CN112119101A - Polymerizable composition, ink, transfer mold, and method for producing electrode member - Google Patents

Polymerizable composition, ink, transfer mold, and method for producing electrode member Download PDF

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Publication number
CN112119101A
CN112119101A CN201980032967.9A CN201980032967A CN112119101A CN 112119101 A CN112119101 A CN 112119101A CN 201980032967 A CN201980032967 A CN 201980032967A CN 112119101 A CN112119101 A CN 112119101A
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China
Prior art keywords
polymerizable composition
ionizing radiation
transfer mold
monofunctional
forming
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Chinese (zh)
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杉原克幸
伊丹节男
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JNC Corp
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JNC Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

Abstract

The invention provides an ionizing radiation curing type polymerizable composition which can properly maintain a cured shape even in a high-temperature environment and can be dissolved by an aqueous solution. A polymerizable composition characterized by comprising: a monofunctional acrylic compound containing one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound; a monofunctional N-vinyl compound; and a polymerization initiator that generates radicals by irradiation of ionizing radiation.

Description

Polymerizable composition, ink, transfer mold, and method for producing electrode member
Technical Field
The present invention relates to a polymerizable composition that can be preferably used when forming electrodes in batches corresponding to high-density mounting, an ink containing the polymerizable composition, a transfer mold containing an ionizing radiation cured product obtained by irradiating the polymerizable composition with ionizing radiation, and a method for producing an electrode member that includes an electrode group formed on a substrate using the polymerizable composition.
Background
Patent document 1 describes a technique for forming electrodes in a batch in a plurality of semiconductor devices (integrated circuits, ICs)) formed on a wafer in a wafer level chip size package (WL-CSP) which is one form of high density mounting, and discloses a two-layer laminated film which has a lower layer containing a non-radiation-sensitive resin composition and an upper layer containing a negative radiation-sensitive resin composition and which can achieve both high resolution and easy peeling, and a method for forming a bump using the two-layer laminated film.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2007-79550
Disclosure of Invention
Problems to be solved by the invention
In the two-layer laminated film described in patent document 1, only the radiation-irradiated portion of the upper layer remains during development, and the portion of the lower layer corresponding to the removed portion (non-radiation-irradiated portion) of the upper layer is dissolved and removed. Therefore, only the radiation-irradiated portion of the two-layer laminated film remains, and the radiation-non-irradiated portion of the two-layer laminated film is removed in the development stage. The portion of the double-layered laminated film removed in this manner is filled with a metal paste, and the metal paste is heated together with the wafer to reflow the metal paste, thereby forming a plurality of bumps in a batch on the wafer. After the bumps are formed in batch in this manner, the bilayer laminated film remaining on the wafer is removed by an organic solvent based stripping solution such as Dimethylsulfoxide (DMSO).
In recent years, the mounting density has been increasing, and therefore, the shape of a negative pattern (transfer mold) formed on a wafer for bump formation has become complicated (including three-dimensional). However, if a negative pattern having a complicated shape is to be formed by a process of forming a negative pattern using the two-layer laminated film as described above, the steps become complicated. Therefore, simplification of the manufacturing steps is expected. Further, it is required to reliably remove the material constituting the negative pattern remaining on the wafer after the formation of the bump, but since the concern on the environmental problem is increased, there is a need for a material which can be removed by an aqueous stripping liquid, particularly an aqueous stripping liquid substantially not containing an inorganic basic substance (sodium hydroxide or the like may be exemplified) or an organic basic substance (tetramethylammonium hydroxide or the like may be exemplified), instead of the above-mentioned organic solvent-based stripping liquid.
Further, in recent high-density mounting technology, a fan-out Wafer Level Package (WLP) in which a rewiring layer is formed in a wide area exceeding a chip area is also used, and a stack module (stack module) in which the fan-out WLP is stacked in a plurality of layers is also realized. In such fan-out WLP, conductive columns containing copper or the like are formed in large numbers in the rewiring layer, and a connecting material such as solder balls is disposed on the conductive columns. Since the arrangement accuracy of the connecting material needs to be increased as the mounting density is increased, it is required to arrange the connecting material on the conductive pillar more accurately.
The present invention has an object to provide an ionizing radiation-curable polymerizable composition which is capable of maintaining a cured shape appropriately even in a high-temperature environment such as a reflow process and is soluble in an aqueous solution, which is required along with the development of such mounting technology. Further, another object of the present invention is to provide an ink containing the polymerizable composition, a transfer mold containing an ionizing radiation cured product obtained by irradiating the polymerizable composition with an ionizing radiation, and a method for manufacturing an electrode member including an electrode group on a substrate using the polymerizable composition. In the present specification, the term "ionizing radiation" refers to a general term for electromagnetic waves such as γ rays, X rays, ultraviolet rays, and visible light, and energy sources that generate radicals by irradiation of electrons, protons, ions, and the like to the polymerization initiator or by collision with the polymerization initiator.
Means for solving the problems
The present invention provided to solve the above problems is as follows.
[1] A polymerizable composition for forming a transfer mold, said polymerizable composition characterized by comprising: a monofunctional acrylic compound containing one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound; a monofunctional N-vinyl compound; and a polymerization initiator that generates radicals by irradiation of ionizing radiation.
[2] The polymerizable composition according to the above [1], wherein the monofunctional N-vinyl compound is a monofunctional N-vinyl amide compound.
[3] The polymerizable composition according to the above [2], wherein the monofunctional type N-vinylamide compound comprises one or two or more compounds selected from the group consisting of N-vinylformamide, N-vinylacetamide, N-vinyl-caprolactam.
[4] The polymerizable composition according to any one of [1] to [3], having a viscosity of 15 mPas or less at 60 ℃.
[5] The polymerizable composition according to any one of [1] to [4], which contains a volatile solvent in an amount of 30% by mass or less based on the entire polymerizable composition.
[6] An ink jet ink comprising the polymerizable composition according to any one of [1] to [5 ].
[7] A transfer mold comprising an ionizing radiation cured product of the polymerizable composition according to any one of [1] to [5 ].
[8] The transfer mold according to the above [7], wherein when the ionizing radiation cured product has a film shape with a thickness of 13 μm to 18 μm formed on a glass substrate, the ionizing radiation cured product has a residual film ratio of 80% or more even if heated at 150 ℃ for 2 hours in the atmosphere.
[9] The transfer mold according to the above [7] or [8], wherein the ionizing radiation cured product is dissolved by immersion in an aqueous solution for 5 minutes or less even when heated at 150 ℃ for 2 hours in the atmosphere.
[10] The transfer mold according to the above [9], wherein the aqueous solution is a water-alcohol mixed solution. The alcohol is preferably an alcohol having miscibility with water, and more preferably an alcohol having 4 or less carbon atoms.
[11] The transfer mold according to the above [9] or [10], wherein the pH of the aqueous solution is 8 or less.
[12] A method for forming an electrode member in which a plurality of electrodes are exposed with recesses on one surface of an insulating substrate having wiring embedded therein, the method comprising: a disposing step of disposing the polymerizable composition according to any one of [1] to [5] on a substrate; a curing step of irradiating the polymerizable composition disposed on the base material with ionizing radiation to cure the polymerizable composition to obtain a transfer mold containing a cured product of the ionizing radiation; a conductive member forming step of forming a conductive member by disposing a conductive material so as to cover the transfer mold; a peeling step of peeling the structure including the transfer mold and the conductive member from the base material to expose the plurality of conductive members corresponding to the plurality of electrodes together with a surface of the transfer mold attached to the conductive member on the base material side; and a dissolving step of dissolving the transfer mold attached to each of the plurality of conductive members with an aqueous dissolving liquid to obtain the plurality of electrodes having the concave portions of the inverted shape including the transfer mold.
[13] The method of forming an electrode member according to [12], further comprising a heating step of heating the reverse casting mold on the base material during a period after the hardening step and before the dissolving step is started.
[14] The method of forming an electrode member according to [12] or [13], wherein in the disposing step, the polymerizable composition is supplied to the base material to dispose the pattern of the coating film of the polymerizable composition on the base material, and in the curing step, the pattern of the coating film of the polymerizable composition on the base material is cured to form the pattern of the ionizing radiation cured product on the base material as the transfer mold.
[15] The method of forming an electrode member according to [14], wherein the polymerizable composition is an ink for inkjet, and in the disposing step, a pattern of a coating film of the polymerizable composition is disposed on the substrate using an inkjet printer.
[16] The method of forming an electrode member according to [12] or [13], wherein in the disposing step, a layer of the polymerizable composition is formed on the base material, and in the hardening step, the layer of the ionizing radiation cured product is formed from the layer of the polymerizable composition, the method of forming an electrode member further includes, before the conductive member forming step starts, a patterning step of irradiating a part of the layer of the ionizing radiation cured product with high-energy rays to remove the ionizing radiation cured product, thereby forming the pattern of the ionizing radiation cured product on the base material as the transfer mold.
[17] The method of forming an electrode member according to any one of [14] to [16], wherein in the conductive member forming step, a plurality of patterns of the conductive members that are electrically independent are formed on the base, the wiring that is electrically connected to the patterns of the plurality of conductive members is further formed, and an insulating material is disposed around the patterns of the plurality of conductive members and the wiring to form the insulating substrate on the base, and in the peeling step, the structure peeled from the base includes the transfer mold and the insulating substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a polymerizable composition which can form a cured ionizing radiation product that can maintain a cured shape properly even in a high-temperature environment and can be dissolved in an aqueous solution. Further, according to the present invention, there are provided an ink containing the polymerizable composition, an ionizing radiation cured product obtained by irradiating the polymerizable composition with ionizing radiation, and a method for manufacturing an electrode member including an electrode group on a substrate using the polymerizable composition.
Drawings
Fig. 1 is a flowchart of the manufacturing method of the present embodiment.
Fig. 2 is a diagram for explaining the arrangement step (step S101) to the hardening step (step S102).
Fig. 3 is a diagram for explaining the arrangement step (step S101), the curing step (step S102), and the patterning step (step S103).
Fig. 4 is a diagram for explaining the conductive member disposing step (step S104), the peeling step (step S105), and the dissolving step (step S106).
Detailed Description
The polymerizable composition, the ink, the ionizing radiation cured product, and the method for producing the electrode member according to the embodiment of the present invention will be described below.
The polymerizable composition according to an embodiment of the present invention is a polymerizable composition for forming a transfer mold, and includes: a monofunctional acrylic compound containing one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound; a monofunctional N-vinyl compound; and a polymerization initiator that generates radicals by irradiation of ionizing radiation.
The monofunctional acrylic compound includes one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound. The monofunctional acrylate compound is a generic name for (meth) acrylates and compounds having a partial structure based on (meth) acrylates and having one ethylenic double bond in the molecule, and specific examples of compounds having a partial structure based on (meth) acrylic acid include methyl (meth) acrylate. In the present specification, the term "acrylic acid" and "methacrylic acid" may be used to denote either one or both of them, and may be referred to as "(meth) acrylic acid". The terms related to (meth) acrylic acid, such as "(meth) acrylate", "meth) acryloyloxy" also have the same meaning.
The monofunctional acrylate compound preferably has a hydroxyl group (-OH) from the viewpoint of ensuring the solubility of an ionizing radiation cured product obtained by irradiating the polymerizable composition with ionizing radiation in an aqueous solution. Specific examples of such a hydroxyl (-OH) -containing monofunctional acrylate compound include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, N-hydroxyethyl (meth) acrylamide, and polyoxyethylene monoacrylate. Among these, 4-hydroxybutylacrylate and 1, 4-cyclohexanedimethanol monoacrylate are preferable from the viewpoint of ensuring the printing suitability and storage stability of the polymerizable composition because of their relatively low volatility, and 4-hydroxybutylacrylate is particularly preferable from the viewpoint of the solubility of the obtained ionizing radiation cured product in an aqueous solution.
Specific examples of the monofunctional acrylamide compound include: n-isopropylacrylamide, N-dimethyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide and (meth) acryloylmorpholine. Among these, from the viewpoint of ensuring the printing suitability and storage stability of the polymerizable composition easily because of the relatively low volatility, and from the viewpoint of the solubility of the obtained ionizing radiation cured product in an aqueous solution, it is preferably (meth) acryloylmorpholine.
The monofunctional N-vinyl compound is a compound having a structure in which an ethylenically unsaturated group is bonded to an amino group, and the amino group may constitute a carbonyl group or an amide bond. In the present specification, such a monofunctional compound in which an amino group to which an ethylenically unsaturated group is bonded forms an amide bond is also referred to as a "monofunctional N-vinylamide compound". The monofunctional N-vinyl amide compound is a preferable example of the monofunctional N-vinyl compound. Specific examples of the monofunctional N-vinylamide compound include N-vinylformamide, N-vinylacetamide, N-vinyl-caprolactam and the like, and specific examples of the monofunctional N-vinyl compound other than the monofunctional N-vinylamide compound include 1-vinylimidazole and 9-vinylcarbazole. Among these compounds, N-vinylformamide, N-vinylacetamide, N-vinyl-caprolactam, and 1-vinylimidazole are preferable from the viewpoint of the ease of solubility of the obtained ionizing radiation cured product in an aqueous solution, and N-vinylformamide, N-vinylacetamide, and N-vinyl-caprolactam are particularly preferable from the viewpoint of the limitation of transportation of the product.
The polymerization initiator is not limited in kind as long as it can generate radicals by irradiation with ionizing radiation and can initiate a polymerization reaction of the monofunctional acrylic compound and the monofunctional N-vinyl compound. The content of the polymerization initiator is also suitably set depending on the kind and content of the monofunctional acrylic compound and monofunctional N-vinyl compound and the kind of the polymerization initiator. By way of non-limiting example, the content of the curing agent is preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and particularly preferably 2 to 12 parts by weight, based on the total amount of the polymerizable composition.
Specific examples of the polymerization initiator include: benzophenone, Michler's ketone, 4' -bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4-diethyl thioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4 ' -isopropylphenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-dimethoxy-1, 2-diphenylethane-1-one, camphorquinone, benzanthrone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -1-one]Phenyl radical]-2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -1-butanone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinylphenyl) -1-butanone, oxy-phenyl-acetic acid 2- (2-oxo-2-phenyl-acetoxy-ethoxy) -ethyl ester, oxy-phenyl-acetic acid 2- (2-hydroxy-ethoxy) -ethyl ester, oxy-phenyl-acetic acid 2- (2-oxo-2-phenyl-acetoxy-ethoxy) -ethyl ester and oxy-phenyl-acetic acid 2- (2-hydroxy- Mixtures of ethoxy) -ethyl esters, methyl phenylglyoxylate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4' -di (tert-butylperoxycarbonyl) benzophenone, 3,4,4' -tri (tert-butylperoxycarbonyl) benzophenone, 3',4,4' -tetra (tert-hexylperoxycarbonyl) benzophenone, 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, methyl 4-dimethylaminobenzoate, methyl 4-dimethyl-aminobenzoate, isoamyl 4,4' -di (tert-butylperoxycarbonyl) benzophenone, 3',4' -, 2- (4' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3',4' -dimethylOxystyrene-based) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2',4' -dimethoxystyrene-based) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 '-methoxystyrene-based) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxyphenylstyrene-based) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl)]-2, 6-bis (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) benzothiazole, 2-mercaptobenzothiazole, 3' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 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, 1-hydroxycyclohexylphenylketone, bis (. eta.).5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1/-pyrrol-1-yl) -phenyl) titanium, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide. These compounds may be used alone, and two or more of them may be used in combination. Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -1-butanone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinylphenyl) -1-butanone, and 2-methyl-1- [4- (methylthio) phenyl ] butanone are preferable from the viewpoints of high sensitivity to an ultraviolet-light emitting diode (UV-LED) light source and photocurability]-2-morpholinyl-1-propanone, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide.
The polymerizable composition of the present embodiment may not substantially contain a volatile solvent from the viewpoint of simplifying the step of forming the ionizing radiation cured product, but may contain a volatile solvent from the viewpoint of adjusting the viscosity of the polymerizable composition, and the like. The volatile solvent may be mixed with other compositions at the time of use to constitute the polymerizable composition. In the case where the polymerizable composition contains a volatile solvent, the volatile solvent may start to volatilize in a state where the polymerizable composition is not cured, and preferably volatilize at least in a stage where the ionizing radiation cured product is formed by heating before, during, and/or after irradiation with the ionizing radiation as appropriate. If the solvent remains excessively unvaporized in a state where the polymerizable composition has been cured to some extent, the final cured product (ionizing radiation cured product) may have a porous structure and the surface properties (surface smoothness) required as an inverse mold (negative pattern) for inverse transfer may be reduced. Therefore, the content of the volatile solvent is preferably 30% by mass or less with respect to the entire polymerizable composition.
Specific examples of the volatile solvent 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-oxopropionate, ethyl 3-oxopropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl ethoxypropionate, n-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 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 monophenyl ether, ethylene glycol monopropyl ether, diethylene glycol monophenyl ether, propylene glycol, 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, glycerol, benzyl alcohol, cyclohexanol, 1, 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, gamma-butyrolactone, N-dimethylacetamide, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monopropyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, n-methyl-2-pyrrolidone, dimethylimidazolidinone, and the like. These compounds may be used alone, and two or more of them may be used in combination.
The polymerizable composition of the present embodiment may contain components other than the above components as other additives. Specific examples of the other additives include surfactants, polymerization inhibitors, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, fillers, pigments, dyes, and the like, but there is no particular limitation as long as the other components can be uniformly mixed without departing from the scope of the present invention.
The polymerizable composition of the present embodiment is supplied onto a substrate by coating, dropping, or the like at the time of use, and thereby has a film-like shape or a predetermined pattern on the substrate. In view of improving the ease of supplying the polymerizable composition onto the substrate in this manner, the viscosity of the polymerizable composition of the present embodiment at 25 ℃ may be preferably 100mPa · s or less. In particular, when the polymerizable composition is supplied onto the substrate by an ink jet printer, it is preferable that the viscosity range is satisfied. Further, the viscosity of the ink jet ink containing the polymerizable composition of the present embodiment at the ejection temperature (for example, 60 ℃) is preferably 15mPa · s or less, and particularly preferably 10mPa · s or less.
The polymerizable composition of the present embodiment is hardened by irradiation with ionizing radiation to become an ionizing radiation hardened substance. The ionizing radiation cured product is soluble in an aqueous solution even after being heated at 150 ℃ for 2 hours in the atmosphere. Specifically, the ionizing radiation cured product after the heat treatment (2 hours at 150 ℃) is dissolved by immersion in an aqueous solution for 15 minutes or less, and in a preferred embodiment, by immersion for 5 minutes or less.
The aqueous solution is a solution containing water and may be composed of water, but is preferably a mixed solvent with a polar solvent, and more preferably a mixed solvent with a protic polar solvent such as alcohol. From the viewpoint of improving the homogeneity of the mixed liquid, the alcohol preferably has a high solubility in water, that is, has miscibility with water. The content of water in the aqueous solution is appropriately set depending on the kind of components other than water contained in the aqueous solution or the composition of the ionizing radiation curing material. When the aqueous dissolving solution contains a water-alcohol mixed solution which is a mixed solution of water and an alcohol, and the alcohol contained in the water-alcohol mixed solution contains a substance having 4 or less carbon atoms such as ethanol or isopropanol, the alcohol content is preferably 25% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 85% by mass or less, and particularly preferably 70% by mass or more and 80% by mass or less.
The aqueous solution may contain an organic solvent other than alcohol. Examples of such an organic solvent 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 the alcohol in the aqueous solution is preferably 20 mass% or less of the total aqueous solution.
The aqueous solution is preferably alkali-free, that is, non-alkali. When the aqueous solution contains an inorganic basic substance such as sodium hydroxide or an organic basic substance such as tetramethylammonium hydroxide in order to make the aqueous solution alkaline, the handleability of the aqueous solution may be lowered. Since a general alkali-based solution has a pH of 9 or more, the alkali-free aqueous solution is a solution having a pH of less than 9 in the present specification. From the viewpoint of being more alkali-free, the pH of the aqueous solution is preferably 8 or less, and more preferably 7.5 or less.
The ionizing radiation cured product of the present embodiment is less likely to change its shape even when heated. Specifically, when the ionizing radiation cured product of the present embodiment has a film shape with a thickness of 13 μm to 18 μm formed on a glass substrate, the residual film ratio defined by (thickness after heat treatment)/(thickness after heat treatment) is 80% or more, in a preferred example 85% or more, and in a more preferred example 90% or more, even when the product is heated at 150 ℃ for 2 hours in the atmosphere. Therefore, even when a metal such as copper is formed directly on the pattern including the ionizing radiation cured product by a dry process such as vapor deposition or sputtering, the shape of the pattern is not easily changed.
Hereinafter, a method of manufacturing an electrode member in which a plurality of electrodes each having a recess are exposed on one surface of an insulating substrate in which wiring is embedded, which can be used as re-distribution layer (RDL) used in fan-out WLP or the like, will be described. The material constituting the electrode includes, for example, copper (Cu), and the material constituting the insulating substrate includes, for example, polyimide.
Fig. 1 is a flowchart of the manufacturing method of the present embodiment. As shown in fig. 1, the present manufacturing method includes, as essential steps, a disposing step (step S101), a hardening step (step S102), a conductive member disposing step (step S104), a peeling step (step S105), and a dissolving step (step S106). The present manufacturing method may optionally include a patterning step (step S103) between the curing step (step S102) and the conductive member disposing step (step S104), and may further include a heating step (step S107) during a period after the curing step (step S102) and before the dissolving step (step S106) is started.
Fig. 2 is a diagram for explaining the arrangement step (step S101) to the curing step (step S102) included in the example of the manufacturing method of the present embodiment.
In the disposing step (step S101), the polymerizable composition 10 is disposed on one main surface of a plate-like or sheet-like base material SB (fig. 2(a)) to be finally peeled off, such as a glass substrate or a silicon substrate. The method of disposing the polymerizable composition 10 is not limited. In fig. 2, as shown in fig. 2(b), the following example is shown: a pattern 11 of a coating of the polymerizable composition is formed on the substrate SB by various known arrangement units such as a screen printer PS (left side), an offset printer PR (center) using a transfer roller, and an ink jet printer PJ (right side).
In the curing step, ionizing radiation LR is irradiated onto the pattern 11 of the coating of the polymerizable composition disposed on the substrate SB (fig. 2(c)), and the pattern 11 of the coating of the polymerizable composition is cured, thereby obtaining a pattern 20 of an ionizing radiation cured product as a transfer mold on the substrate SB (fig. 2 (d)). The type of the ionizing radiation LR is not particularly limited, and examples thereof include visible light, ultraviolet light, X-ray, γ -ray, electron beam, ion beam, and the like. The irradiation device LS can be set as appropriate according to the type of the ionizing radiation LR. Specific examples thereof include an LED, a halogen lamp, a radiation irradiation device, an electron beam irradiation device, and an ion beam generation source. From the viewpoint of acquisition easiness, handling easiness, or the like, a UV-LED or a halogen lamp having an emission peak around 350nm to 400nm may be preferably used.
Fig. 3 is a diagram for explaining the arrangement step (step S101), the curing step (step S102), and the patterning step (step S103) included in another example of the manufacturing method of the present embodiment.
In the disposing step (step S101), a layer 12 of a polymerizable composition is formed on one of the main surfaces (fig. 3(a)) of the substrate SB as shown in fig. 3 (b). Examples of the method for forming the layer 12 of the polymerizable composition include spin coating, dipping, and spray coating. Thereafter, by performing the curing step (step S102), a layer 21 of an ionizing radiation cured product is formed on one of the main surfaces of the substrate SB as shown in fig. 3 (c).
Thereafter, a part of the layer 21 of the ionizing radiation curing material is irradiated with high-energy rays PE (specifically, laser beam or ion beam is exemplified) to remove unnecessary ionizing radiation curing material 12 d. In this manner, a patterning step of forming a transfer mold including a pattern 20 of an ionizing radiation cured product on the substrate SB is performed (step S103).
Fig. 4 is a diagram for explaining the conductive member disposing step (step S104), the peeling step (step S105), and the dissolving step (step S106) included in one example of the manufacturing method of the present embodiment.
After obtaining a structure in which the pattern 20 of the ionizing radiation hardened substance is formed on the substrate SB through the manufacturing steps shown in fig. 2 or 3, a conductive member forming step (step S104) of forming a film 30 of a conductive member by disposing a conductive material so as to cover the pattern 20 of the ionizing radiation hardened substance on the substrate SB is performed. Fig. 3(a) shows a case where a film 30 of a film-like conductive member is formed by uniformly disposing a conductive material on one main surface of a substrate SB as a specific example of the conductive member forming step (step S104).
The type of the conductive material is not particularly limited, but is preferably set in a more flexible manner in the subsequent process as long as the film 30 of the conductive member is impermeable to water and has a function of a protective layer for ionizing the pattern 20 of the radiation cured product. From this viewpoint, examples of the conductive material include metallic 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 method of manufacturing the film 30 of the conductive member is appropriately set according to the kind of the conductive material. When the conductive material is made of a metal material such as copper (Cu), the following methods can be exemplified: a method of forming the entire film 30 of the conductive member by a dry process such as evaporation or sputtering; a method of forming a thin layer of a conductive material so as to cover the pattern 20 of the ionizing radiation cured product on the substrate SB by a dry process such as vapor deposition or sputtering, and then depositing the conductive material by a wet process such as plating, thereby forming a film 30 of a conductive member on the substrate SB.
When the conductive material is deposited by the dry process, the conductive material facing 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 product may also be at a high temperature on the substrate SB. In this case, the heating step (step S107) is substantially performed in the conductive member forming step (step S104). Even when the heating step (step S107) is substantially performed in this manner, the pattern 20 of the ionizing radiation cured product can be appropriately dissolved by the aqueous dissolving liquid in the dissolving step described later as described above, and the shape change due to heat is small.
After the film 30 of the conductive member is formed on the substrate SB in this manner, a high-energy beam such as a laser beam is irradiated to remove a part of the film 30 of the conductive member, thereby obtaining a pattern 31 of the conductive member formed so as to cover each pattern 20 of the ionizing radiation cured product (fig. 4 (b)). In this process, the irradiated high-energy line may heat the substrate SB or the pattern 31 of the conductive member. In this case, the heating step (step S107) may be substantially performed in the conductive member forming step (step S104). As described above, even if the pattern 20 transferred to the ionizing radiation cured product is heated in this manner, the solubility in the aqueous solution can be appropriately maintained, and the shape change is less likely to occur.
In fig. 4 a and 4 b, the conductive member film 30 is formed in the conductive member forming step (step S104) and then the conductive member pattern 31 is formed. The pattern 31 of the conductive member may also be directly formed by using an appropriate mask material or the like.
Then, in order to further facilitate the lamination of the member on the pattern 31 of the conductive member provided on the substrate SB, an insulating material 40 such as polyimide is disposed around the pattern 31 of the conductive member on the substrate SB as shown in fig. 4 (c). The specific method of the process is any method. For example, the insulating material 40 may be disposed by photolithography (including hardening) in which coating is performed by spin coating or the like and heat treatment is performed. In this case, since the heating process is performed, the pattern 20 of the ionizing radiation cured product covered with the pattern 31 of the conductive member in contact with the insulating material 40 is also heated. Therefore, the heating process corresponds to a heating step (step S107) performed before the start of the peeling step (step S105) described below. As described above, the ionizing radiation cured product of the present embodiment is less likely to have a reduced solubility in an aqueous solution and less likely to have a shape change due to heating even when heated, and therefore, a heating step (step S107) for performing such a heating treatment can be performed.
After the insulating material 40 is appropriately disposed around the conductive member pattern 31 in this manner, the conductive material is further laminated and patterned (or laminated simultaneously with the patterning), so that the wiring member 32 is formed on the conductive member pattern 31, and the insulating material 41 such as polyimide is disposed around the wiring member 32 (fig. 4 (d)). A plurality of layers including the wiring member 32 and the insulating material 41 may be provided. As described above, even if the process of forming the layer including the wiring member 32 and the insulating material 41 includes a heating treatment and substantially becomes a heating step (step S107), the ionizing radiation cured product maintains the solubility in the aqueous solution appropriately and is less likely to cause a shape change due to heating. In this manner, the following structure 200 is disposed on the substrate SB: the pattern 20 of the ionizing radiation curing material constituting the transfer mold, the pattern 31 of the conductive member constituting the electrode, the wiring member 32 constituting the wiring, and the insulating substrate 50 including the insulating portion 42 composed of the insulating material 40 and the insulating material 41 are included.
The structure 200 thus obtained is inverted so that the substrate SB is positioned above the structure 200 (fig. 4(e)), and the substrate SB is peeled off, so that the surface 20S of the pattern 20 of the ionizing radiation cured product in the structure 200 on the substrate SB side (the surface disposed opposite to the substrate SB) is exposed (fig. 4 (f)). The pattern 20 of the ionizing radiation curing product including the exposed surface 20S is brought into contact with an aqueous solution, whereby the pattern 20 of the ionizing radiation curing product can be dissolved and removed. As a result, as shown in fig. 4(g), the pattern 31 of the conductive member having the surface of the concave portion 31R of the inverted shape as the pattern 20 of the ionizing radiation curing substance is exposed, and the patterns 31 of the conductive members respectively serve as the electrodes of the electrode member. In this way, the electrode member 100 is obtained in which the plurality of electrodes (the patterns 31 of the conductive member) are exposed with the concave portions 31R on the one surface of the insulating substrate 50 in which the wiring (the wiring member 32) is embedded.
In the case where the exposed portion of the electrode has the concave portion 31R as described above, when the electrode member is used as the rewiring, the concave portion 31R functions as a receiving portion for the solder ball, and therefore, the stability of the solder ball placed thereon is improved. Therefore, the arrangement density of the electrodes in the redistribution lines can be increased, and the mounting density can be increased.
By the above manufacturing method, an electrode member can be manufactured in which each conductive member constituting the pattern 31 of conductive members serves as an electrode, and the electrode and a wiring electrically connected to the electrode are embedded in a support member (including the insulating material 40 and the insulating material 41).
The present invention has been described with reference to the above embodiments, but the present invention is not limited to the above embodiments, and may be modified or changed for the purpose of improvement or within the scope of the idea of the present invention.
Examples
The present invention will be described in more detail with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
(example 1)
A polymerizable composition containing 7.06 parts by mass of Acryloylmorpholine (ACMO) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 3.55 parts by mass of N-vinyl formamide (NVF) as a monofunctional N-vinyl compound, 1.27 parts by mass of gazel (IRGACURE)379EG (manufactured by BASF corporation, hereinafter simply referred to as "IRG 379") as a polymerization initiator, and 0.0053 parts by mass of Birk (BYK)342 (manufactured by BYK chemical (chek mie Japan)) as a surfactant was prepared. In the polymerizable composition, the monofunctional acrylic compound and the monofunctional N-vinyl compound are equimolar (molar ratio is 1: 1). In the following other examples and comparative examples, the content of each compound in the polymerizable composition was set so that the number of ethylenically unsaturated bonds in each of the two compounds having ethylenically unsaturated bonds contained in the polymerizable composition was equal to each other (so that the number of functional groups was equimolar). In the polymerizable composition, the polymerization initiator was in an amount of 12% and the surfactant was in an amount of 500ppm, respectively, based on the total mass part of the monofunctional acrylic compound and the monofunctional N-vinyl compound. In the following other examples and comparative examples, the content of the polymerization initiator and the content of the surfactant were also set so as to satisfy the relationship of the total mass part. The resultant polymerizable composition had a viscosity of 10.4 mPas at 25 ℃ and 8.8 mPas at 30 ℃. Therefore, the polymerizable composition of example 1 is particularly preferable as an ink for inkjet if it is 30 ℃ or higher.
(example 2)
A polymerizable composition containing 7.06 parts by mass of Acryloylmorpholine (ACMO) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 6.96 parts by mass of N-vinyl caprolactamate (NVC) as a monofunctional N-vinyl compound, 3791.68 parts by mass of IRG as a polymerization initiator, and 3420.0070 parts by mass of BYK (BYK) as a surfactant was prepared. The resultant polymerizable composition had a viscosity of 10.8 mPas at 25 ℃ and 9.0 mPas at 30 ℃. Therefore, the polymerizable composition of example 2 is particularly preferable as an ink for inkjet if it is 30 ℃ or higher.
(example 3)
A polymerizable composition containing 7.06 parts by mass of Acryloylmorpholine (ACMO) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 4.26 parts by mass of N-vinyl acetamide (NVAc) as a monofunctional N-vinyl compound, 3791.36 parts by mass of IRG as a polymerization initiator, and 3420.0057 parts by mass of BYK (BYK) as a surfactant was prepared. The resultant polymerizable composition had a viscosity of 6.8 mPas at 25 ℃. Therefore, the polymerizable composition of example 3 is particularly preferable as an ink for inkjet if it is 25 ℃ or higher.
(example 4)
A polymerizable composition containing 7.06 parts by mass of Acryloylmorpholine (ACMO) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 4.71 parts by mass of N-vinylimidazole (NVIM) as a monofunctional N-vinyl compound, 3791.41 parts by mass of IRG as a polymerization initiator, and 3420.0059 parts by mass of BYK (BYK) as a surfactant was prepared. The resultant polymerizable composition had a viscosity of 7.5 mPas at 25 ℃. Therefore, the polymerizable composition of example 4 is particularly preferable as an ink for inkjet if it is 25 ℃ or higher.
(example 5)
A polymerizable composition containing 7.21 parts by mass of 4-hydroxybutylacrylate (4HBA) as a monofunctional acrylate compound which is one of monofunctional acrylic compounds, 3.55 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, 3791.29 parts by mass of IRG as a polymerization initiator, and 3420.0054 parts by mass of BYK (BYK) as a surfactant was prepared. The resultant polymerizable composition had a viscosity of 9.0 mPas at 25 ℃. Therefore, the polymerizable composition of example 5 is particularly preferable as an ink for inkjet if it is 25 ℃ or higher.
(example 6)
A polymerizable composition containing 6.36 parts by mass of diethylacrylamide (diethylacetamide, DEAA) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 3.55 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, 3791.19 parts by mass of IRG as a polymerization initiator, and 3420.0050 parts by mass of BYK (BYK) as a surfactant was prepared. The resultant polymerizable composition had a viscosity of 3.7 mPas at 25 ℃. Therefore, the polymerizable composition of example 6 is particularly preferable as an ink for inkjet if it is 25 ℃ or higher.
Comparative example 1
A polymerizable composition containing 7.06 parts by mass of Acryloylmorpholine (ACMO) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 7.21 parts by mass of 4-hydroxybutylacrylate (4HBA) as a monofunctional acrylate compound which is one of monofunctional acrylic compounds, 3791.71 parts by mass of IRG as a polymerization initiator, and 3420.0071 parts by mass of BYK (BYK) as a surfactant was prepared. The resultant polymerizable composition had a viscosity of 12.8 mPas at 25 ℃ and 7.9 mPas at 40 ℃. Therefore, the polymerizable composition of comparative example 1 is particularly preferable as an ink for inkjet if it is 40 ℃ or higher.
Comparative example 2
A polymerizable composition containing 7.06 parts by mass of Acryloylmorpholine (ACMO) as a monofunctional acrylamide compound which is one of monofunctional acrylic compounds, 6.53 parts by mass of polyethylene glycol #400 diacrylate (9EG-a) as a bifunctional acrylic compound, 3791.21 parts by mass of IRG as a polymerization initiator, and 3420.0071 parts by mass of Birk (BYK) as a surfactant was prepared. The molar ratio of the monofunctional acrylic compound to the difunctional acrylic compound in the polymerizable composition is set to 1: 0.5. the resultant polymerizable composition had a viscosity of 52.8 mPas at 25 ℃ and 14.9 mPas at 60 ℃. Therefore, the polymerizable composition of comparative example 2 is particularly preferable as an ink for inkjet if it is 60 ℃ or higher.
Comparative example 3
A polymerizable composition containing 6.53 parts by mass of polyethylene glycol #400 diacrylate (9EG-a) as a bifunctional acrylic compound, 1.78 parts by mass of N-vinylformamide (NVF) as a monofunctional N-vinyl compound, 3791.00 parts by mass of IRG as a polymerization initiator, and 3420.0042 parts by mass of BYK (BYK) as a surfactant was prepared. The molar ratio of the bifunctional acrylic compound to the monofunctional N-vinyl compound in the polymerizable composition was set to 0.5: 1. the resultant polymerizable composition had a viscosity of 52.8 mPas at 25 ℃ and 14.6 mPas at 60 ℃. Therefore, the polymerizable composition of comparative example 3 is particularly preferable as an ink for inkjet if it is 60 ℃ or higher.
(evaluation example 1) evaluation of Photocurability
The polymerizable compositions of examples 1 to 6 and comparative examples 1 to 3 were applied to a glass substrate by spin coating for 10 seconds to obtain coating films.
The obtained coating film of the polymerizable composition was cured under the following conditions to obtain an ionizing radiation cured product.
UV irradiation device: "ASM 1503 NM-UV-LED" manufactured by Asumi Giken "
Wavelength of the lamp: 365nm
Exposure amount: 500mJ/cm2、1000mJ/cm2、1500mJ/cm2、2000mJ/cm2
Illuminance: 700mW/cm2
For the measurement of UV light, a UV monitor ("UV-Pad" manufactured by Opsytec) for measuring UVA (315nm to 400nm) was used.
The polymerizable compositions of examples 1 to 6 and comparative examples 1 to 3 were coated and exposed to light to form a film of an ionizing radiation-cured product on a glass substrate. Thereafter, the surface of the cured film was touched with a finger to determine the exposure amount when the cured film was completely in a non-tacky state. The results are shown in Table 1.
[ Table 1]
Figure BDA0002781653220000181
As shown in Table 1, the amount of the non-tacky exposure was 1500mJ/cm in examples 1 to 6 and comparative examples 2 and 32Among them, examples 1,3, 4 and 6 and comparative examples 2 and 3 are 500mJ/cm2But is particularly good. In contrast, in comparative example 1, the exposure amount was set to 2000mJ/cm2However, the non-viscous state is not achieved, and the curing of the polymerizable composition is not completed.
(evaluation example 2) evaluation of residual film ratio after Heat treatment
The polymerizable compositions of examples 1 to 6 and comparative examples 2 and 3 were coated and cured under the same conditions as in evaluation example 1, respectively, to obtain films of ionizing radiation-cured products. As the photo-curing conditions, exposure was performed under the exposure amount which was the non-tacky exposure amount confirmed in evaluation example 1. Thereafter, the obtained film of the ionizing radiation cured product was further subjected to heat treatment under the following conditions. In comparative example 1, the exposure amount was set to 2000mJ/cm2However, the non-adhesive state was not achieved, and therefore, the evaluation target was not obtained and no additional heat treatment was performed.
Cleaning an oven: "DT 610" manufactured by Yamato Scientific Inc "
Temperature: 150 ℃ C
Heating time: 2 hours
The film thickness (unit:%) of the cured product of ionizing radiation was measured before and after the heat treatment, and the residual film ratio (unit:%) defined as (thickness after heat treatment)/(thickness after heat treatment) was measured. The film thickness and the residual film ratio before and after the heat treatment are shown in table 2.
[ Table 2]
Figure BDA0002781653220000191
As shown in table 2, the film residue ratios in examples 1 to 6 and comparative examples 2 and 3 were 80% or more, and those in examples 1 and 5 and comparative examples 2 and 3 were particularly preferable because the film residue ratios were 90% or more.
(evaluation example 3) evaluation of solubility
The polymerizable compositions of examples 1 to 6 and comparative examples 2 and 3 were coated and cured under the same conditions as in evaluation example 2, respectively, to obtain ionizing radiation cured products. Thereafter, the obtained cured product of ionizing radiation was subjected to heat treatment under the same conditions as in evaluation example 2. In comparative example 1, the exposure amount was set to 2000mJ/cm2While non-tackiness has not yet been achievedTherefore, the evaluation was not performed, and the solubility was not evaluated.
Then, a mixed solution of water and ethanol (EtOH) (mixing ratio: water/EtOH: 25/75) was prepared as a solution, and the ionizing radiation cured product after the heat treatment was immersed in the solution at 25 ℃. The evaluation criteria are as follows.
A: dissolve in less than 5 minutes
B: dissolving in 5-15 min
C: remained undissolved after 15 minutes
[ Table 3]
Solubility in water
Example 1 A
Example 2 A
Example 3 A
Example 4 A
Example 5 A
Example 6 A
Comparative example 1 -
Comparative example 2 C
Comparative example 3 C
In the cured ionizing radiation products of examples 1 to 6, the cured ionizing radiation products after the heat treatment were well dissolved within 5 minutes. In contrast, in the cured ionizing radiation products of comparative examples 2 and 3, the cured ionizing radiation products after the heat treatment were not dissolved even after 15 minutes had elapsed after immersion.
Description of the symbols
10: polymerizable composition
11: pattern of coating film of polymerizable composition
12: layer of a polymerizable composition
12 d: unwanted ionizing radiation curing product
20: pattern of ionizing radiation curing article
20S: exposed surface
21: layer of ionizing radiation curing substance
30: film of conductive member
31: pattern of conductive members
31R: concave part
32: wiring member
40. 41: insulating material
42: insulating part
50: insulating substrate
100: electrode member
200: structural body
LR: ionizing radiation
LS: irradiation device
PE: high energy ray
PJ: ink-jet printer
PR: offset printing press
PS: screen printer
SB: base material

Claims (17)

1. A polymerizable composition for forming a transfer mold, comprising:
a monofunctional acrylic compound containing one or more compounds selected from the group consisting of a monofunctional acrylate compound and a monofunctional acrylamide compound;
a monofunctional N-vinyl compound; and
the polymerization initiator generates radicals by irradiation of ionizing radiation.
2. The polymerizable composition according to claim 1, wherein the monofunctional N-vinyl compound is a monofunctional N-vinyl amide compound.
3. The polymerizable composition according to claim 2, wherein the monofunctional type N-vinyl amide compound comprises one or two or more compounds selected from the group consisting of N-vinyl formamide, N-vinyl acetamide, N-vinyl-caprolactam.
4. The polymerizable composition according to any one of claims 1 to 3, having a viscosity at 60 ℃ of 15 mPa-s or less.
5. The polymerizable composition according to any one of claims 1 to 4, which contains a volatile solvent in an amount of 30% by mass or less based on the entire polymerizable composition.
6. An inkjet ink comprising the polymerizable composition as claimed in any one of claims 1 to 5.
7. A transfer mold comprising an ionizing radiation cured product of the polymerizable composition according to any one of claims 1 to 5.
8. The transfer mold according to claim 7, wherein in a case where the ionizing radiation hardened substance has a film shape with a thickness of 13 μm to 18 μm formed on a glass substrate, the ionizing radiation hardened substance has a residual film ratio of 80% or more even if heated at 150 ℃ for 2 hours in the atmosphere.
9. The transfer mold according to claim 7 or 8, wherein the ionizing radiation cured product is dissolved by immersion in an aqueous solution for 5 minutes or less even when heated at 150 ℃ for 2 hours in the atmosphere.
10. The transfer mold according to claim 9, wherein the aqueous solution is a water-alcohol mixed solution.
11. The transfer mold according to claim 9 or 10, wherein the pH of the aqueous solution is 8 or less.
12. A method for forming an electrode member, characterized in that the method for manufacturing an electrode member in which a plurality of electrodes are exposed with concave portions on one surface of an insulating substrate in which wiring is embedded, includes:
a disposing step of disposing the polymerizable composition according to any one of claims 1 to 5 on a substrate;
a curing step of irradiating the polymerizable composition disposed on the base material with ionizing radiation to cure the polymerizable composition to obtain a transfer mold containing a cured product of the ionizing radiation;
a conductive member forming step of forming a conductive member by disposing a conductive material so as to cover the transfer mold;
a peeling step of peeling the structure including the transfer mold and the conductive member from the base material to expose the plurality of conductive members corresponding to the plurality of electrodes together with a surface of the transfer mold attached to the conductive member on the base material side; and
a dissolving step of dissolving the transfer mold attached to each of the plurality of conductive members with an aqueous dissolving liquid to obtain the plurality of electrodes having the concave portions including the inverted shape of the transfer mold.
13. The method of forming an electrode member according to claim 12, further comprising a heating step of heating the reverse casting mold on the base material during a period after the hardening step and before the dissolving step is started.
14. The method for forming an electrode member according to claim 12 or 13, wherein
In the disposing step, the polymerizable composition is supplied to the base material, thereby disposing a pattern of a coating film of the polymerizable composition on the base material,
in the curing step, the pattern of the coating film of the polymerizable composition on the base material is cured, and the pattern of the ionizing radiation cured product is formed on the base material as the transfer mold.
15. The method for forming an electrode member according to claim 14, wherein the polymerizable composition is an ink-jet ink, and in the disposing step, a pattern of a coating film of the polymerizable composition is disposed on the substrate using an ink-jet printer.
16. The method for forming an electrode member according to claim 12 or 13, wherein
In the disposing step, a layer of the polymerizable composition is formed on the base material,
in the curing step, a layer of the ionizing radiation cured product is formed from the layer of the polymerizable composition,
the method of forming an electrode member further includes a patterning step of irradiating a portion of the layer of the ionizing radiation cured product with high-energy rays to remove the ionizing radiation cured product, thereby forming the pattern of the ionizing radiation cured product on the base material as the transfer mold, before the step of forming the conductive member starts.
17. The method of forming an electrode member according to any one of claims 14 to 16, wherein in the conductive member forming step, a plurality of electrically independent patterns of the conductive members are formed on the base, the wiring electrically connected to the patterns of the plurality of conductive members is further formed, and an insulating material is disposed around the patterns of the plurality of conductive members and the wiring to form the insulating substrate on the base, and in the peeling step, the structure peeled from the base includes the transfer mold and the insulating substrate.
CN201980032967.9A 2018-06-14 2019-06-11 Polymerizable composition, ink, transfer mold, and method for producing electrode member Pending CN112119101A (en)

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