Polymerizable composition, inkjet ink, cured product, and electronic component

Abstract

To provide an ionizing radiation curable polymerizable composition which enables appropriate maintenance of a post-curing shape even after being in a high temperature environment, and which can be dissolved by a water-containing solution.SOLUTION: A polymerizable composition contains (A) a first component comprising a (meth)acryloylmorpholine represented by formula (1) and (B) a second component comprising a compound represented by formula (2), wherein in formula (1), R1 represents hydrogen or methyl, and in formula (2), R2 represents hydrogen or a group having 1-6 carbon atoms, R3 and R4 each independently represent hydrogen or a group having 3 or less carbon atoms, and n represents 1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition that can be suitably used when forming electrodes all at once in response to high-density packaging; an ink comprising such a polymerizable composition; a transfer matrix comprising an ionizing radiation-cured product obtained by irradiating the polymerizable composition with ionizing radiation; and a method for producing an electrode member comprising an electrode group formed on a substrate using the polymerizable composition. [Background technology]

[0002] Patent Document 1 describes a double-layered film that has a lower layer made of a non-radiation-sensitive resin composition and an upper layer made of a negative-tone radiation-sensitive resin composition and is capable of achieving both high resolution and easy peelability, as a technology for simultaneously forming electrodes on multiple semiconductor devices (ICs) formed on a wafer in WL-CSP (wafer level-chip size package), which is a form of high-density packaging, and a method for forming bumps using such a double-layered film. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2007-79550 A Summary of the Invention [Problem to be solved by the invention]

[0004] In the bilayer film described in Patent Document 1, during development, only the irradiated portions of the upper layer remain, while the portions of the lower layer corresponding to the removed portions (non-irradiated portions) of the upper layer are dissolved and removed. Therefore, only the irradiated portions of the bilayer film remain, while the non-irradiated portions of the bilayer film are removed during development. A metal paste is embedded in the removed portions of the bilayer film, and the wafer is heated to reflow the metal paste, forming multiple bumps on the wafer in one batch. After the bumps are formed in one batch, the bilayer film remaining on the wafer is removed using an organic solvent-based stripper such as dimethyl sulfoxide (DMSO).

[0005] In recent years, as packaging density has increased, the shapes of the negative patterns (transfer molds) formed on wafers to form bumps have become more complex (including three-dimensional). However, attempting to form complex negative patterns using the above-mentioned double-layered film process for forming negative patterns makes the process cumbersome. Therefore, there is a need to simplify the manufacturing process. Furthermore, the material that makes up the negative pattern remaining on the wafer must be reliably removed after the bumps are formed. However, growing concern about environmental issues has led to a demand for materials that can be removed with aqueous stripping solutions rather than the organic solvent-based stripping solutions mentioned above.

[0006] Furthermore, recent high-density packaging technologies have adopted fan-out WLP, which forms a redistribution layer over an area larger than the chip surface area, and have even realized stack modules in which these fan-out WLPs are stacked in multiple layers. In such fan-out WLPs, numerous conductive pillars made of copper or other materials are formed in the redistribution layer, and connecting materials such as solder balls are placed on the conductive pillars. Since the placement accuracy of these connecting materials increases with increasing packaging density, there is a demand for more accurate placement of the connecting materials on the conductive pillars.

[0007] The present invention aims to provide an ionizing radiation-curable polymerizable composition that can appropriately maintain its shape after curing even in high-temperature environments such as reflow processes (herein referred to as "heat-resistant"), a property that is required with the advancement of packaging technology. It is also an object of the present invention to provide an ink comprising such a polymerizable composition, a transfer matrix comprising an ionizing radiation-cured product obtained by irradiating the polymerizable composition with ionizing radiation, and a method for producing an electrode member comprising an electrode group on a substrate using the polymerizable composition. In this specification, "ionizing radiation" refers collectively to electromagnetic waves such as gamma rays, X-rays, ultraviolet light, and visible light, as well as energy sources such as electrons, protons, and ions that can generate radicals when irradiated with or colliding with a polymerization initiator. In this specification, "acryloylmorpholine" and "methacryloylmorpholine" or both may be referred to as "(meth)acryloylmorpholine." Terms related to (meth)acryloylmorpholine, such as "(meth)acrylate" and "(meth)acryloxy", have similar meanings. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention is provided as follows. [1] A polymerizable composition comprising (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), and (B) a second component consisting of a compound represented by the following formula (2), wherein the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more. [ka] In formula (1), R 1 is hydrogen or methyl. [ka] In equation (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 20 or less carbon atoms, and n is an integer of 1 to 6.

[0009] [2] The polymerizable composition according to the above [1], wherein n in the compound represented by the formula (2) is 1. [3] In the compound represented by the formula (2), R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms. [4] In the compound represented by the formula (2), R 2 is hydrogen and R 3 and R 4 The polymerizable composition according to the above [3], wherein is methyl.

[0010] [5] The polymerizable composition according to any one of [1] to [4], wherein the total content of the first component and the second component in the solid content of the polymerizable composition is 74% by weight or more. [6] The polymerizable composition according to any one of [1] to [5], wherein the molar ratio of the first component to the second component in the polymerizable composition, expressed as first component / second component, is 1 / 5 to 5 / 1.

[0011] [7] The polymerizable composition according to any one of [1] to [6] above, further comprising (C) a third component consisting of a compound represented by the following formula (3): [ka] In equation (3), R 6 is a group having 25 or less carbon atoms, and R 5 and R 7 are each independently hydrogen or alkyl having 6 or less carbon atoms. [8] In the compound represented by the formula (3), R 6The polymerizable composition according to the above [7], wherein is a group containing oxyalkylene. [9] In the compound represented by the formula (3), R 6 The polymerizable composition according to the above [7], wherein is a group consisting of oxyalkylene.

[0012]

[10] The polymerizable composition according to any one of [1] to [9], further comprising a fourth component consisting of (D) a polymerization initiator, wherein the content of the fourth component in the solid content of the polymerizable composition is 5 to 20 wt %.

[11] The polymerizable composition according to any one of [1] to

[10] above, further comprising (E) an antioxidant, wherein the content of the antioxidant in the solid content of the polymerizable composition is 0.01 to 10 wt %.

[12] The polymerizable composition according to any one of the above [1] to

[11] , which has a viscosity at 25°C of 2 to 30 mPa·s.

[0013]

[13] An inkjet ink comprising the polymerizable composition according to any one of [1] to

[12] above.

[14] A cured product obtained by photocuring the polymerizable composition according to any one of [1] to

[12] above.

[15] An electronic component produced using the cured product described in

[14] above.

[0014]

[16] A method for manufacturing an electrode member in which a plurality of electrodes, each having a recess, are exposed on one side of an insulating substrate in which wiring is embedded, the method comprising: a disposing step of disposing the polymerizable composition according to any one of [1] to

[12] above on a substrate; a curing step of irradiating the polymerizable composition disposed on the substrate with ionizing radiation to cure the polymerizable composition and obtain a transfer matrix made of an ionizing radiation-cured product; a conductive member forming step of forming a conductive member by disposing a conductive material to cover the transfer matrix; a peeling step of peeling a structure including the transfer matrix and the conductive members from the substrate to expose a plurality of the conductive members corresponding to the plurality of electrodes together with the surface of the transfer matrix facing the substrate that is attached to the conductive member; and a dissolving step of dissolving the transfer matrix attached to each of the plurality of conductive members using an aqueous solvent containing poly(oxyethylene) alkyl ether to obtain a plurality of electrodes having the recesses that are the inverse shapes of the transfer matrix.

[0015]

[17] The method for manufacturing an electrode member according to

[16] above, further comprising a heating step of heating the inverted matrix on the substrate after the curing step and before the start of the dissolving step.

[18] The method for producing an electrode member according to

[16] or

[17] above, wherein in the disposing step, the polymerizable composition is supplied to the substrate to dispose a pattern of the polymerizable composition coating on the substrate, and in the curing step, the pattern of the polymerizable composition coating on the substrate is cured to form a pattern of the ionizing radiation-cured product on the substrate as the transfer mold.

[18] The method for producing an electrode member according to

[18] above, wherein the polymerizable composition is an inkjet ink, and in the placing step, an inkjet printer is used to place a pattern of the applied polymerizable composition on the substrate.

[20] The method for producing an electrode member according to

[16] or

[17] above, further comprising a patterning step of forming a layer of the polymerizable composition on the substrate in the disposing step, forming a layer of the ionizing radiation-cured material from the layer of the polymerizable composition in the curing step, and, before starting the conductive member forming step, irradiating a part of the layer of the ionizing radiation-cured material with high-energy rays to remove the ionizing radiation-cured material, thereby forming a pattern of the ionizing radiation-cured material on the substrate as the transfer mold.

[21] A method for manufacturing an electrode member described in any one of

[16] to

[20] above, wherein the conductive member forming step includes forming a pattern of a plurality of electrically independent conductive members on the substrate, further forming wiring electrically connected to each of the patterns of the plurality of conductive members, and arranging an insulating material around the patterns of the plurality of conductive members and the wiring to form the insulating substrate on the substrate, and the structure peeled off from the substrate in the peeling step consists of the transfer mold and the insulating substrate. [Effects of the Invention]

[0016] According to the present invention, there is provided a polymerizable composition that can appropriately maintain its shape after curing even in a high-temperature environment (having heat resistance) and can form an ionizing radiation-cured product that can be dissolved in an aqueous solvent. Also provided according to the present invention are an ink comprising the polymerizable composition, an ionizing radiation-cured product obtained by irradiating the polymerizable composition with ionizing radiation, and a method for producing an electrode member having an electrode group on a substrate using the polymerizable composition. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a flowchart of a manufacturing method according to the present embodiment. [Figure 2] FIG. 1 is a diagram for explaining the steps from the placement step (step S101) to the curing step (step S102). [Figure 3]1A to 1C are diagrams for explaining a placement step (step S101), a curing step (step S102), and a patterning step (step S103). [Figure 4] 10A and 10B are diagrams for explaining a conductive member arranging step (step S104), a peeling step (step S105), and a dissolving step (step S106). DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, methods for producing the polymerizable composition, ink, ionizing radiation-cured product, and electrode member according to the embodiments of the present invention will be described. A polymerizable composition according to one embodiment of the present invention is used to form a transfer mold, and is a polymerizable composition containing (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), and (B) a second component represented by the following formula (2): [ka] In formula (1), R 1 is hydrogen or methyl. [ka] In equation (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms (organic group), and R 3 and R 4 are each independently hydrogen or a group having 20 or less carbon atoms, and n is an integer of 1 to 6.

[0019] By containing the (meth)acryloylmorpholine represented by formula (1) and the compound represented by formula (2), the polymerizable composition can impart appropriate heat resistance to the ionizing radiation-cured product while ensuring curability and solubility of the ionizing radiation-cured product in an aqueous solution.

[0020] When the polymerizable composition is irradiated with ionizing radiation, the polymerization initiator generates radicals, which act as initiators for radical polymerization of the acryloyl groups contained in the polymerizable composition, resulting in a solid component of an ionizing radiation-cured product. When light is used as the ionizing radiation, the polymerizable composition is a photocurable composition.

[0021] By including the first and second components, which are monofunctional compounds, in the polymerizable composition, it is possible to ensure photocurability and heat resistance, as well as solubility of the ionizing radiation-cured product in an aqueous solvent.

[0022] By ensuring that the total content of the first component and the second component (hereinafter also referred to as the "total content") in the solid content of the polymerizable composition (the components contained in the polymerizable composition that constitute the ionizing radiation-cured product) is 50% by weight or more, it is possible to improve the curability, heat resistance of the ionizing radiation-cured product, and solubility in an aqueous solvent. From the viewpoint of achieving a good balance of curability, heat resistance, and solubility, the total content is more preferably 74% by weight or more, and even more preferably 80% by weight or more. Furthermore, from the viewpoint of improving photocurability, the total content is preferably 96% by weight or less, and more preferably 94% by weight or less. The content of the first component in the solid content of the polymerizable composition is preferably 25 to 75% by weight, and the content of the second component is preferably 15 to 65% by weight.

[0023] In the polymerizable composition, the molar ratio of the first component to the second component (first component / second component) is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1, from the viewpoint of realizing an ionizing radiation-cured product that has curability, heat resistance, and solubility in an aqueous solvent.

[0024] From the viewpoint of more stably ensuring the solubility of the ionizing radiation-cured product in the aqueous solution, the second component is preferably a compound in which n in formula (2) is 1, and 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and in formula (2), R 2 is hydrogen and R3 and R 4 More preferred are compounds where is methyl.

[0025] Specific examples of preferred second components include N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylmethacrylamide, N-methylmethacrylamide, and N-methylacrylamide. N,N-dimethylacrylamide is particularly preferred because it dissolves in an aqueous solution (aqueous stripping solution) containing a non-volatile water-soluble compound that is not a so-called volatile organic compound (VOC). By configuring the aqueous solution to be free of volatile organic compounds, the burden on the environment can be further reduced.

[0026] From the viewpoint of increasing the residual film rate of the ionizing radiation-cured product after a high-temperature process, the polymerizable composition preferably further contains a third component consisting of a compound represented by formula (3). [ka] In equation (3), R 6 is a group having 25 or less carbon atoms, and R 5 and R 7 are each independently hydrogen or alkyl having 6 or less carbon atoms.

[0027] The residual film ratio is defined as (thickness after heat treatment) / (thickness before heat treatment) before and after the ionizing radiation-cured product according to this embodiment is heated in the atmosphere (for example, at 200°C for 2 hours, at 230°C for 2 hours, etc.). By increasing the residual film ratio, the shape of the pattern is less likely to change, even when a metal such as copper is formed directly on a pattern made of the ionizing radiation-cured product by a dry process such as vapor deposition or sputtering.

[0028] Specific examples of the third component consisting of the compound represented by formula (3) include bisphenol F ethylene oxide-modified diacrylate (available as "Aronix M-208" manufactured by Toagosei Co., Ltd.), bisphenol A ethylene oxide-modified diacrylate (available as "Aronix M-211B" manufactured by Toagosei Co., Ltd.), PEG200# diacrylate (available as "Light Acrylate 4EG-A" manufactured by Kyoeisha Chemical Co., Ltd.), tripropylene glycol diacrylate (available as "Viscoat #310HP" manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 1,6-hexanediol diacrylate (available as "Light Acrylate 1,6-HXA" manufactured by Kyoeisha Chemical Co., Ltd.). Among these, from the viewpoint of solubility of the ionizing radiation-cured product in a water-containing solution, the R 6 is a group containing oxyalkylene (alkylene oxide), bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, PEG200# diacrylate, and tripropylene glycol diacrylate are preferred. Furthermore, since the solubility can be further increased, R 6 is a group consisting of oxyalkylene, PEG200# diacrylate and tripropylene glycol diacrylate are preferred.

[0029] In the polymerizable composition, a bifunctional acrylate compound having, for example, an aliphatic polycyclic structure rather than a bisphenol structure can be used in place of the third component, which is a monomer of a bifunctional acrylate compound, as long as the solubility of the ionizing radiation-cured product in an aqueous solution is not impaired.

[0030] When the polymerizable composition contains a third component, from the viewpoints of maintaining the residual film rate of the ionizing radiation-cured product after a high-temperature process and of solubility of the ionizing radiation-cured product in an aqueous solution, the content of the third component in the solid content is preferably from 5 to 35% by weight, more preferably from 8 to 33% by weight, and particularly preferably from 10 to 30% by weight. Furthermore, the molar ratio of the third component to the total of the first and second components, expressed as third component / (total of the first and second components), is preferably 1 / 20 to 1 / 2, more preferably 1 / 15 to 1 / 3, and even more preferably 1 / 10 to 1 / 5.

[0031] The polymerizable composition of the present invention may contain compounds other than those described above, as long as the heat resistance and solubility of the ionizing radiation-cured product can be appropriately ensured. Examples of acrylic compounds that can be considered as optional additives include monofunctional acrylic compounds having an aliphatic polycyclic structure such as a norbornene skeleton or a dicyclopentadiene skeleton (in this specification, these acrylic compounds are referred to as "aliphatic polycyclic monoacrylic compounds"). When the polymerizable composition contains an aliphatic polycyclic monoacrylic compound, the glass transition temperature of the ionizing radiation-cured product formed from the polymerizable composition may be increased.

[0032] Specific examples of such aliphatic polycyclic monoacrylic compounds include dicyclopentanyl methacrylate (available as "FA-513M" manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl acrylate (available as "FA-513AS" manufactured by Hitachi Chemical Co., Ltd.), isobornyl acrylate (available as "Light Ester IB-XA" manufactured by Kyoeisha Chemical Co., Ltd.), and isobornyl methacrylate (available as "Light Ester IB-X" manufactured by Kyoeisha Chemical Co., Ltd.) When the polymerizable composition contains an aliphatic polycyclic monoacrylic compound, its content is preferably 20% by weight or less, and more preferably 15% by weight or less, of the solid content of the polymerizable composition, from the viewpoint of appropriately ensuring the heat resistance and solubility of the ionizing radiation-cured product.

[0033] The polymerizable composition of the present invention may further contain a fourth component (D) consisting of a polymerization initiator. The type of polymerization initiator is not limited as long as it is capable of generating radicals upon irradiation with ionizing radiation and is capable of initiating the polymerization reaction between the first and second components.

[0034] The content of the polymerization initiator in the solid content of the polymerizable composition is preferably 5% by weight or more from the viewpoint of solubility of the ionizing radiation-cured product, and preferably 20% by weight or less from the viewpoint of heat resistance. From the viewpoint of obtaining an ionizing radiation-cured product having a good balance between solubility and heat resistance, the content is more preferably 8% by weight or more and 15% by weight or less.

[0035] Specific examples of the polymerization initiator include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2, 2-Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1'-(methylene-di-4,1-phenylene)bis(2-hydroxy-2-methyl-1-propanone), camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one )-Butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s -triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-Bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4 ,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(ter tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(tert-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(tert-butylperoxycarbonyl)benzophenone, etc. These compounds may be used alone, or a mixture of two or more of them is also effective. Commercially available products include, for example, BASF's product names: Irgacure 379EG, Irgacure 127, Irgacure 184, and IGM Resins B.V.'s product names: Omnirad 379EG, Omnirad 127, Omnirad 184. Among these, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferred.

[0036] The polymerizable composition according to this embodiment may be substantially free of a volatile solvent to simplify the process of forming an ionizing radiation-cured product. However, it may contain a volatile solvent to adjust the viscosity of the polymerizable composition. The volatile solvent may be mixed with other components during use to form the polymerizable composition. When the polymerizable composition contains a volatile solvent, the volatilization may begin while the polymerizable composition is still uncured. Preferably, the volatilization occurs at least by the time an ionizing radiation-cured product is formed by appropriate heating before, during, and / or after irradiation with ionizing radiation. If excessive unvolatilized solvent remains even after the polymerizable composition has been cured to a certain extent, the final cured product (ionizing radiation-cured product) may have a porous structure, which may reduce the surface properties (surface smoothness) required for a reversal matrix (negative pattern) for reversal transfer. Therefore, the volatile solvent content is preferably 30 wt % or less of the total polymerizable composition.

[0037] Specific examples of volatile solvents include methanol, ethanol, propanol, butanol, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-oxypropionate, Methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, Propyl 2-hydroxypropionate, Methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, Methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetoacetate Ingredients: ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, methyl 2-hydroxyisobutyrate, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, benzyl alcohol, cyclohexanol, 1,Examples of suitable solvents include 4-butanediol, triethylene glycol, tripropylene glycol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, anisole, γ-butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylimidazolidinone. These compounds may be used alone, or a mixture of two or more of them may be used.

[0038] The polymerizable composition according to this embodiment may contain additives other than those described above. Specific examples of the additives include surfactants, polymerization inhibitors, plasticizers, antioxidants, UV absorbers, antistatic agents, flame retardants, flame retardant aids, fillers, pigments, and dyes. However, the additives are not particularly limited as long as they can be uniformly mixed with the other components within the scope of the present invention. Specific examples of surfactants include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (trade names, all manufactured by Kyoeisha Chemical Co., Ltd.); Disperbake 161, Disperbake 162, Disperbake 163, Disperbake 164, Disperbake 166, Disperbake 170, Disperbake 180, Disperbake 181, Disperbake 182, BYK300, BYK306, and BYK 310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade names, all manufactured by BYK Japan Co., Ltd.); KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (trade names, all manufactured by Shin-Etsu Chemical Co., Ltd.); Surflon SC-101, Surflon KH-40 (trade names, all manufactured by Seimi Chemical Co., Ltd.); Ftergent 222F, Ftergent 251, FTX-218 (trade names, all manufactured by Neos Co., Ltd.); TEGO Rad2100, 2200N, 2250, 2500, 2600, 2700 (trade names, all manufactured by Evonik Degussa); EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade names, all manufactured by Mitsubishi Materials Corporation); Megafac F-171, Megafac F-177, Megafac F-444, Megafac F-475, Megafac F-477, Megafac F-556, Megafac R-08, Megafac R-30 (trade names, all manufactured by DIC Corporation);Fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, perfluoroalkylethylene oxide adduct, diglycerin tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxy Ethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, and alkyl diphenyl ether disulfonates may be mentioned;

[0039] Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, and phenothiazine.

[0040] Preferable antioxidants include hindered phenol-based antioxidants, phosphorus-based processing heat stabilizers, metal deactivators, sulfur-based heat stabilizers, hydroquinone derivatives, etc. Specific examples include Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF (W&C), Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259, Irganox 3114, and Irganox 565 (trade names, all manufactured by BASF); Nocrac 200 and Nocrac NS-6 (trade names, all manufactured by BASF); Examples of suitable acrylic acid esters include those manufactured by Ouchi Shinko Chemical Industry Co., Ltd.; Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-60, Adeka Stab AO-80, Adeka Stab AO-330, Adeka Stab HP-10, and Adeka Arcles GPA5001 (trade names, all manufactured by ADEKA Corporation); KEMINOX101 (trade name, manufactured by Chemipro Chemical Co., Ltd.); Cyanox CY-1790 (trade name, manufactured by Sun Chemical Co., Ltd.); Antiox 10 (trade name, manufactured by NOF Corporation); dibutylhydroxytoluene, and 4-methoxyphenol. Among these, Irganox 1330 (melting point: 240 to 245°C), which has a high melting point and low volatility, is particularly preferred.

[0041] From the viewpoint of improving the solubility of the cured polymerizable composition, the content of the antioxidant is preferably 0.01 to 10 wt %, more preferably 0.1 to 5 wt %, and even more preferably 0.4 to 2 wt %, based on the solid content of the polymerizable composition.

[0042] When used, the polymerizable composition according to this embodiment is applied to a substrate by coating, dripping, or the like, and thereby forms a film or a predetermined pattern on the substrate. From the viewpoint of facilitating application of the polymerizable composition to the substrate, the viscosity of the polymerizable composition according to this embodiment at 25°C may preferably be 2 to 30 mPa·s. In particular, when the polymerizable composition is applied to the substrate using an inkjet printer, it is preferable that the viscosity be within the above range. Furthermore, the viscosity of the inkjet ink made from the polymerizable composition according to this embodiment at the discharge temperature (e.g., 25°C) is preferably 25 mPa·s or less, and particularly preferably 10 mPa·s or less. The viscosity of the polymerizable composition can be reduced by heating.

[0043] The polymerizable composition according to this embodiment is cured by irradiation with ionizing radiation to form an ionizing radiation-cured product. Such an ionizing radiation-cured product remains soluble in an aqueous solvent even after being heated in the atmosphere at 200°C for 2 hours. Specifically, the ionizing radiation-cured product after the heat treatment (200°C for 2 hours) is dissolved by immersion in an aqueous solvent for 15 hours or less, and in a preferred embodiment, for 30 minutes or less.

[0044] The aqueous solution is a solution containing water, and may consist of water, but is preferably a mixed solvent with a water-soluble compound that is highly soluble in water. Any water-soluble compound can be used as long as it has a boiling point of 70°C or higher, but from the viewpoint of ease of handling, it is preferable to contain a compound with a boiling point of 150°C or higher, and from the viewpoint of VOCs, it is even more preferable to contain a compound with a boiling point of 260°C or higher.

[0045] Examples of water-soluble compounds with high solubility in water include protic polar solvents such as alcohols and compounds containing an oxyethylene group, such as poly(oxyethylene) alkyl ethers, from the viewpoint of improving the homogeneity of the mixed solution. From the viewpoints of safety and reducing the environmental load, non-volatile poly(oxyethylene) alkyl ethers are more preferred. The water content in the aqueous solution is appropriately set depending on the types of components other than water contained in the aqueous solution and the composition of the ionizing radiation-cured product.

[0046] When the aqueous solution is a mixture of water and poly(oxyethylene) alkyl ether, the poly(oxyethylene) alkyl ether (H 2m+1 C m -O-(CH2-CH2-O) n In -H), the number of moles n of ethylene oxide added is not particularly limited, but is preferably 2 to 35, more preferably 15 to 30, and even more preferably 20 to 25. The alkyl chain length m is preferably 4 to 15, and more preferably 12 to 13.

[0047] Examples of poly(oxyethylene) alkyl ethers include diethylene glycol butyl ether (CAS No. 112-34-5) with an added mole number of ethylene oxide, n = 2, triethylene glycol monododecyl ether (CAS No. 3055-94-5) with an added mole number of ethylene oxide, n = 3, and polyoxyethylene (23) lauryl ether (CAS No. 9002-92-0) with an added mole number of ethylene oxide, n = 23. From the viewpoints of safety and reducing the environmental load, it is preferable to use polyoxyethylene (23) lauryl ether as the poly(oxyethylene) alkyl ether, and its content in the aqueous solution is preferably 10% by weight or more and 90% by weight or less, more preferably 30% by weight or more and 80% by weight or less, and particularly preferably 50% by weight or more and 70% by weight or less.

[0048] When the aqueous solution is a water-alcohol mixture, which is a mixture of water and alcohol, and the alcohol contained in the water-alcohol mixture is a substance having four or fewer carbon atoms, such as ethanol or isopropanol, the alcohol content is preferably 25% by weight or more and 90% by weight or less, more preferably 40% by weight or more and 80% by weight or less, and particularly preferably 45% by weight or more and 75% by weight or less.

[0049] The aqueous solution may contain an organic solvent other than alcohol. Examples of such organic solvents include aprotic organic solvents such as N-methylpyrrolidone, acetone, acetonitrile, and dimethyl sulfoxide. From the viewpoint of reducing the environmental load, the content of the organic solvent other than alcohol in the aqueous solution is preferably 20% by weight or less of the total aqueous solution.

[0050] It may be preferable that the aqueous solution is alkaline, i.e., an alkaline solution. Examples of substances that can make the aqueous solution alkaline include inorganic alkaline substances such as sodium hydroxide and potassium hydroxide, and organic alkaline substances such as tetramethylammonium hydroxide. Note that a typical alkaline solution has a pH of 9 or higher, and it may be preferable that the aqueous solution also have a pH of 9 or higher, and more preferably 10 or higher. From the viewpoint of achieving such a pH, it may be preferable that the content of the alkaline substance in the aqueous solution be 5% by weight or more and 20% by weight or less.

[0051] Hereinafter, we will explain a manufacturing method of an electrode member in which multiple electrodes, each with a recess, are exposed on one surface of an insulating substrate with embedded wiring, which can also be used as a redistribution line (RDL) for fan-out WLP, etc. The material constituting the electrodes includes, for example, copper (Cu), and the material constituting the insulating substrate includes, for example, polyimide.

[0052] 1 is a flowchart of a manufacturing method according to this embodiment. As shown in FIG. 1, this manufacturing method includes, as essential steps, a placement step (step S101), a curing step (step S102), a conductive member formation step (step S104), a peeling step (step S105), and a dissolving step (step S106). If necessary, this manufacturing method may include a patterning step (step S103) between the curing step (step S102) and the conductive member placement step (step S104), or may further include a heating step (step S107) after the curing step (step S102) and before the start of the dissolving step (step S106).

[0053] FIG. 2 is a diagram for explaining the steps from the placement step (step S101) to the curing step (step S102) included in an example of the manufacturing method according to this embodiment. In the disposing step (step S101), the polymerizable composition 10 is disposed on one main surface of a plate- or sheet-shaped substrate SB (FIG. 2(a)), such as a glass substrate or a silicon substrate, which will eventually be peeled off. The method for disposing the polymerizable composition 10 is not limited. FIG. 2 shows an example in which a pattern 11 of a coating of the polymerizable composition is formed on the substrate SB using various known disposing means, such as a screen printer PS (left side), an offset printer PR (center) using a transfer roll, or an inkjet printer PJ (right side), as shown in FIG. 2(b).

[0054] In the curing step, the pattern 11 of the polymerizable composition coating placed on the substrate SB is irradiated with ionizing radiation LR (FIG. 2(c)), curing the pattern 11 of the polymerizable composition coating, and obtaining a pattern 20 of the ionizing radiation-cured product on the substrate SB as a transfer matrix (FIG. 2(d)). The type of ionizing radiation LR is not particularly limited, and examples include visible light, ultraviolet light, X-rays, gamma rays, electron beams, and ion beams. The irradiation device LS is appropriately configured depending on the type of ionizing radiation LR. Specific examples include LEDs, halogen lamps, radiation irradiation devices, electron beam irradiation devices, and ion beam generators. From the standpoint of availability and ease of handling, UV-LEDs and halogen lamps with emission peaks at approximately 350 nm to 400 nm are preferably used.

[0055] FIG. 3 is a diagram for explaining the placement step (step S101), the curing step (step S102), and the patterning step (step S103) included in another example of the manufacturing method according to this embodiment.

[0056] In the disposing step (step S101), a layer 12 of a polymerizable composition is formed on one main surface of the substrate SB (FIG. 3(a)), as shown in FIG. 3(b). Examples of methods for forming this layer 12 of the polymerizable composition include spin coating, dipping, and spray coating. Thereafter, a curing step (step S102) is carried out, and as shown in FIG. 3(c), a layer 21 of an ionizing radiation-cured material is formed on one main surface of the substrate SB.

[0057] Thereafter, a part of the layer 21 of the ionizing radiation-cured material is irradiated with high-energy rays PE (specifically, a laser or an ion beam is exemplified) to remove unnecessary ionizing radiation-cured material 12d. In this way, a patterning step (step S103) is performed to form a transfer matrix consisting of the pattern 20 of the ionizing radiation-cured material on the substrate SB.

[0058] FIG. 4 is a diagram for explaining the conductive member arranging step (step S104), the peeling step (step S105), and the dissolving step (step S106) included in the example of the manufacturing method according to this embodiment.

[0059] 2 or 3, a structure having a pattern 20 of ionizing radiation-cured material formed on the substrate SB is obtained, and then a conductive member forming step (step S104) is carried out in which a conductive material is disposed so as to cover the pattern 20 of the ionizing radiation-cured material on the substrate SB, thereby forming a conductive member film 30. Figure 4(a) shows, as a specific example of the conductive member forming step (step S104), a case in which a conductive material is disposed uniformly on one main surface of the substrate SB to form a film-like conductive member film 30.

[0060] While the type of conductive material is not particularly limited, it is preferable that the conductive member film 30 be water-impermeable and function as a protective layer for the ionizing radiation-cured pattern 20, as this increases the flexibility of subsequent process settings. From this perspective, examples of conductive materials include metal-based materials such as copper (Cu) and aluminum (Al), inorganic oxide-based materials such as indium tin oxide (ITO) and zinc oxide (ZnO), and conductive materials in which conductive nanowires are dispersed in a resin. The manufacturing method of the conductive member film 30 is appropriately determined depending on the type of conductive material. When the conductive material is a metal-based material such as copper (Cu), examples include a method of forming the entire conductive member film 30 by a dry process such as vapor deposition or sputtering, and a method of forming a thin layer of conductive material on the substrate SB so as to cover the ionizing radiation-cured pattern 20 by a dry process such as vapor deposition or sputtering, and then depositing the conductive material by a wet process such as plating to form the conductive member film 30 on the substrate SB.

[0061] When depositing a conductive material by a dry process, the conductive material moving toward the substrate SB may be at a high temperature or have high kinetic energy. In this case, the substrate SB is heated, and as a result, the pattern 20 of the ionizing radiation-cured material on the substrate SB may also become hot. In such a case, the heating step (step S107) is essentially carried out in the conductive member forming step (step S104). Even when the heating step (step S107) is essentially carried out in this way, as described above, the pattern 20 of the ionizing radiation-cured material can be appropriately dissolved in the subsequent dissolving step using an aqueous dissolving liquid containing poly(oxyethylene) alkyl ether, and there is little change in shape due to heat.

[0062] Once the conductive material film 30 has been formed on the substrate SB in this way, high-energy rays such as a laser are irradiated to remove portions of the conductive material film 30, thereby obtaining conductive material patterns 31 formed so as to individually cover the ionizing radiation-cured material patterns 20 (FIG. 4(b)). The high-energy rays irradiated in this process may heat the substrate SB or the conductive material patterns 31. Even in such cases, the conductive material formation step (step S104) may actually involve the heating step (step S107). As described above, even if heat is transmitted to the ionizing radiation-cured material pattern 20, it is possible for the ionizing radiation-cured material pattern 20 to maintain its solubility in an aqueous solvent appropriately, and it is unlikely to change shape.

[0063] 4(a) and 4(b), the conductive member pattern 31 is formed after the conductive member film 30 is formed in the conductive member formation step (step S104), but this is not limitative. The conductive member pattern 31 may be formed directly by using an appropriate mask material, for example.

[0064] Next, to facilitate stacking of additional components on the conductive member pattern 31 provided on the substrate SB, an insulating material 40 such as polyimide is disposed around the conductive member pattern 31 on the substrate SB, as shown in FIG. 4(c). The specific method for this process is arbitrary. For example, the insulating material 40 may be applied by spin coating or the like, and then disposed by photolithography (including curing) that involves a heat treatment. In this case, the heat treatment also heats the ionizing radiation-cured material pattern 20 covered by the conductive member pattern 31 that contacts the insulating material 40. Therefore, this heat treatment corresponds to the heating step (step S107) performed before the peeling step (step S105) described next is started. As described above, the ionizing radiation-cured material according to this embodiment is unlikely to lose its solubility in a water-containing solvent even when heated, and is unlikely to undergo shape changes due to heating, so the heating step (step S107) in which such a heat treatment is performed can be carried out.

[0065] After the insulating material 40 is appropriately arranged around the conductive member pattern 31 in this way, lamination and patterning of the conductive material (lamination may be performed while patterning) is further performed to form the wiring member 32 on the conductive member pattern 31, and the insulating material 41, such as polyimide, is arranged around the wiring member 32 (FIG. 4(d)). A plurality of layers each consisting of the wiring member 32 and the insulating material 41 may be provided. Even if the process of forming the layer each consisting of the wiring member 32 and the insulating material 41 includes a heat treatment and essentially involves the heating step (step S107), the ionizing radiation-cured material maintains its appropriate solubility in a water-containing solvent and is unlikely to change shape due to heating, as described above. In this way, a structure 200 is arranged on the substrate SB, the structure 200 including the ionizing radiation-cured material pattern 20 constituting the transfer matrix, the insulating substrate 50 including the conductive member pattern 31 constituting the electrode, the wiring member 32 constituting the wiring, and the insulating portion 42 composed of the insulating materials 40 and 41.

[0066] The resulting structure 200 is inverted, and the substrate SB is positioned on top of the structure 200 ( FIG. 4( e) ). The substrate SB is then peeled off. At this time, the pattern 20 of the ionizing radiation-cured material remains attached to the pattern 31 of the conductive material; that is, the transfer matrix is ​​attached to each of the multiple conductive materials. Therefore, in the structure 200, the surface 20S of the pattern 20 of the ionizing radiation-cured material facing the substrate SB (the surface that was positioned facing the substrate SB) is exposed ( FIG. 4( f) ). The pattern 20 of the ionizing radiation-cured material, including this exposed surface 20S, is brought into contact with an aqueous dissolving solution, whereby the pattern 20 of the ionizing radiation-cured material can be dissolved and removed. As a result, as shown in FIG. 4( g ), the pattern 31 of the conductive material, which has a surface with a recess 31R that is the inverse shape of the pattern 20 of the ionizing radiation-cured material, is exposed, and each of these patterns 31 of the conductive material becomes an electrode of the electrode member. In this way, an electrode member 100 is obtained in which a plurality of electrodes (conductive member patterns 31) each having a recess 31R are exposed on one surface of the insulating substrate 50 in which the wiring (wiring member 32) is embedded.

[0067] When the exposed portion of the electrode has the recess 31R, the recess 31R functions as a receiving portion for the solder ball when the electrode member is used as a rewiring, improving the stability of the placed solder ball. This allows for a higher electrode arrangement density in the rewiring, and thus allows for an improved packaging density.

[0068] By the above manufacturing method, an electrode member can be manufactured in which the individual conductive members constituting the conductive member pattern 31 become electrodes, and the electrodes and wiring electrically connected to the electrodes are embedded in a support member (made of insulating material 40 and insulating material 41).

[0069] Although the present invention has been described with reference to the above-mentioned embodiment, the present invention is not limited to the above-mentioned embodiment, and improvements or modifications can be made within the scope of the invention or the spirit of the invention. [Example]

[0070] The present invention will be explained in more detail below with reference to examples, but the scope of the present invention is not limited to these examples. The following materials were prepared: (A) First component: (meth)acryloylmorpholine ACMO (CAS No. 5117-12-4) Acryloylmorpholine (Tg: 145°C)

[0071] (B) Second component DMAA (CAS No. 2680-03-7) N,N-dimethylacrylamide (Tg: 119°C) DEAA (CAS No. 2675-94-7) N,N-diethylacrylamide (Tg: 81°C) NIPA (CAS No. 2210-25-5) Isopropylacrylamide (Tg: 150°C)

[0072] (C) Third component 4EG-A (CAS No. 26570-48-9) PEG#200 diacrylate (Tg: 40°C) M208 (CAS No. 120750-67-6) Bisphenol F EO modified diacrylate (Tg: 75°C)

[0073] (other compounds) NVC (CAS No. 2235-00-9) N-vinyl-ε-caprolactam (Tg: 145°C) 4HBA (CAS No. 2478-10-6) 4-hydroxybutyl acrylate (Tg: -40°C)

[0074] (D) Fourth component: Polymerization initiator Irg379EG: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (BASF, "IRGACURE 379EG") (E) Antioxidants Irganox 1330 (BASF) (surfactant) BYK342 (BYK Japan)

[0075] (Examples 1 to 15 and Comparative Examples 1 to 6) Polymerizable compositions were prepared by blending various materials as shown in Tables 1 to 4. The values ​​in each table are in parts by weight.

[0076] [Table 1]

[0077] [Table 2]

[0078] [Table 3]

[0079] [Table 4]

[0080] The solid content (solid content concentration) of each component contained in the polymerizable compositions according to the examples and comparative examples and the evaluation results are shown in Tables 5 to 8. In Tables 5 to 8, for ease of comparison, the total content of the first component (A) and the second component (B) in the solid content of the polymerizable composition is shown in the (A) + (B) column, the molar ratio of each component is shown in the (A / B / C / other) column, the first component / second component (molar ratio) is shown in the (A / B) column, and the third component / (total of the first and second components) (molar ratio) is shown in the (C / (A+B)) column. In Tables 5 to 8, % means % by weight.

[0081] [Table 5]

[0082] [Table 6]

[0083] [Table 7]

[0084] [Table 8]

[0085] (Evaluation Example 1) Viscosity measurement The viscosity of each of the polymerizable compositions according to the Examples and Comparative Examples was measured at room temperature (25° C.). The measurement results are shown in Tables 5 to 8.

[0086] (Evaluation Example 2) Evaluation of photocurability For each of the polymerizable compositions according to the Examples and Comparative Examples, a coating film was obtained using a bar coater under the following conditions: The exposure dose was varied and the minimum exposure dose required for the coating film to become tackless was measured. Substrate: Aluminum foil Bar coater: #42 (target film thickness 70-80μm) The resulting coating of the polymerizable composition was cured under the following conditions to obtain an ionizing radiation-cured product. UV irradiation device: Asumi Giken "ASM1503NM-UV-LED" Lamp wavelength: 365nm The photocurability of the polymerizable composition was evaluated according to the following criteria based on the amount of exposure required for curing the coating film. ○: Exposure amount 100mJ / cm 2 It hardened in less than 100°C. △: Exposure amount 100mJ / cm 2 More than 500mJ / cm 2 It hardened in less than 100°C. ×: Exposure amount 500 mJ / cm 2 More than 2000mJ / cm 2 It hardened in less than 100°C. ××: exposure dose 2000 mJ / cm 2 It hardened as above.

[0087] (Evaluation Example 3) Evaluation of heat resistance (measurement of glass transition temperature (Tg)) For each of the polymerizable compositions according to the Examples and Comparative Examples, a coating film was obtained using a bar coater under the following conditions. Substrate: Aluminum foil Bar coater: #42 (target film thickness 70-80μm) The resulting coating of the polymerizable composition was cured under the following conditions to obtain an ionizing radiation-cured product. UV irradiation device: Asumi Giken "ASM1503NM-UV-LED" Lamp wavelength: 365nm Exposure dose: 1000mJ / cm 2 Illuminance: 700mW / cm 2 For measuring UV light, a UV monitor ("UV-Pad" manufactured by Opsytec) that measures UVA (315 to 400 nm) was used.

[0088] The glass transition temperature (Tg) of the obtained ionizing radiation-cured product was measured by dynamic viscoelasticity measurement (DMA method) under the following conditions. Measurement device: DMS6000 (Hitachi High-Tech Science Corporation) Frequency mode: Sine wave Frequency: 10kHz Heating rate: 10°C / min The heat resistance of the polymerizable composition was evaluated based on the measured glass transition temperature according to the following criteria. ◎: Glass transition temperature 150℃ or higher ○: Glass transition temperature 120℃ or higher, less than 150℃ △: Glass transition point 100℃ or higher, less than 120℃ ×: Glass transition temperature 50℃ or higher, less than 100℃ ××: Glass transition temperature below 50°C

[0089] (Evaluation Example 4-1) Evaluation of solubility Each of the polymerizable compositions according to the Examples and Comparative Examples was applied to a silicon substrate (silicon wafer) and cured under the same conditions as in Evaluation Example 2 to obtain an ionizing radiation-cured product. The obtained ionizing radiation-cured product was then subjected to a heat treatment under the following conditions. Clean oven: Yamato Scientific "DT610" Temperature: 200℃ Cooking time: 2 hours Next, two aqueous dissolving solutions were prepared: (A) an alkaline solution (KOH / water / POE ether solution) consisting of a mixture of potassium hydroxide (KOH), water, and polyoxyethylene (23) lauryl ether (POE ether) (mixing weight ratio: KOH / water / POE ether = 5 / 35 / 60), and (B) an alkaline solution (KOH / water / EtOH solution) consisting of a mixture of potassium hydroxide (KOH), water, and ethanol (EtOH) (mixing weight ratio: KOH / water / EtOH = 5 / 35 / 60). The ionizing radiation-cured product after heat treatment was immersed in the KOH / water / POE ether solution at 70°C, and the KOH / water / EtOH solution at 25°C, and the state of dissolution of the ionizing radiation-cured product was observed. The evaluation criteria were as follows. The evaluation results are shown in Tables 5 to 8. ◎: Dissolved within 30 minutes. ○: Dissolved between 30 minutes and 3 hours. △: Dissolved between 3 hours and 15 hours. ×: Not dissolved even after 15 hours.

[0090] (Evaluation Example 4-2) Evaluation of solubility The dissolution state of the ionizing radiation-cured product was observed in the same manner as in Evaluation Example 4-1, except that the conditions for heat-treating the obtained ionizing radiation-cured product were changed to the following conditions and only a KOH / water / POE ether solution was prepared as the aqueous dissolving liquid into which the heat-treated ionizing radiation-cured product was immersed. Clean oven: Yamato Scientific "DT610" Temperature: 230℃ Cooking time: 2 hours

[0091] As shown in Tables 5 to 8, the polymerizable compositions according to the examples had a viscosity of 10 mP·s or less at room temperature, making them suitable for use as inkjet inks. In addition, all of the compositions had good photocurability. The glass transition temperature (Tg) of the ionizing radiation-cured product formed from the polymerizable composition according to the example was 120°C or higher, and it was confirmed that the glass transition temperature (Tg) of the obtained ionizing radiation-cured product was high. The ionizing radiation-cured products formed from the polymerizable compositions of the Examples had good solubility in a KOH / water / EtOH solution even after heat treatment. Examples 1 to 3, 6 to 8, and 10 to 15 were soluble in a KOH / water / POE ether solution as well as a KOH / water / EtOH solution, and exhibited good photocurability and heat resistance.

[0092] In contrast, the ionizing radiation-cured products formed from the polymerizable compositions of Comparative Examples 1 to 6 tended to have reduced solubility in a KOH / water / EtOH solution after heat treatment. Comparative Examples 2 and 5 were soluble in a KOH / water / POE ether solution, but both or either of the photocurability and heat resistance were rated x or △. From the results of Examples 2, 10 and 11 to 13, it can be said that the content of the polymerization initiator is preferably 5% by weight or more from the viewpoint of photocurability, and is preferably 20% by weight or less from the viewpoint of heat resistance. From the comparison between Examples 6 and 8 and Comparative Example 5, it can be said that, from the viewpoint of obtaining a polymerizable composition excellent in photocurability, heat resistance, and solubility, the total content of (A) and (B) in the solid content of the polymerizable composition is preferably 50% by weight or more, and more preferably 70% by weight or more.

[0093] The polymerizable compositions of Example 6, which did not contain an (E) antioxidant, and Examples 14 and 15, which contained an (E) antioxidant, showed dissolution times of 4 hours, 1 hour, and 0.25 hours in a KOH / water / POE ether solution (70°C) when cured at 200°C, respectively; and dissolution times of 1.5 hours, 0.5 hours, and 0.25 hours in a KOH / water / EtOH solution (25°C). Furthermore, when cured at 230°C, the dissolution times of the compositions in a KOH / water / POE ether solution (70°C) were × (insoluble), 2 hours, and 0.5 hours. These results suggest that the antioxidant improves the solubility of the cured product in aqueous solvents, and that the antioxidant content is preferably 0.3 wt%, and more preferably 0.7 wt% or more.

[0094] The present invention includes the following aspects. [1] A polymerizable composition comprising (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), and (B) a second component consisting of a compound represented by the following formula (2), wherein the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more, the polymerizable composition does not contain a polyfunctional acrylic monomer, and the polymerizable composition satisfies either one of the following conditions: the polymerizable composition is free of a volatile solvent, or the polymerizable composition contains the volatile solvent in an amount of 30% by weight or less relative to the total weight of the polymerizable composition (except for the case where the polymerizable composition contains an aqueous solvent containing 18% by weight or more of water relative to the total weight of the polymerizable composition). [ka] In formula (1), R 1 is hydrogen or methyl. [ka] In equation (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and n is 1. [2] A polymerizable composition containing (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), and (B) a second component consisting of a compound represented by the following formula (2), wherein the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more, and the polymerizable composition does not contain a polyfunctional acrylic monomer (except when a water-soluble photosensitizer is contained). [ka] In formula (1), R 1 is hydrogen or methyl. [ka] In equation (2), R 2is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and n is 1. [3] A polymerizable composition containing (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), (B) a second component consisting of a compound represented by the following formula (2), and (D) a fourth component consisting of a polymerization initiator, wherein the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more, the polymerizable composition does not contain a polyfunctional acrylic monomer, and the content of the fourth component in the solid content of the polymerizable composition is 5% by weight or more. [ka] In formula (1), R 1 is hydrogen or methyl. [ka] In equation (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and n is 1. [4] The polymerizable composition according to [3] above, wherein the content of the fourth component in the solid content of the polymerizable composition is 20% by weight or less. [5] The polymerizable composition according to any one of [1] to [4] above, wherein the polymerizable composition is applied to a substrate made of a glass plate, dried at a drying temperature of 60°C for 6 minutes to obtain a coating, and then irradiated with ultraviolet light having a wavelength of 395 nm at a tack-free minimum irradiation dose to obtain a coating, and the coating is immersed in ion-exchanged water for 1 minute, and the state of the coating is visually observed to find that the coating is not dissolved. [6] The polymerizable composition according to [1] or [2] above, further comprising a fourth component consisting of (D) a polymerization initiator. [7] The polymerizable composition according to [6] above, wherein the content of the fourth component in the solid content of the polymerizable composition is 5 to 20 wt %. [8] In the compound represented by the formula (2), R 2 is hydrogen and R 3 and R 4 [7] The polymerizable composition according to any one of [1] to [7] above, wherein is methyl. [9] The polymerizable composition according to any one of [1] to [8], wherein the total content of the first component and the second component in the solid content of the polymerizable composition is 74% by weight or more.

[10] The polymerizable composition according to any one of [1] to [9], wherein the molar ratio of the first component to the second component in the polymerizable composition, in terms of first component / second component, is 1 / 5 to 5 / 1.

[11] The polymerizable composition according to any one of [1] to

[10] above, further comprising (E) an antioxidant, wherein the content of the antioxidant in the solid content of the polymerizable composition is 0.01 to 10 wt %.

[12] The polymerizable composition according to any one of [1] to

[11] above, which has a viscosity at 25°C of 2 to 30 mPa·s.

[13] An inkjet ink comprising the polymerizable composition according to any one of [1] to

[12] above.

[14] A cured product obtained by photocuring the polymerizable composition according to any one of [1] to

[12] above.

[15] An electronic component produced using the cured product described in

[14] above. [Explanation of symbols]

[0095] 10: Polymerizable composition 11: Pattern of polymerizable composition coating 12: Layer of polymerizable composition 12d: Unnecessary ionizing radiation cured material 20: Pattern of ionizing radiation cured product 20S: Exposed surface 21: Layer of ionizing radiation cured material 30: Conductive material film 31: Conductive material pattern 31R: Recess 32: Wiring material 40, 41: insulating material 42: Insulation part 50: Insulating substrate 100: Electrode member 200 :Structure LR: ionizing radiation LS: Irradiation device PE: High energy rays PJ: Inkjet printer PR: Offset printing press PS: Screen printing machine SB: Base material

Claims

1. A polymerizable composition comprising (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), and (B) a second component consisting of a compound represented by the following formula (2): the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more, Does not contain a polyfunctional acrylic monomer, The polymerizable composition is characterized by satisfying either of the following: it does not contain a volatile solvent; or it contains the volatile solvent in an amount of 30% by weight or less based on the entire polymerizable composition (except for the case where the polymerizable composition contains an aqueous solvent containing 18% by weight or more of water based on the entire polymerizable composition). 【Chemical 1】 In formula (1), R 1 is hydrogen or methyl. 【Chemistry 2】 In formula (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and n is 1.

2. A polymerizable composition comprising (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1), and (B) a second component consisting of a compound represented by the following formula (2): the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more, A polymerizable composition characterized by not containing a polyfunctional acrylic monomer (unless a water-soluble photosensitizer is contained). 【Chemistry 3】 In formula (1), R 1 is hydrogen or methyl. 【Chemistry 4】 In formula (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and n is 1.

3. A polymerizable composition comprising: (A) a first component consisting of (meth)acryloylmorpholine represented by the following formula (1); (B) a second component consisting of a compound represented by the following formula (2); and (D) a fourth component consisting of a polymerization initiator, the total content of the first component and the second component in the solid content of the polymerizable composition is 50% by weight or more, Does not contain a polyfunctional acrylic monomer, A polymerizable composition, wherein the content of the fourth component in the solid content of the polymerizable composition is 5% by weight or more. 【Chemistry 5】 In formula (1), R 1 is hydrogen or methyl. 【Chemistry 6】 In formula (2), R 2 is hydrogen or a group having 1 to 6 carbon atoms, and R 3 and R 4 are each independently hydrogen or a group having 3 or less carbon atoms, and n is 1.

4. The polymerizable composition according to claim 3 , wherein the content of the fourth component in the solid content of the polymerizable composition is 20% by weight or less.

5. 5. The polymerizable composition according to claim 1, wherein the polymerizable composition is applied to a substrate made of a glass plate, dried at a drying temperature of 60°C for 6 minutes to obtain a coating, and then irradiated with ultraviolet light having a wavelength of 395 nm at a tack-free minimum irradiation dose to obtain a coating. The coating is then immersed in ion-exchanged water for 1 minute, and the state of the coating is visually observed to find that the coating is not dissolved.

6. The polymerizable composition according to claim 1 or 2, further comprising a fourth component (D) consisting of a polymerization initiator.

7. 7. The polymerizable composition according to claim 6, wherein the content of the fourth component in the solid content of the polymerizable composition is 5 to 20% by weight.

8. In the compound represented by formula (2), R 2 is hydrogen, and R 3 and R 4 The polymerizable composition of claim 1 , wherein is methyl.

9. 9. The polymerizable composition according to claim 1, wherein a total content of the first component and a content of the second component in a solid content of the polymerizable composition is 74% by weight or more.

10. 10. The polymerizable composition according to claim 1, wherein a molar ratio of the first component to the second component in the polymerizable composition, expressed as first component / second component, is 1 / 5 to 5 / 1.

11. 11. The polymerizable composition according to claim 1, further comprising: (E) an antioxidant; and a content of the antioxidant in a solid content of the polymerizable composition is 0.01 to 10 wt %.

12. The polymerizable composition according to any one of claims 1 to 11, having a viscosity at 25°C of 2 to 30 mPa·s.

13. An inkjet ink comprising the polymerizable composition according to any one of claims 1 to 12.

14. A cured product obtained by photocuring the polymerizable composition according to claim 1 .

15. An electronic component produced using the cured product according to claim 14.

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