is improved.

[0262] reference Examples 29 and 30 are examples in which, after the additional step (light irradiation) in both cases, the first curable composition applied in a thin film shape on the copper-clad laminate for printed wiring boards remains in an uncured state without reaching this curing and the tackiness remains. reference The difference between Example 29 and 30 is reference In Example 30, an effect measure by light irradiation is applied in Step 3, and from this, it can be seen that the pencil hardness is reference Example 30 is more improved. Also, reference Examples 29 and 30 use curable composition 5 as the first curable composition in the same manner as these. reference It can be seen that the interlayer adhesion is inferior compared to Example 10.

[0263] Reference Examples 33, 34 Example 3 5 ~41 are examples using the first curable composition containing a gelling agent. From the comparison with the above various reference example and Examples, it can be seen that bleeding is improved, etc.

[0264] reference Examples 31 and 42 are examples using the first curable composition not containing a thermosetting agent. referenceComparison between Examples 20 and 31 and between Example 37 and reference example 42 shows that Examples 31 and 42 without a thermosetting agent reference have no practical problems in terms of overall performance, but Examples 20 and reference 37 with a thermosetting agent example show improved substrate adhesion and pencil hardness compared to reference Examples 31 and reference 42.

[0265] reference Example 32 has poor evaluation of interlayer adhesion and pencil hardness because neither the first curable composition nor the second curable composition contains a polyfunctional polymerizable compound. From this, it can be seen that by containing a polyfunctional polymerizable compound in the first curable composition and the second curable composition, the interlayer adhesion and pencil hardness are improved.

[0266] Comparative Examples 1 and 2 are examples in which, in an additional step after Step 1, under the same conditions as the light irradiation conditions in Step 3, light irradiation is performed to fully cure the layer of the first curable composition. reference Comparison between Example 7 and Comparative Example 1 and reference comparison between Example 33 and Comparative Example 2 show 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.

[0267] In addition, reference considering the evaluation results of Examples 29 and 30 together, it can be seen that the timing of applying the second curable composition is the uncured state when no curing measures have been taken on the first curable composition.

Industrial Applicability

[0268] A recording method capable of improving the adhesion between a plurality of curable compositions and suppressing delamination between layers, and a method for producing a printed matter using the recording method can be provided.

Explanation of Symbols

[0269] P substrate, base material H head HU head unit HU1 head unit 1 HU2 head unit 2 Conveying direction of Q substrate Conveying direction of R head carriage L conveying rail

Claims

1. A recording method using a curable composition, comprising: a step of applying a first curable composition in a thin film form onto a recording medium; a step of applying a second curable composition onto the applied first curable composition; a step of curing the first and second curable compositions at least by heat or light, wherein the second curable composition is applied while the first curable composition is in an uncured state, wherein the first and second curable compositions are at least a thermosetting composition or a photocurable composition, and wherein the first curable composition contains an N - oxyl polymerization inhibitor as a polymerization inhibitor and at least one of an epoxy resin or a blocked isocyanate compound as a thermosetting agent, wherein at least one of the first curable composition and the second curable composition contains a polyfunctional polymerizable compound A recording method characterized by the above.

2. A recording method according to claim 1, further comprising a step of photocuring after the step of applying the second curable composition and before the step of thermally curing the first and second curable compositions. A recording method according to claim 1, characterized by the above.

3. A recording method according to claim 1 or claim 2, wherein the content of the hydrogen abstraction type radical polymerization initiator is higher than that of the α - cleavage type radical polymerization initiator as the photopolymerization initiator contained in the first curable composition. A recording method according to claim 1 or claim 2, characterized by the above.

4. A recording method according to any one of claims 1 to 3, wherein the first curable composition contains a gelling agent. A recording method according to any one of claims 1 to 3, characterized by the above.

5. A recording method according to any one of claims 1 to 4, wherein the recording method using the curable composition is an inkjet recording method. A recording method according to any one of claims 1 to 4, characterized by the above.

6. A method for producing a printed matter, characterized by producing a printed matter using the recording method according to any one of claims 1 to 5.

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