CN113383274A - Alkali development type photocurable thermosetting resin composition - Google Patents
Alkali development type photocurable thermosetting resin composition Download PDFInfo
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- CN113383274A CN113383274A CN201980091234.2A CN201980091234A CN113383274A CN 113383274 A CN113383274 A CN 113383274A CN 201980091234 A CN201980091234 A CN 201980091234A CN 113383274 A CN113383274 A CN 113383274A
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- photopolymerization initiator
- alkali
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- resin composition
- oxime bond
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- 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
- G03F7/004—Photosensitive materials
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- 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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
[ problem ] to provide: an alkali developable curable resin composition which can suppress the deterioration of performance even under severe storage conditions. [ solution ] an alkali-developable curable resin composition characterized by containing at least: (A) an alkali-soluble resin, (B) a photopolymerization initiator having an oxime bond, (C) a reactive diluent, and (D) a thermosetting resin, and is composed of (B) a photopolymerization initiator having an oxime bond and (A) an alkali-soluble resin, and is blended in at least two-component systems of different compositions, wherein at least 1 kind of (E) orthoester compound is blended together with (B) a photopolymerization initiator having an oxime bond.
Description
Technical Field
The present invention relates to an alkali-developable photocurable thermosetting resin composition, a cured product obtained by curing the composition, and an electronic component having the cured product.
Background
Conventionally, a solder resist has been used as a protective material for a circuit board circuit in a printed wiring board, and an example of the material composition is an alkali development type photocurable thermosetting resin composition (hereinafter, also simply referred to as a curable resin composition).
In order to form a more precise pattern in the curable resin composition, a photopolymerization initiator having higher sensitivity may be used to increase the sensitivity at the time of exposure and to allow photocuring to the depth of the coating film.
As such a photopolymerization initiator, for example, a technique using a photopolymerization initiator having an oxime bond has been proposed (patent document 1).
On the other hand, however, the photopolymerization initiator having an oxime bond has a property that its performance is easily lowered by contact with a resin having a carboxyl group, and there is a concern that it may be thickened by contact with a reactive diluent. As a result, the quality of the composition containing the compound may be deteriorated.
Therefore, the technique of patent document 1 is characterized by forming a curable resin composition having a two-component system composition in which a photopolymerization initiator having an oxime bond and a resin having a carboxyl group or a reactive diluent are compounded as separate components. By forming such a two-component system, a curable resin composition having excellent storage stability is provided.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2004/048434
Disclosure of Invention
Problems to be solved by the invention
Therefore, from the viewpoint of exhibiting its stable performance, a composition containing a highly photosensitive compound such as the photopolymerization initiator having an oxime bond is desired to have higher quality stability during storage. Thereby, it is possible to provide: for example, a curable resin composition which is easily brought to a relatively high temperature by storage such as transportation on a ship and which has stable quality even after the transportation time has reached a long and severe storage condition. When such storage conditions are assumed, it is considered that the performance of the curable resin composition must be maintained as much as possible even after 5 days or more at 50 ℃.
In this regard, the technique described in patent document 1 forms a two-component system as described above, and thereby can suppress the performance degradation of the photopolymerization initiator having an oxime bond, and the like, and can maintain the performance of the curable resin composition containing the photopolymerization initiator.
However, this technique does not even assume that the curable resin composition is left at least at 50 ℃ for 5 days or more.
Accordingly, an object of the present invention is to provide: a curable resin composition which is suppressed in performance deterioration even under such severe storage conditions.
Means for solving the problems
First, a two-component curable resin composition containing a photopolymerization initiator having an oxime bond was subjected to a test with time at 50 ℃ for 5 days, but the pattern formation by exposure/development was not possible due to the decrease in sensitivity.
Therefore, the mechanism of deterioration of the photopolymerization initiator having an oxime bond in the curable resin composition has been investigated again, and as a result, the following findings have been obtained: a trace amount of moisture contained in the composition adversely affects an oxime bond in the chemical structure of a photopolymerization initiator having an oxime bond. The decomposition of the oxime bond due to the moisture results in deactivation of the photopolymerization initiator having an oxime bond, which also undesirably affects the formation of a cured film. Further, even when the photopolymerization initiator having an oxime bond, the resin having a carboxyl group, and the reactive diluent are compounded as separate components in a two-component system as described above, adverse effects due to the presence of moisture cannot be sufficiently avoided.
In view of this, when a photopolymerization initiator having an oxime bond is blended in a two-component curable resin composition, it has been attempted to blend a dehydrating agent such as zeolite or silica gel. However, these problems are another problem that dispersion in the composition is difficult, and therefore, they cannot be directly used for suppressing deactivation of the photopolymerization initiator having an oxime bond.
Therefore, further intensive studies have been conducted, and as a result, it has been found that: the present inventors have found that a photopolymerization initiator having an oxime bond and an alkali-soluble resin are separately prepared, and a specific orthoester compound is blended with the photopolymerization initiator having an oxime bond in a curable resin composition, whereby the deactivation of the photopolymerization initiator having an oxime bond can be effectively suppressed even when the composition is stored at 50 ℃ for 5 days, whereby the storage stability of the composition can be improved, and the present invention has been completed.
That is, the object of the present invention can be achieved by an alkali development type curable resin composition characterized by containing at least: (A) an alkali-soluble resin, (B) a photopolymerization initiator having an oxime bond, (C) a reactive diluent, and (D) a thermosetting resin, and is composed of (B) a photopolymerization initiator having an oxime bond and (A) an alkali-soluble resin, and the photopolymerization initiator and the alkali-soluble resin are blended in different compositions,
wherein at least 1 kind of (E) orthoester compound is blended together with the (B) photopolymerization initiator having an oxime bond.
In the alkali developable curable resin composition of the present invention, the (E) orthoester compound is preferably at least 1 selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, propyl orthopropionate and butyl orthopropionate, more preferably at least 1 selected from the group consisting of trimethyl orthoformate, triethyl orthoformate and triethyl orthoacetate, and most preferably triethyl orthoformate.
Further, the present invention provides: a cured product obtained by curing the alkali-developable curable resin composition, and an electronic component having the cured product.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a curable resin composition of a two-component system in which a decrease in properties, such as sensitivity, is effectively suppressed after at least 5 days at 50 ℃.
Therefore, for example, it is suitable for storage of the composition under severe conditions such as transportation by ship.
Detailed Description
The curable resin composition of the present invention is an at least two-component system in which (B) a photopolymerization initiator having an oxime bond and (a) an alkali-soluble resin are blended in different compositions.
For example, the main agent composition and the curing agent composition are prepared separately and mixed at the time of use, and thus can be used. It is needless to say that these compositions may be further formed into a composition of a three-component system or more, as required.
Examples of the components of the main agent composition include an alkali-soluble resin, a reactive diluent, a solvent, a pigment, and a photopolymerization initiator. On the other hand, examples of the components of the curing agent composition include a thermosetting resin, a solvent, and a photopolymerization initiator having an oxime bond.
Further, according to the present invention, not only (B) the photopolymerization initiator having an oxime bond and (a) the alkali-soluble resin are compounded in different compositions, but also (E) the orthoester compound is compounded together with (B) the photopolymerization initiator having an oxime bond. It is presumed that the decomposition of the oxime bond by moisture in the composition is effectively suppressed, that is, the sensitivity thereof can be maintained.
The curable resin composition of the present invention thus compounded can effectively suppress the deterioration of the properties even after 5 days at least at 50 ℃.
Hereinafter, each component will be described.
[ (A) alkali-soluble resin ]
(A) The alkali-soluble resin is a resin containing 1 or more functional groups of phenolic hydroxyl group, mercapto group and carboxyl group and soluble in an alkali solution, and preferable examples thereof include: a compound having 2 or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, a compound having 2 or more mercapto groups. As the alkali-soluble resin (a), a carboxyl group-containing resin and a phenolic hydroxyl group-containing resin can be used, and a carboxyl group-containing resin is preferable.
The carboxyl group-containing resin preferably has an ethylenically unsaturated bond in the molecule in addition to the carboxyl group, and a carboxyl group-containing resin having no ethylenically unsaturated double bond may be used, from the viewpoint of photocurability and development resistance. As the ethylenic unsaturated bond, acrylic acid or methacrylic acid or a derivative thereof is preferably derived. Among the carboxyl group-containing resins, a carboxyl group-containing resin having a copolymerized structure, a carboxyl group-containing resin having a urethane structure, a carboxyl group-containing resin using an epoxy resin as a starting material, and a carboxyl group-containing resin using a phenol compound as a starting material are preferable. Specific examples of the carboxyl group-containing resin include the following compounds (both oligomers and polymers).
(1) A carboxyl group-containing photosensitive resin obtained by reacting a 2-functional or higher polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to a hydroxyl group present in a side chain. Here, the 2-functional or higher polyfunctional epoxy resin is preferably a solid.
(2) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional epoxy resin with epichlorohydrin with (meth) acrylic acid and adding a dibasic acid anhydride to the resulting hydroxyl group. Here, the 2-functional epoxy resin is preferably a solid.
(3) A carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having 2 or more epoxy groups in 1 molecule, a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, or the like.
(4) A carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule, such as bisphenol a, bisphenol F, bisphenol S, novolak-type phenol resins, polyparahydroxystyrene, condensate of naphthol and aldehydes, or condensate of dihydroxynaphthalene and aldehydes, with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.
(5) A carboxyl group-containing photosensitive resin obtained by reacting a compound having 2 or more phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the obtained reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride.
(6) A carboxyl-group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, wherein the terminal of the urethane resin is reacted with an acid anhydride.
(7) In the synthesis of a carboxyl group-containing urethane resin obtained by addition polymerization of a diisocyanate with a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid and a diol compound, a carboxyl group-containing urethane resin having a terminal (meth) acryloyl group is synthesized by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) propionate.
(8) In the synthesis of a carboxyl group-containing polyurethane resin obtained by a polyaddition reaction of a diisocyanate, a carboxyl group-containing diol compound, and a diol compound, a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol trisropionate, is added, and a carboxyl group-containing polyurethane resin having a terminal (meth) acryloyl group is performed.
(9) A carboxyl group-containing photosensitive resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) propionate, or isobutylene.
(10) A carboxyl group-containing photosensitive resin is obtained by reacting a polyfunctional oxetane resin described later with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid to add a dibasic acid anhydride to the primary hydroxyl group formed, and then adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule, such as glycidyl (meth) propionate or α -methylglycidyl (meth) propionate, to the carboxyl group-containing polyester resin obtained.
(11) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in 1 molecule to any of the carboxyl group-containing resins (1) to (10).
Here, the term (meth) propionate is a general term referring to propionate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.
The acid value of the carboxyl group-containing resin is preferably 40 to 150 mgKOH/g. The acid value of the carboxyl group-containing resin is set to 40mgKOH/g or more, whereby alkali development is favorable. In addition, by setting the acid value to 150mgKOH/g or less, a normal resist pattern can be easily drawn. More preferably 50 to 130 mgKOH/g.
(A) The mass average molecular weight of the alkali-soluble resin also depends on the resin skeleton, and is preferably in the range of 1500 to 150000, more preferably 1500 to 100000. When the mass average molecular weight is 1500 or more, the tack free property is good, the moisture resistance of the coating film after exposure is good, the film loss at the time of development can be suppressed, and the decrease in resolution can be suppressed. On the other hand, when the mass average molecular weight is 150000 or less, the developability is good and the storage stability is also excellent.
In the present invention, the content of the alkali-soluble resin (a) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, based on the entire composition. When the amount is 10 to 60% by mass, the coating film strength is good, the viscosity of the composition is moderate, and the coating property can be improved.
These (a) alkali-soluble resins may be used alone in 1 kind or in combination of 2 or more kinds.
[ (B) photopolymerization initiator having oxime bond ]
As the photopolymerization initiator (B) having an oxime bond, for example, known ones such as o-acyloxime ester compounds, oxime sulfonate compounds, ketoxime ether compounds, and the like can be used.
Examples of commercially available products include CGI-325, TOE-04-A3 (Nippon chemical Co., Ltd.), Irgacure OXE01 and Irgacure OXE02 (both of BASF Japan Co., Ltd.), and N-1919 and NCI-831 (both of ADEKA CORPORATION), but are not limited thereto.
(B) The content of the photopolymerization initiator having an oxime bond is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, based on the alkali-soluble resin (a). (B) When the content of the photopolymerization initiator having an oxime bond is 0.01% by mass or more, photocurability on copper is good, the coating film is not easily peeled off, and coating film characteristics such as chemical resistance are good. On the other hand, when the content of the photopolymerization initiator having an oxime bond (B) is 30% by mass or less, the photopolymerization initiator having an oxime bond (B) has good light absorption and improved deep curability.
[ (C) reactive diluent ]
The reactive diluent (C) used in the present invention is used for the purpose of adjusting the viscosity of the composition to improve workability, increasing the crosslinking density, and obtaining a coating film having adhesion and the like. Examples of the reactive diluent (C) include: compounds having 1 or more unsaturated double bonds in 1 molecule, for example, alkyl (meth) propionate esters such as 2-ethylhexyl (meth) propionate and cyclohexyl (meth) propionate; hydroxyalkyl (meth) propionate esters such as 2-hydroxyethyl (meth) propionate and 2-hydroxypropyl (meth) propionate; mono-or di (methyl) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc.; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and trihydroxyethylisocyanurate, and polyhydric (meth) acrylates of ethylene oxide or propylene oxide adducts thereof; (meth) acrylic acid esters of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) propionate and polyethoxydi (meth) propionate of bisphenol A; (meth) acrylic acid esters of glycidyl ethers such as glycerol diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth) propionate, and the like. Among them, liquid ones are preferable in view of reactivity and dilutability.
In addition, a compound having an unsaturated double bond in 1 molecule and further having a carboxyl group may be used as the (C) reactive diluent. As such a compound, a reaction product of a saturated or unsaturated dibasic acid anhydride and a (meth) propionic acid ester having 1 hydroxyl group in 1 molecule, for example, a reaction product obtained by reacting a saturated or unsaturated dibasic acid anhydride such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like, and a reaction product obtained by reacting a (meth) propionic acid ester having 1 hydroxyl group in 1 molecule, such as hydroxyethyl (meth) propionate, hydroxypropyl (meth) propionate, hydroxybutyl (meth) propionate, polyethylene glycol mono (meth) propionate, glycerol di (meth) propionate, trimethylolpropane di (meth) propionate, pentaerythritol tri (meth) propionate, dipentaerythritol penta (meth) propionate, and (meth) propionate of phenyl glycidyl ether, in an equimolar ratio The resulting half-esters. These (C) reactive diluents may be used alone or in combination of 2 or more.
From the viewpoint of the properties and sensitivity of the formed coating film, the content of the reactive diluent (C) is preferably in the range of approximately 2 to 60 mass%, more preferably 10 to 40 mass%, relative to the alkali-soluble resin (a).
[ (D) thermosetting resin ]
Examples of the thermosetting resin (D) include: examples of the thermosetting resin include known thermosetting resins such as polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like, which have 2 or more cyclic ether groups and/or cyclic thioether groups in the molecule, compounds having 2 or more isocyanate groups in 1 molecule such as polyisocyanate compounds and blocked isocyanate compounds, or compounds having blocked isocyanate groups, amine resins such as melamine resins and benzoguanamine resins, and derivatives thereof, bismaleimides, oxazines, cyclic carbonate compounds, and carbodiimide resins.
As the epoxy resin, a publicly known and commonly used multifunctional epoxy resin having at least 2 epoxy groups in 1 molecule can be used. The epoxy resin may be liquid, solid or semi-solid. Examples of the polyfunctional epoxy resin include: bisphenol a type epoxy resin; brominated epoxy resins; a novolac type epoxy resin; bisphenol F type epoxy resins; hydrogenated bisphenol a type epoxy resin; glycidyl amine type epoxy resins; hydantoin type epoxy resins; an alicyclic epoxy resin; trihydroxyphenyl methane type epoxy resin; a bixylenol-type or biphenol-type epoxy resin or a mixture thereof; bisphenol S type epoxy resin; bisphenol a novolac type epoxy resin; tetrahydroxyphenylethane-type epoxy resins; a heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl toloyl ethane resin; a naphthyl-containing epoxy resin; an epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives; CTBN-modified epoxy resins, etc., but are not limited thereto. The epoxy resin is preferably a bisphenol a-type or bisphenol F-type novolac-type epoxy resin, a bixylenol-type epoxy resin, a biphenol novolac-type (biphenyl aralkyl-type) epoxy resin, a naphthalene-type epoxy resin, or a mixture thereof.
Among them, an epoxy resin having a hydrogenated cyclic skeleton is preferable from the viewpoint of improving resolution/light resistance.
Examples of the epoxy resin having a hydrogenated cyclic skeleton include YX-8000, YX-8034 and YX-8040 manufactured by Mitsubishi chemical, ST-3000 manufactured by Nippon iron chemical, and EP-4080 manufactured by ST-4000D, ADEKA.
The content of the thermosetting resin (D) described above is preferably in a range of approximately 30 to 90% by mass, and more preferably 40 to 70% by mass, relative to the alkali-soluble resin (a).
[ (E) orthoester Compound ]
The orthoester compound (E) found in the present invention does not react with the base material or ink components, and volatilizes and does not remain in the composition in the first drying step after the solder resist composition containing the orthoester compound (E) is applied to the substrate. Therefore, the following advantages are also provided: not only deactivation of the photopolymerization initiator having an oxime bond (B) can be suppressed, but also there is no fear of an undesirable influence on developability and the characteristics of the cured coating.
As described above, in the present invention, (E) an orthoester compound is blended in the same system together with (B) a photopolymerization initiator having an oxime bond.
The orthoester compound (E) used in the present invention is preferably trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, propyl orthopropionate, or butyl orthopropionate.
Among them, trimethyl orthoformate, triethyl orthoformate and triethyl orthoacetate are more preferable, and triethyl orthoformate is most preferable.
The ortho ester compound (E) is contained in the composition of the two-component system in an amount of preferably 1 to 10% by mass, more preferably 3 to 6% by mass, based on the total amount of the curing agent composition, from the viewpoint of effectively exhibiting the performance thereof.
[ coloring agent ]
As the colorant, a known colorant can be used. Further, 1 kind of the colorant may be used alone, or 2 or more kinds may be used in combination.
As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments can be used. More specifically, The colorant includes colorants having The following color index (C.I.; issued by The Society of Dyers and Colourists).
As red colorants, there are: monoazo systems, disazo systems, azo lake systems, benzimidazolone systems, perylene systems, diketopyrrolopyrrole systems, condensed azo systems, anthraquinone systems, quinacridone systems, and the like. As the blue colorant, there are: phthalocyanine-based and anthraquinone-based, and compounds classified as pigments (pigments) can be used as the Pigment system. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. As green colorants, there are likewise: phthalocyanine, anthraquinone, and perylene. Besides, a metal-substituted or unsubstituted phthalocyanine compound can also be used. As yellow colorants, there are: monoazo systems, disazo systems, condensed azo systems, benzimidazolone systems, isoindolinone systems, anthraquinone systems, and the like. Examples of the white colorant include rutile type and anatase type titanium oxide. As black colorants, there are: carbon black, graphite, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, aniline, molybdenum sulfide, bismuth sulfide, and the like. Further, for the purpose of adjusting the color tone, a coloring agent of violet, orange, brown, or the like may also be added.
When the curable resin composition of the present invention is used as a solder resist composition, the content of the colorant is 0.03 to 7% by mass, more preferably 0.05 to 5% by mass in terms of solid content, based on the total amount of the curable resin composition of the present invention.
Here, the curable resin composition of the present invention can be suitably used for a black mask agent or the like using a highly sensitive photopolymerization initiator so as to be able to suppress deactivation of (B) the photopolymerization initiator having an oxime bond.
When the curable resin composition of the present invention is used as a black masking agent or the like, the content of the colorant is preferably 5 to 50% by mass in terms of solid content relative to the total amount of the curable resin composition of the present invention from the viewpoint of improving the hiding property of a cured product, so that both the hiding property and the resolution can be satisfied. More preferably 10 to 30% by mass.
When the curable resin composition of the present invention is used as a black masking agent or the like, carbon black is preferably contained as a colorant, and carbon black and a mixed-color black colorant are preferably used in combination. In particular, when carbon black and a mixed-color black colorant are used in combination, it is preferable that the carbon black is contained in an amount of 4 to 10% by mass and the mixed-color black colorant is contained in an amount of 8 to 20% by mass in terms of solid content with respect to the total amount of the curable resin composition.
The mixed-color black-based colorant is a colorant obtained by mixing colorants such as a red colorant, a blue colorant, a green colorant, a yellow colorant, a violet colorant, and an orange colorant to obtain a color of black or a color close to black. The mixed black colorant is preferably added to the resin composition after mixing the colorants in advance, and the colorants constituting the mixed black colorant may be added to the resin composition separately.
[ other ingredients ]
In the curable resin composition of the present invention, if necessary, further additives may be blended as other components within the range not departing from the object of the present invention.
Examples of such components include: (B) a photopolymerization initiator other than the photopolymerization initiator having an oxime bond, a solvent, a thermal polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/antifungal agent, a leveling agent, a thickener, an adhesion imparting agent, a thixotropy imparting agent, a photo-initiation aid, a sensitizer, a photobase generator, an organic filler such as a thermoplastic resin, an elastomer, urethane beads and the like, an inorganic filler, a mold release agent, a surface treating agent, a dispersant, a dispersion aid, a surface modifying agent, a stabilizer, a phosphor, a cellulose resin and the like.
[ cured product ]
When a cured product is formed using the curable composition of the present invention, the composition is applied to a substrate, the solvent is evaporated and dried, and the obtained resin layer is exposed (irradiated with light), whereby the exposed portion (the portion irradiated with light) is cured. Specifically, a resist pattern is formed by selectively exposing the substrate with an active energy ray through a photomask having a pattern formed thereon by a contact or non-contact method, or directly exposing the substrate with a pattern by a laser direct exposure machine, and developing the unexposed portion with an aqueous alkali solution (for example, an aqueous sodium carbonate solution of 0.3 to 3 mass%) to form a resist pattern. Further heating to a temperature of about 100 to 180 ℃ to thermally cure (post-cure) the composition, thereby forming a cured coating (cured product) having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.
[ electronic component ]
The present invention also provides an electronic component having the cured product.
By using the curable resin composition of the present invention, an electronic component having high quality, durability and reliability can be provided.
In the present invention, the electronic component means a component used in an electronic circuit, and includes not only an active component such as a printed circuit board, a transistor, a light emitting diode, or a laser diode, but also a passive component such as a resistor, a capacitor, an inductor, or a connector.
[ methods for producing and Using the curable resin composition of the present invention ]
The curable resin composition of the present invention can be prepared as follows: these 2 compositions are prepared by mixing and dispersing the respective components of the main agent composition and the curing agent composition in predetermined amounts by, for example, a three-roll mill, and then these 2 compositions are mixed at the time of use.
The formation of a coating film using the curable resin composition of the present invention is performed as follows.
First, a curable resin composition is applied onto a substrate, a solvent is evaporated and dried, and then the obtained resin layer is exposed (irradiated with light), whereby an exposed portion (a portion irradiated with light) is cured. Specifically, the exposure is selectively performed by an active energy ray through a photomask having a pattern formed thereon by a contact or non-contact method, or the pattern exposure is directly performed by a laser direct exposure machine. Then, the unexposed portion is developed with an alkali aqueous solution (e.g., a 0.3 to 3 mass% sodium carbonate aqueous solution) to form a resist pattern. Further heating to a temperature of about 100 to 180 ℃ to thermally cure (post-cure) the composition, thereby forming a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.
Here, the curable resin composition of the present invention may be formed into a tack-free resin layer by adjusting the viscosity to a viscosity suitable for a coating method using an organic solvent, applying the composition onto a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating, and then volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ℃.
Examples of the base material include a printed wiring board and a flexible printed wiring board on which a circuit is formed in advance with copper or the like, and further include: copper-clad laminates of all grades (FR-4 and the like) made of materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, and copper-clad laminates for high-frequency circuits made of fluororesin/polyethylene/polyphenylene oxide (polyphenylene oxide)/cyanate ester, as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, and the like.
The volatilization drying or the heat curing can be performed by, for example, a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like (a method of bringing hot air in a drying machine into convection contact by using a device having a heat source of an air heating system using steam and a method of blowing the hot air onto a support by a nozzle).
The exposure machine used for the irradiation with active energy rays may be a device that is equipped with a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like and irradiates ultraviolet rays in the range of 350 to 450nm, and may further be a direct drawing device (for example)Such as a laser direct imaging device that directly laser traces an image using CAD data from a computer). As a lamp light source or a laser light source of the line drawing machine, the maximum wavelength can be in the range of 350-410 nm. The exposure amount for image formation varies depending on the film thickness, and generally 20 to 2000mJ/cm2Preferably 20 to 1500mJ/cm2Within the range of (1).
As the developing method, a dipping method, a spraying method, a brush coating method, or the like can be used, and as the developing solution, an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like can be used.
Examples
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples.
Unless otherwise stated, "parts" and "%" are based on mass.
A two-component curable resin composition comprising a base composition and a curing agent composition was prepared as follows.
Example 1
100 parts of alkali-soluble resin, 7.2 parts of photopolymerization initiator, 3.8 parts of additive, 28.6 parts of reactive diluent, 553.3 parts of solvent A, 10.0 parts of carbon black, 10.0 parts of perylene Red and 10.0 parts of phthalocyanine blue were mixed and dispersed by a three-roll mill to obtain the base composition of example 1.
On the other hand, 56.7 parts of a thermosetting resin, 4.0 parts of a photopolymerization initiator a having an oxime bond, 20.0 parts of a solvent B, and 4.0 parts of trimethyl orthoformate were mixed and dispersed by a three-roll mill to obtain a curing agent composition of example 1.
Example 2
The same procedure as in example 1 was repeated to obtain the base composition of example 2.
On the other hand, a curing agent composition of example 2 was obtained in the same manner as in example 1 except that triethyl orthoformate was replaced with trimethyl orthoformate.
Example 3
The same procedure as in example 1 was repeated to obtain the base composition of example 3.
On the other hand, a curing agent composition of example 3 was obtained in the same manner as in example 1 except that triethyl orthoacetate was replaced with trimethyl orthoformate.
Example 4
The same procedure as in example 1 was repeated to obtain the base composition of example 4.
On the other hand, a curing agent composition of example 4 was obtained in the same manner as in example 1 except that the photopolymerization initiator a having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond.
Example 5
The same procedure as in example 1 was repeated to obtain the base composition of example 5.
On the other hand, a curing agent composition of example 5 was obtained in the same manner as in example 2 except that the photopolymerization initiator a having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond.
Example 6
The same procedure as in example 1 was repeated to obtain the base composition of example 6.
On the other hand, a curing agent composition of example 6 was obtained in the same manner as in example 3, except that the photopolymerization initiator a having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond.
Example 7
The same procedure as in example 1 was repeated to obtain the base composition of example 6.
On the other hand, a curing agent composition of example 7 was obtained in the same manner as in example 2 except that triethyl orthoformate was replaced with 0.8 parts.
Example 8
The same procedure as in example 1 was repeated to obtain the base composition of example 6.
On the other hand, a curing agent composition of example 7 was obtained in the same manner as in example 2 except that triethyl orthoformate was replaced with 9.0 parts.
Comparative example 1
100 parts of alkali-soluble resin, 7.2 parts of photopolymerization initiator, 3.8 parts of additive, 28.6 parts of reactive diluent, 553.3 parts of solvent A, 10.0 parts of carbon black, 10.0 parts of perylene Red and 10.0 parts of phthalocyanine blue were mixed and dispersed by a three-roll mill to obtain the main agent composition of comparative example 1.
On the other hand, 56.7 parts of a thermosetting resin, 4.0 parts of a photopolymerization initiator a having an oxime bond, and 20.0 parts of a solvent B were mixed and dispersed by a three-roll mill to obtain a curing agent composition of comparative example 1.
Comparative example 2
The same procedure as in comparative example 1 was carried out to obtain the base composition of comparative example 2.
On the other hand, a curing agent composition of comparative example 2 was obtained in the same manner as in comparative example 1 except that the amount of the photopolymerization initiator a having an oxime bond was changed to 8.0 parts.
Comparative example 3
A base composition of comparative example 3 was obtained in the same manner as in comparative example 1.
On the other hand, a curing agent composition of comparative example 3 was obtained in the same manner as in comparative example 1 except that the amount of the photopolymerization initiator a having an oxime bond was changed to 12.0 parts.
Comparative example 4
A base composition of comparative example 4 was obtained in the same manner as in comparative example 1.
On the other hand, a curing agent composition of comparative example 4 was obtained in the same manner as in comparative example 1, except that the photopolymerization initiator a having an oxime bond was replaced with the photopolymerization initiator B having an oxime bond.
The compositions of examples 1 to 8 and comparative examples 1 to 4 are shown in Table 1 below.
[ Table 1]
TABLE 1 composition of curable resin composition
Alkali-soluble resin: cyclomer P (ACA) Z250(Daicel co., Ltd.) (carboxyl group-containing acrylic copolymer having alicyclic skeleton)
Photopolymerization initiator: omnirad TPO (IGM Resins Co.)
Additive: BYK-361N (nonionic surfactant; BYK Co., Ltd.)
Reactive diluents: LR8863 (EO-modified trimethylolpropane triacrylate; BASF Japan K.K.)
Solvent A: DOWANOL PM (propylene glycol monomethyl ether; Dow Chemical Japan Co., Ltd.)
Carbon black: MA-100 (carbon Black, Mitsubishi chemical corporation)
Perylene Red (perylene Red colorant) (C.I. pigment Red 149)
Phthalocyanine Blue (phthalocyanine-based Blue colorant) (C.I. pigment Blue 15: 3)
Thermosetting resin: YX-8034 (hydrogenated bisphenol A epoxy resin; Mitsubishi chemical Co., Ltd.)
Photopolymerization initiator having oxime bond a: TOE-04-A3 (Nippon chemical industry Co., Ltd.)
Photopolymerization initiator B having oxime bond: irgacure OXE02(BASF Japan K.K.)
Solvent B: propylene carbonate (propylene carbonate; Kanto chemical Co., Ltd.)
Test examples
Tests concerning the sensitivity of the coating films produced from these samples before and after being left at 50 ℃ for 7 days were conducted on the curable resin compositions of examples 1 to 8 and comparative examples 1 to 4, and it was confirmed how much the deactivation of the photopolymerization initiator having an oxime bond can be suppressed.
Test method
< preparation of coating film >
After the obtained base composition and the curing agent composition of each of examples 1 to 8 and comparative examples 1 to 4 were mixed well, the mixture was coated on a glass substrate with an applicator so that the film thickness after drying became 10 μm, and then dried in a hot air circulation type drying oven at 80 ℃ for 30 minutes to prepare each coating film (initial).
On the other hand, each of the base composition and the curing agent composition was prepared separately, and the mixture was allowed to stand at 50 ℃ for 7 days in a thermostatic bath, and then mixed and dried in the same manner as described above to prepare a coating film (after 7 days at 50 ℃).
< sensitivity >
The dried coating films were closely attached to STEP Tablet (Kodak No.2), and exposed to 1000mJ/cm using an exposure machine of a metal halide lamp2Exposure was carried out at an exposure amount of (1%) and sensitivity was evaluated on the basis of the number of residual STEPs and the number of gloss STEPs obtained from STEP Tablet after development at 30 ℃ for 1 minute under a spray pressure of 0.2MPa with a 1% by mass aqueous solution of sodium carbonate.
The results are shown in table 2 below.
[ Table 2]
TABLE 2 sensitivity of coating film
[ OD value ]
The coated side of the glass substrate (initially, after 7 days at 50 ℃) prepared in the above coating film preparation was faced to a measuring instrument, and mounted on a transmission concentration meter (model: X-Rite 361T, manufactured by SAKATAINX CORPORATION, light source wavelength: 400 to 800nm) to evaluate OD value. The evaluation criteria are as follows.
O. OD value exceeding 4
Delta. OD value of 3 to 4
OD value less than 3
< results >
In examples 1 to 8, it was found that the decrease in the sensitivity was effectively suppressed in both the number of initial residual steps and the number of gloss steps after 7 days at 50 ℃. This is considered to be because the incorporation of the (E) orthoester compound effectively suppresses the deactivation of the photopolymerization initiator having an oxime bond with time. It was thus confirmed that the curable resin composition of the present invention has excellent storage stability under severe conditions.
In addition, as for the evaluation results of OD value, the description in Table 2 is omitted, but examples 1 to 8 show that both the initial OD value and the OD value after 7 days at 50 ℃ are more than 4 (evaluation standard: good).
The evaluation results of OD values of comparative examples 1 to 4 were similarly omitted from Table 2, but initial OD values were more than 4 (evaluation standard: good), but no coating film was formed after 7 days at 50 ℃ and evaluation was impossible.
As described above, since the photopolymerization initiator having an oxime bond in the curable resin composition of the present invention is effectively inhibited from being deactivated with time, the composition can be suitably used as a black masking agent without change in initial OD value or OD value after 7 days at 50 ℃.
Claims (6)
1. An alkali-developable curable resin composition comprising at least: (A) an alkali-soluble resin, (B) a photopolymerization initiator having an oxime bond, (C) a reactive diluent, and (D) a thermosetting resin, and is composed of (B) a photopolymerization initiator having an oxime bond and (A) the alkali-soluble resin blended in different compositions,
wherein at least 1 kind of (E) orthoester compound is compounded together with the photopolymerization initiator having an oxime bond.
2. The alkali developable curable resin composition according to claim 1, wherein the (E) orthoester compound is at least 1 selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, propyl orthopropionate, and butyl orthopropionate.
3. The alkali developable curable resin composition according to claim 1 or 2, wherein the (E) orthoester compound is at least 1 selected from the group consisting of trimethyl orthoformate, triethyl orthoformate, and triethyl orthoacetate.
4. The alkali developable curable resin composition according to any one of claims 1 to 3, wherein the (E) orthoester compound is triethyl orthoformate.
5. A cured product obtained by curing the alkali developable curable resin composition according to any one of claims 1 to 4.
6. An electronic component comprising the cured product according to claim 5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019037477A JP7330719B2 (en) | 2019-03-01 | 2019-03-01 | Alkali developable photocurable thermosetting resin composition |
| JP2019-037477 | 2019-03-01 | ||
| PCT/JP2019/047553 WO2020179163A1 (en) | 2019-03-01 | 2019-12-05 | Alkali developable photocurable thermosetting resin composition |
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| CN113383274A true CN113383274A (en) | 2021-09-10 |
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| CN201980091234.2A Pending CN113383274A (en) | 2019-03-01 | 2019-12-05 | Alkali development type photocurable thermosetting resin composition |
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| Country | Link |
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| JP (1) | JP7330719B2 (en) |
| KR (1) | KR20210135991A (en) |
| CN (1) | CN113383274A (en) |
| TW (1) | TWI813829B (en) |
| WO (1) | WO2020179163A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04368949A (en) * | 1991-06-18 | 1992-12-21 | Sumitomo Chem Co Ltd | Positive resist composition |
| TW200417294A (en) * | 2002-11-28 | 2004-09-01 | Taiyo Ink Mfg Co Ltd | Photo- and thermo-setting resin composition and printed wiring boards made by using the same |
| JP4893527B2 (en) * | 2007-08-10 | 2012-03-07 | Ｊｓｒ株式会社 | Photosensitive resin composition |
| JP5740832B2 (en) * | 2009-06-08 | 2015-07-01 | Jsr株式会社 | Radiation-sensitive composition, protective film, interlayer insulating film, and method for forming them |
| JP6010484B2 (en) * | 2013-02-28 | 2016-10-19 | 株式会社カネカ | Photosensitive resin composition preparation kit and use thereof |
| JP6248561B2 (en) * | 2013-11-14 | 2017-12-20 | 日本ゼオン株式会社 | Radiation sensitive resin composition and laminate |
| TWI495956B (en) * | 2014-01-28 | 2015-08-11 | Daxin Materials Corp | Photosensitive resin composition, electronic element and method of fabricating the same |
| JP6281826B2 (en) * | 2015-06-15 | 2018-02-21 | 東洋インキＳｃホールディングス株式会社 | Photosensitive composition, photosensitive composition for color filter, and color filter |
| JP7112827B2 (en) * | 2015-12-25 | 2022-08-04 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, method for producing resin pattern, method for producing cured film pattern, and display device |
| KR102146312B1 (en) * | 2016-02-29 | 2020-08-20 | 후지필름 가부시키가이샤 | Composition, manufacturing method of composition, cured film, color filter, light shielding film, solid-state image sensor, and image display device |
| KR102160018B1 (en) * | 2016-03-31 | 2020-09-25 | 후지필름 가부시키가이샤 | Composition, cured film, color filter, light shielding film, solid-state image sensor and image display device |
| WO2017208771A1 (en) * | 2016-05-31 | 2017-12-07 | 富士フイルム株式会社 | Composition, cured film, color filter, light blocking film, solid-state imaging device and image display device |
| JP7194492B2 (en) * | 2016-10-24 | 2022-12-22 | 東京応化工業株式会社 | Photosensitive composition, method for producing photosensitive composition, photopolymerization initiator, and method for preparing photopolymerization initiator |
-
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- 2019-03-01 JP JP2019037477A patent/JP7330719B2/en active Active
- 2019-12-05 WO PCT/JP2019/047553 patent/WO2020179163A1/en active Application Filing
- 2019-12-05 KR KR1020217022297A patent/KR20210135991A/en not_active Application Discontinuation
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| TWI813829B (en) | 2023-09-01 |
| WO2020179163A1 (en) | 2020-09-10 |
| KR20210135991A (en) | 2021-11-16 |
| JP7330719B2 (en) | 2023-08-22 |
| TW202043917A (en) | 2020-12-01 |
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