CN110461920A - Etching solution and engraving method for resin combination - Google Patents
Etching solution and engraving method for resin combination Download PDFInfo
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- CN110461920A CN110461920A CN201880021886.4A CN201880021886A CN110461920A CN 110461920 A CN110461920 A CN 110461920A CN 201880021886 A CN201880021886 A CN 201880021886A CN 110461920 A CN110461920 A CN 110461920A
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- resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
- G03F7/2043—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means with the production of a chemical active agent from a fluid, e.g. an etching agent; with meterial deposition from the fluid phase, e.g. contamination resists
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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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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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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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Problem of the present invention is that, in processing of the removal comprising the resin combination of alkali-insoluble resin and inorganic filler, defect caused by not generating because of excessive heating containing resin composition layer made of the resin combination is provided and can only remove the etching solution or engraving method of resin composition layer.Etching solution, to contain in the etching solution of alkali-insoluble resin and the resin combination of the inorganic filler of 50 ~ 80 mass %, which contains the alkali metal hydroxide of 15 ~ 45 mass %, more preferably further containing the ethanolamine compound of 5 ~ 40 mass %.In addition, engraving method, using the etching solution, removal includes the resin combination of alkali-insoluble resin and inorganic filler.
Description
Technical field
The present invention relates to the resin combinations to contain alkali-insoluble resin and the inorganic filling material of 50 ~ 80 mass %
Etching solution and engraving method.
Background technique
In recent years, with the miniaturization of electronic equipment, high performance, in circuit substrate, strong request forms fine match
Line reduces thermal expansion coefficient.Wherein, the means as the low thermal coefficient of expansion of insulating materials, it is known that fill out insulating materials height
Filling, i.e. improve insulating materials in inorganic filling material content method.Further, as insulating materials, proposing makes
With including epoxy resin, phenol novolacs system curing agent, phenoxy resin, cyanate ester resin etc. and the excellent alkali of moisture-proof
Insoluble resin.These include the insulating properties of inorganic filling material and alkali-insoluble resin resin combination have heat resistance,
The excellent physical property such as dielectric property, mechanical strength, chemical resistance is widely used as making on the superficies of circuit substrate
Solder resist, the interlayer dielectic used in multilayer increasing layer distributing board.
Fig. 1 is the resistance for covering the part resin composition layer 4 other than the connection gasket 3 welded on circuit substrate
The outline cross section structure figure of solder flux pattern.Structure shown in FIG. 1 is referred to as SMD, and (Solder Masked Defined, welding are covered
Film limits) structure, which is characterized in that the opening portion of resin composition layer 4 is smaller compared with connection gasket 3.Structure quilt shown in Fig. 2
Referred to as NSMD (Non Solder Masked Defined, non-solder exposure mask limit) structure, which is characterized in that resin combination
The opening portion of layer 4 is bigger compared with connection gasket 3.
The opening portion of resin composition layer 4 in Fig. 1 is formed by a part in removal resin composition layer.As
Processing of the removal containing resin composition layer obtained from the resin combination comprising inorganic filling material and alkali-insoluble resin
Method well known to drilling, laser, plasma, sandblasting etc. can be used in method.In addition, as needed, these can also be combined
Method.Wherein, carbon dioxide laser, excimer laser, UV laser, YAG laser etc. are most conventional using the processing of laser, are led to
Laser irradiation is crossed, a part in resin composition layer 4 is removed, is capable of forming and is used to form the through hole of through-hole, is used to form
The through holes such as the opening portion of via hole, the opening portion for being used to form connection gasket 3, non-through hole are (referring for example to 1 He of patent document
2)。
However, in the processing using the irradiation of laser, such as using carbon dioxide laser, need a large amount of
Irradiation number need to carry out at desmearing using the oxidant of the aqueous solution comprising chromic acid, permanganate etc. as post-processing
Reason.In addition, it is very long to process the required time using excimer laser.Further, in the feelings of UV-YAG laser
Under condition, compared with other laser, can have superiority in terms of microfabrication, but the problem is that, not only removal tree
Oil/fat composition layer also while removing existing metal layer nearby.
In addition, if laser irradiation on resin composition layer, is then absorbed in irradiated site luminous energy by object, according to specific heat
And lead to object excessive heating, by the fever, the defects of the dissolution of resin occurs sometimes, deformation, goes bad, change colour.In addition, needle
To the fever, propose using thermosetting resin in resin composition layer, but if being then sometimes prone to using thermosetting resin
It is cracked in resin composition layer.
As the method other than laser irradiation, it can enumerate and resin composition layer is removed by wet blast method
Method.In insulative substrate, after forming resin composition layer on the circuit substrate with connection gasket, implement curing process,
After setting is used to form the resin layer of wet blast mask on resin composition layer, by exposing, developing, to form figure
The wet blast mask of case shape.Then, by carrying out wet blast, to remove resin composition layer, opening portion is formed, is connect
, it removes wet blast mask (see, for example patent document 3).
However, the thickness that can be ground by 1 blasting treatment is few in the processing using wet blast, need anti-
Multiple multiple blasting treatment.Therefore, the time for not only grinding consuming is very long, it is also difficult to so that the amount of grinding in face is uniform.Into one
Step, on connection gasket, in insulative substrate not the residue of cull composition layer and be completely exposed high-precision processing be pole
It is difficult.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-101244 bulletin
Patent document 2: No. 2017/038713 separate edition of International Publication No.
Patent document 3: Japanese Unexamined Patent Publication 2008-300691 bulletin.
Summary of the invention
Problems to be solved by the invention
Problem of the present invention is that in the processing of resin combination of the removal comprising alkali-insoluble resin and inorganic filler,
There is provided the defect caused by not generating because of excessive heating in containing resin composition layer made of the resin combination and can
Only remove the etching solution and engraving method of resin composition layer.
The means to solve the problem
The inventors of the present invention's discovery, by following means, is able to solve the above subject.
1 > etching solution of <, which is characterized in that in the inorganic filler to contain alkali-insoluble resin and 50 ~ 80 mass %
Resin combination etching solution in, which contains the alkali metal hydroxide of 15 ~ 45 mass %.
2 > of < is used for the etching solution of resin combination according to 1 > of <, which is characterized in that alkali metal hydroxide
It is at least one kind of compound in potassium hydroxide, sodium hydroxide and lithium hydroxide.
3 > of < is used for the etching solution of resin combination according to 2 > of < 1 > or <, which is characterized in that inorganic fill
Material is at least one kind of in silica, glass, clay and aluminium hydroxide.
4 > of < etching solution according to any one of 1 > of < ~ <, 3 >, which is characterized in that aforementioned etching solution contains 5 ~
The ethanolamine compound of 40 mass %.
5 > of < etching solution according to 4 > of <, which is characterized in that ethanolamine compound is selected from ethanol amine, N- (β-
Amino-ethyl) in ethanol amine, N- methylethanolamine, N- ehtylethanolamine, N methyldiethanol amine and N- ethyldiethanolamine
At least one kind of compound.
6 > of < is used for the etching solution of resin combination according to 4 > of <, which is characterized in that ethanolamine compound is
Selected from ethanol amine, N- (beta-aminoethyl) ethanol amine, N- methylethanolamine, N- ehtylethanolamine, N methyldiethanol amine and N-
At least two kinds of compounds in ethyldiethanolamine.
7 > of < is used for the etching solution of resin combination according to 6 > of <, wherein as ethanolamine compound, at least
Contain N- (beta-aminoethyl) ethanol amine.
8 > engraving method of <, which is characterized in that in the inorganic filler comprising alkali-insoluble resin and 50 ~ 80 mass %
In the engraving method of resin composition layer, including removing the resin by etching solution described in any one of 1 > of < ~ <, 7 >
The step of composition layer.
9 > engraving method of <, which is characterized in that the tree of the inorganic filler comprising alkali-insoluble resin and 50 ~ 80 mass %
In the engraving method of oil/fat composition layer, include: in order
(A) step of a part in the resin composition layer is removed by etching solution described in any one of 4 > of < ~ <, 7 >
Suddenly；
(B) liquid is removed by the inclusion of the washing of alkali metal hydroxide and ethanolamine compound and completely remove remaining resin group
The step of closing nitride layer；
Here, the content of the alkali metal hydroxide in aforementioned washing removal liquid and the alkali metal hydroxide in aforementioned etching solution
Content compared to less；In addition, the content of the ethanolamine compound in aforementioned washing removal liquid and the ethyl alcohol in aforementioned etching solution
The content of amine compounds is compared to less.
10 > of < engraving method according to 9 > of < 8 > or <, wherein the step of removing resin composition layer is leaching
Stain processing.
The effect of invention
Etching solution and engraving method through the invention include the resin combination of alkali-insoluble resin and inorganic filler in removal
In the processing of object, defect caused by not generating because of excessive heating can be removed only containing resin made of the resin combination
Composition layer.
Detailed description of the invention
Fig. 1 is the outline cross section structure figure of blocker pattern.
Fig. 2 is the outline cross section structure figure of blocker pattern.
Fig. 3 is the section block diagram of an example for showing engraving method of the invention.
Specific embodiment
Hereinafter, being illustrated for mode for carrying out the present invention.Etching solution of the invention is insoluble to contain alkali
The etching solution of the resin combination of the inorganic filling material of property resin and 50 ~ 80 mass %, is the alkali metal containing 15 ~ 45 mass %
The aqueous alkali of hydroxide.Alkali-insoluble resin has the undissolved property in aqueous alkali, therefore can not pass through originally
Aqueous alkali and remove.But by using etching solution of the invention, the resin combination comprising alkali-insoluble resin can be removed
Object.The reason for this is that inorganic filling material in the resin combination of high fillingization, i.e. in resin combination with 50 ~ 80 mass %
The inorganic filling material of this high-content filling is dissolved and goes by the inclusion of the aqueous solution of the alkali metal hydroxide of high concentration
It removes.
In the case that the content of alkali metal hydroxide is lower than 15 mass %, the dissolubility of inorganic filling material is poor, if alkali
The content of metal hydroxides be greater than 45 mass %, then easily cause the precipitation of alkali metal hydroxide, thus sometimes liquid with
Time stability is poor.The content of alkali metal hydroxide is more preferably 20 ~ 45 mass %, further preferably 25 ~ 40 mass %.
In etching solution of the invention, it can also be properly added coupling agent, levelling agent, colorant, surface-active as needed
Agent, defoaming agent, organic solvent etc..As organic solvent, the ketones such as acetone, methyl ethyl ketone, cyclohexanone can be enumerated；Ethyl acetate,
The acetate esters such as butyl acetate, cellosolve acetate, propylene glycol monomethyl ether, carbitol acetate；Cellosolve, butyl
The carbitols class such as carbitol；The aromatic hydrocarbons such as toluene, dimethylbenzene；Dimethylformamide, dimethyl acetamide, N- crassitude
Acid amides series solvents such as ketone etc..Wherein, the alkali-insoluble tree of dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone etc.
The swellability of rouge is big, so it is preferred that.
Etching solution of the invention is the etching of the resin combination to contain alkali-insoluble resin and inorganic filling material
Liquid.The content of inorganic filling material in the resin combination is relative to the 100 mass % of nonvolatile component in resin combination
50 ~ 80 mass %.In the case that the content of inorganic filling material is lower than 50 mass %, relative to resin combination entirety, as logical
The inorganic filling material in site crossing the aqueous solution containing alkali metal hydroxide and dissolving is very few, therefore etching can not be into
Row.If the content of inorganic filling material is greater than 80 mass %, because the mobility of resin combination reduces, lead to that there are flexible
Property reduce tendency, the practicability is poor.
As above-mentioned alkali metal hydroxide, it is suitble to use in potassium hydroxide, sodium hydroxide and lithium hydroxide extremely
Few a kind of compound.As alkali metal hydroxide, it can be used alone a kind in these, two or more can also be applied in combination.
Further, etching solution of the invention further preferably contains the ethyl alcohol of 5 ~ 40 mass % other than alkali metal hydroxide
Amine compounds.In the case where using the etching solution containing ethanolamine compound, ethanolamine compound permeates in resin combination,
Thus the swelling for promoting resin combination, accelerates the dissolution of inorganic filling material to remove, improves the removal speed of resin combination.
In the case that the content of ethanolamine compound is lower than 5 mass %, the swellability of alkali-insoluble resin is poor, with ethanol amine
The case where content of compound is 0 mass % is compared, and the removal speed of resin combination is constant.The content of ethanolamine compound is big
It in the case where 40 mass %, is lower to the compatibility of water, easily causes and mutually separate, therefore etching solution sometimes is stable at any time
Property is poor.The content of ethanolamine compound is more preferably 20 ~ 40 mass %, further preferably 25 ~ 35 mass %.
As above-mentioned ethanolamine compound, it is suitble to use the ethanol amine selected from as primary amine；As the mixed of primary amine and secondary amine
Close (there is primary amino group and secondary amino group in an intramolecular) N- (beta-aminoethyl) ethanol amine of object；N- methyl as secondary amine
Ethanol amine, N- ehtylethanolamine；As at least one kind of chemical combination in the N- ethyldiethanolamine and N methyldiethanol amine of tertiary amine
Object.As ethanolamine compound, it can be used alone a kind in these, two or more can also be applied in combination.It is applied in combination 2 kinds
In the case where above, wherein a kind is preferably N- (beta-aminoethyl) ethanol amine.The reason for this is that N- (beta-aminoethyl) ethyl alcohol
Amine promotes the effect of the swelling of resin combination higher compared with other ethanolamine compounds.
Illustrate the effect that etching solution of the invention can be realized by containing ethanolamine compound of more than two kinds.Promote
The high ethanol amine of the effect of the swelling of resin combination is easy to produce in the cross sectional shape of the resin composition layer of etched removal
Raw undercut.Therefore, it is combined by the ethanolamine compound low with the effect for the swelling for promoting resin combination, can be realized inhibition
The effect of undercut.
The high ethanol amine of the effect of swelling as promotion resin combination, can enumerate N- (beta-aminoethyl) ethyl alcohol
Amine, N- methylethanolamine etc..In addition, the ethanolamine compound that the effect of the swelling as promotion resin combination is low, Ke Yiju
Ethanol amine, N- ehtylethanolamine, N- ethyldiethanolamine etc. out.
Etching solution of the invention is aqueous alkali.As water used in etching solution of the invention, can be used tap water,
Industrial water, pure water etc..Wherein, it is preferable to use pure water.In the present invention, it is however generally that can be used pure used in industrial use
Water.
Etching solution of the invention preferably uses in the range of 60 ~ 90 DEG C.According to the type of resin combination, contain resin
The shape of the thickness of resin composition layer made of composition, the pattern as obtained from the processing for implementing removal resin combination
Different Deng, optimum temperature, the temperature of etching solution is more preferably 60 ~ 85 DEG C, further preferably 70 ~ 85 DEG C.
In the present invention, as inorganic filling material, it can be cited for example that the silicic acid such as silica, glass, clay, mica
Salt；The oxides such as aluminium oxide, magnesia, titanium oxide, silica；The carbonate such as magnesium carbonate, calcium carbonate；Aluminium hydroxide, hydrogen-oxygen
Change the hydroxide such as magnesium, calcium hydroxide；Sulfate such as barium sulfate, calcium sulfate etc..In addition, as inorganic filling material, Ke Yijin
One step enumerates aluminium borate, aluminium nitride, boron nitride, strontium titanates, barium titanate etc..Among these, it is selected from silica, glass, clay
It is dissolved in the aqueous solution containing alkali metal hydroxide at least one kind of compound in aluminium hydroxide, so more preferably use.
Silica is it is further preferred that particularly preferably spheroidal fused silica at the excellent aspect of low heat expansion.As nothing
Machine packing material can be used alone a kind in these, two or more can also be applied in combination.
It is illustrated for the alkali-insoluble resin in the present invention.Alkali-insoluble resin is in addition to insoluble for aqueous alkali
Except solution or the property of dispersion, it is not particularly limited.Specifically, being tree containing carboxyl required for being dissolved for aqueous alkali
The considerably less resin of the content of rouge etc., as become resin in free carboxy content index acid value (JIS K2501:
2003), it is lower than 40mgKOH/g.More specifically, alkali-insoluble resin is comprising epoxy resin and the heat for making epoxy resin cure
The resin of curing agent.As aqueous alkali, can enumerate containing alkali silicate, alkali metal hydroxide, alkali metal phosphoric acid
The aqueous solutions of inorganic alkaline compounds such as salt, alkali carbonate, ammonium phosphate, ammonium carbonate contain monoethanolamine, diethanol
Amine, triethanolamine, methyl amine, dimethyl amine, ethylamine, diethylamide, triethylamine, cyclo-hexylamine, tetramethylammonium hydroxide
(TMAH), the organic basic compounds such as tetraethyl ammonium hydroxide, trimethyl -2- hydroxyethylammonium hydroxide (choline) is water-soluble
Liquid.
As epoxy resin, it can be cited for example that bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy
The bisphenol-type epoxy resins such as resin；The novolaks such as phenol novolak type epoxy resin, cresol novolak type epoxy resin
Type epoxy resin etc..In addition, can further enumerate biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type as epoxy resin
Epoxy resin, phenoxy group type epoxy resin, fluorenes type epoxy resin etc..As epoxy resin, 1 in these can be used alone
Kind, two or more can also be applied in combination.
As thermal curing agents, as long as having the function of epoxy resin cure, it is not particularly limited, as preferred heat
Curing agent can enumerate phenol system curing agent, naphthols system curing agent, active ester system curing agent, benzoxazine system curing agent, cyanic acid
Ester resin etc..As thermal curing agents, it can be used alone a kind in these, two or more can also be applied in combination.
Other than above-mentioned curing agent, it can also further contain curing accelerator.As curing accelerator, can enumerate
Such as organic phosphine compound, organophosphorated salt compound, imidazolium compounds, amine adduct compound, tertiary amine compound etc..As
Curing accelerator can be used alone a kind in these, two or more can also be applied in combination.It should be noted that as heat cure
Agent and use cyanate ester resin in the case where, in order to shorten curing time, the organic metal of curing catalysts can be added as
Compound.As organo-metallic compound, organocopper compound, organic zinc compound, organic cobalt compounds etc. can be enumerated.
As described above, if using etching solution of the invention, to inorganic comprising alkali-insoluble resin and 50 ~ 80 mass %
The resin combination of packing material is etched, then the inorganic filling material in the resin combination of high fillingization is by the inclusion of height
The aqueous solution of the alkali metal hydroxide of concentration and be dissolved removal, thus carry out resin combination removal.Further, this hair
In the case that bright etching solution includes ethanolamine compound, ethanolamine compound permeates in resin combination, thus promotes tree
The swelling of oil/fat composition accelerates the dissolution of inorganic filling material to remove.
On the other hand, the resin combination comprising alkali-insoluble resin and inorganic filling material being capable of shape by heat cure
A stage (before the beginning of curing reaction) or B-stage are etched at insualtion resin composition layer, but using etching solution of the invention
It is carried out in the state of (intermediate stage of curing reaction).In A stage or B-stage, alkali-insoluble resin is not in the present invention
Etching solution in dissolve or dispersion, but inorganic filling material etching solution through the invention and be dissolved removal, thus set
The removal of oil/fat composition.In the state of reaching C-stage, resin is fully cured, even if including ethyl alcohol in etching solution of the invention
In the case where amine compounds, because the swelling of resin composition layer caused by ethanolamine compound is also minimum, it is difficult to using inorganic
The dissolution of packing material is removed and is etched.
It is 10 ~ 60 minutes, more preferably 100 ~ 130 DEG C at 100 ~ 160 DEG C as the heat cure condition in A stage to B-stage
It is 10 ~ 60 minutes lower, but not limited to this.If heated at a high temperature of being greater than 160 DEG C, further progress heat cure, resin erosion
Quarter becomes difficult.
Hereinafter, being illustrated for engraving method of the invention.Fig. 3 is section for showing an example of engraving method of the invention
Face block diagram.In the engraving method, part or all in the welded connecting pad 3 on circuit substrate, which is capable of forming, to be set
The blocker pattern that oil/fat composition layer 4 covers.
In step (I), the copper foil positioned at the surface of copper-clad laminated board carries out pattern by etching and is formed, and is consequently formed and leads
Body pattern, being formed has the circuit substrate 1 for being welded to connect pad 3.
In step (II), in the surface of circuit substrate 1, by cover it is entire in a manner of form the resin group with copper foil 6
Close nitride layer 4.
In step (III), the copper foil 6 on resin composition layer 4 carries out pattern by etching and is formed, and is formed and is used for resin
The metal mask 5 of composition layer etching.
In step (IV), via metal mask 5, resin combination is etched and the etching solution for resin composition layer
Layer 4, until part or all of exposing being welded to connect in pad 3.
In step (V), metal mask 5 is removed by etching, is formed part or all being welded to connect in pad 3 and is set
The blocker pattern that oil/fat composition layer 4 covers.
8 > of engraving method < of the invention includes described in any one of 1 > of etching solution < ~ 7 > of < through the invention
Etching solution and the step of remove resin composition layer.
In addition, 9 > of engraving method < of the invention includes: by 4 > of etching solution < (A) of the invention ~ 7 > of < in order
Any one of described in etching solution and remove the step of a part in resin composition layer；
(B) by the inclusion of the alkali gold in alkali metal hydroxide and ethanolamine compound and its content and respective aforementioned etching solution
Belong to hydroxide to compare few washing removal liquid with the content of ethanolamine compound and completely remove remaining resin composition layer
The step of.
In 9 > of < of the present invention, resin composition layer includes alkali-insoluble resin and inorganic filler, inorganic filling material
Content is 50 ~ 80 mass % relative to resin composition layer, and inorganic filling material is filled in resin composition layer with high-content
In.The inorganic filling material by the inclusion of the alkali metal hydroxide of 15 ~ 45 mass % this high concentration aqueous solution, etch
Liquid and be dissolved removal.Further, the ethanolamine compound for including in etching solution permeates in resin composition layer, promotes resin
The swelling of composition layer thereby speeds up the dissolution removal of inorganic filling material, improves the removal speed of resin composition layer.
It is carried out here, the removal of resin composition layer refers to by following manner: the inorganic fill being filled with high-content
Agent is slowly dissolved from the surface layer of resin composition layer, while alkali-insoluble resin dispersion, to carry out.Engraving method of the invention
Etching solution used in step (A) in 9 > of < includes the alkali metal hydroxide of the high concentration of 15 mass % or more, big water
Resultant force plays a role, therefore will not remove the alkali-insoluble resin dispersion at the more deep of resin composition layer close to table
The part of layer.That is, " a part in the layer of removal resin combination " in step (A) refers to removal close to resin composition layer
Surface layer part.
After step (A), then in step (B), by removing liquid using the poor washing of alkali metal hydroxide
It is handled, promotes the dispersion of alkali-insoluble resin, completely remove remaining resin composition layer.
In the engraving method of resin composition layer in 9 > of < of the present invention, using including the water-soluble of alkali metal hydroxide
The dissolution removal of the inorganic filler of liquid and connected using infiltration of the ethanolamine compound in resin composition layer and swelling
It is continuous to carry out, but it carries out speed and according to the type and content of alkali metal hydroxide or the type of ethanolamine compound and contains
It measures and changes.
Washing removal liquid is comprising alkali metal hydroxide and ethanolamine compound and its content involved in step (B)
Respectively less washing removes liquid compared with the content of alkali metal hydroxide and ethanolamine compound in etching solution.Step
(B) alkali metal hydroxide of washing removal liquid and the content of ethanolamine compound used in are to lose used in step (A)
In the case where carving the content of the alkali metal hydroxide and ethanolamine compound in liquid or more, occur to be difficult to control resin combination
The problem of etch quantity of layer.Alkali metal hydroxide used in step (A) and ethanolamine compound are used with step (B)
Alkali metal hydroxide and ethanolamine compound can be identical or different, but usual 2 steps are carried out continuously, in transfer step
When, it is contemplated that cause washing of the etching solution from step (A) to step (B) to remove being mixed into for liquid, it is however generally that comprising identical
Alkali metal hydroxide and ethanolamine compound.
In 9 > of < of the present invention, the treatment temperature of step (A) is preferably 60 ~ 90 DEG C, and the treatment temperature of step (B) is preferably
15~50℃.It is gone here, " treatment temperature " refers to wash used in the temperature and step (B) of etching solution used in step (A)
Except the temperature of liquid.According to the type of resin combination, the thickness of resin composition layer, by implementing removal resin composition layer
The shape etc. of pattern obtained from processing, optimum treatmenting temperature are different.The treatment temperature of step (A) be more preferably 60 ~ 85 DEG C, into
One step is preferably 70 ~ 85 DEG C.In addition, the treatment temperature of step (B) is more preferably 15 ~ 40 DEG C, further preferably 15 ~ 30 DEG C.
In 8 > of < and 9 > of < of the present invention, remove resin composition layer the step of in, can be used impregnation, clap paddle at
The methods of reason, spraying treatment, scrub, scraping.Wherein, preferably impregnation.In method other than impregnation, it is easy
Bubble is generated in etching solution, which is attached to the surface of resin composition layer, and it is bad that etching occurs sometimes.In addition, this hair
In the step of bright 9 > of < (A), in the method other than impregnation, the temperature change of etching solution is tended to get bigger, and is being set sometimes
Deviation is generated in terms of the removal speed of oil/fat composition layer.
After the step of the step of removal resin combination of 8 > of < of the present invention and 9 > of < of the present invention (B), pass through washing
The etching solution of processing washing remaining attachment on the surface of resin composition layer.As the method for washing process, from diffusion velocity
From the perspective of the uniformity of liquid supply, preferably spray pattern.As washing water, tap water, industrial can be used
Water, pure water etc..Wherein, it is preferable to use pure water.In general pure water used in industrial use can be used in pure water.Wherein, excellent
Choosing uses pure water.In general pure water used in industrial use can be used in pure water.In addition, the temperature of washing water is etching solution
Temperature hereinafter, and preferably its temperature difference be 40 ~ 50 DEG C, its more preferable temperature difference is 50 ~ 60 DEG C.
Embodiment
Hereinafter, present invention will be further described in detail through examples, but the present invention is not limited to this embodiment.
(embodiment 1 ~ 3)
It adds as the 78 mass % of fused silica of inorganic filling material, as the biphenyl aralkyl type epoxy of epoxy resin
10 mass % of resin, as the 10 mass % of phenol novolak type cyanate ester resin of thermal curing agents, as the three of curing accelerator
In addition to this 1 mass % of Phenylphosphine adds coupling agent, levelling agent, total amount is denoted as 100 mass %, mixes methyl ethyl ketone and cyclohexanone
As medium, liquid resin composition is obtained.
Then, after being coated with liquid resin composition on polyethylene terephthalate film (38 μm of thickness), at 100 DEG C
Lower drying 5 minutes and remove medium.20 μm of film thickness is formed as a result, and by including alkali-insoluble resin and inorganic filler and tree
The resin composition layer in the A stage that oil/fat composition is formed.
Then, preparation is laminated with 3 μm of thickness of copper foil, the peelable metal foil of peeling layer and carrier foils in order, with copper
After the mode that foil is contacted with above-mentioned resin composition layer is thermally compressed the two, peeling layer and carrier foils are removed, are obtained with copper foil
Resin composition layer.
To positioned at glass fabric of epoxy resin substrate copper-clad laminated board (area 170mm × 255mm, 12 μm of copper thickness, substrate
Thickness 0.1mm) a surface copper foil, by etching carry out pattern formed, obtain the epoxy resin for being formed with conductive pattern
Glass cloth base material.Then, polyethylene terephthalate film is removed from the resin composition layer with copper foil, is led being formed with
On the glass fabric of epoxy resin substrate of body pattern, using heating in vacuum compression joint type laminating machine, in 100 DEG C of temperature, pressure 1.0MPa
Under conditions of carry out Vacuum Heat crimping after, heated 30 minutes at 100 DEG C, form the resin composition layer of B-stage.
Then, it carries out pattern by etching to the copper foil on resin composition layer to be formed, in the defined region shape of copper foil
Prepare the resin composition layer with metal mask as the metal mask etched for resin composition layer at opening portion.
Then, via metal mask, by etching solution recorded in table 1, to resin composition layer using impregnation into
Row etching process.After etching process, by the etching solution of the remaining attachment on the surface of resin composition layer by utilizing pure water
Spraying treatment is washed.Time required for the temperature and etching process of etching solution is shown in table 1.
In the opening portion of metal mask, " whether there is or not resin residues " and " whether there is or not undercuts " comments according to the benchmark of following records
Valence.
(whether there is or not resin residues on conductive pattern surface)
Zero: the non-cull composition on conductive pattern surface.
△: the resin combination of denier is remained on conductive pattern surface, but can easily be washed by plasma
The level washing the post-processing such as processing and removing.
×: a large amount of resin combination residuals on conductive pattern surface can not pass through the level of post-processing removal.
(whether there is or not resin residues on glass fabric of epoxy resin substrate)
Zero: the non-cull composition on substrate.
△: the resin combination of denier is remained on substrate, but can easily pass through plasma carrying out washing treatment etc.
The level of post-processing and removal.
×: a large amount of resin combination residuals on substrate can not pass through the level of post-processing removal.
(whether there is or not undercuts)
◎: undercut is not found in resin composition layer.
Zero: small undercut is found in the bottom surface of resin composition layer.
△: small undercut is found in the bottom surface of resin composition layer.
×: the practical upper big undercut as problem is found in the bottom surface of resin composition layer.
(embodiment 4)
The content of fused silica is set as 65 mass %, the content of biphenyl aralkyl-type epoxy resin is set as 23 mass %,
In addition to this, it by method same as Example 1, is etched.
(embodiment 5)
The content of fused silica is set as 50 mass %, the content of biphenyl aralkyl-type epoxy resin is set as 38 mass %,
In addition to this, it by method same as Example 1, is etched.
(embodiment 6 ~ 8)
As inorganic filling material, substitute fused silica, using glass, clay, aluminium hydroxide, in addition to this, by with
The identical method of embodiment 5, is etched.
(embodiment 9 ~ 21)
As etching solution, using etching solution described in table 1, in addition to this, by method same as Example 1, it is etched
Processing.
(comparative example 1)
The content of fused silica is set as 48 mass %, the content of biphenyl aralkyl-type epoxy resin is set as 40 mass %,
In addition to this, it by method same as Example 1, is etched.Etching period is extended to 30 minutes, but in conductor
On patterned surfaces and there are a large amount of resin residues on glass fabric of epoxy resin substrate, can not be etched to resin composition layer
Processing.As a result it is shown in table 2.
(comparative example 2 ~ 4)
In comparative example 2, the content of the potassium hydroxide of etching solution is set as 10 mass %, in comparative example 3 and 4, is further used as ethyl alcohol
Amine compounds and add 40 mass % of N- (beta-aminoethyl) ethanol amine and N- methylethanolamine respectively, in addition to this, by with reality
The identical method of example 1 is applied, is etched.Etching period is extended to 30 minutes, but on conductive pattern surface and epoxy
There are a large amount of resin residues on plexiglas cloth base material, and processing can not be etched to resin composition layer.As a result it is shown in table
2。
(comparative example 5)
The resin composition layer with metal mask obtained by method same as Example 1 is carried out by laser processing method
Etching process removes mask pattern thereafter.By its with optical microscopy observe as a result, being removed there are conductive pattern
Part, in addition, confirming the defect of deformation, rotten etc in resin composition layer.
(comparative example 6)
The resin composition layer with metal mask obtained by method same as Example 1 is lost by wet blast
Quarter processing removes mask pattern thereafter.By its with optical microscopy observe as a result, resin composition layer etch quantity
There are deviations for aspect, and there are the remaining positions of resin combination on glass fabric of epoxy resin substrate.In addition, one in surface
In the conductive pattern partly or entirely exposed, the scar assigned by blasting treatment is largely confirmed.
In embodiment 1 ~ 21, compared with comparative example 5 or comparative example 6, it is not deformed in resin composition layer, goes bad it
The defect of class does not generate scar on connection gasket, in addition, will not go together conductive pattern in the etching of resin composition layer
It removes, does not remain the practical upper horizontal resin combination as problem on glass fabric of epoxy resin substrate, it can be to resin group
It closes nitride layer and is etched processing.
Compared with Example 1 by embodiment 10,12 ~ 16, by adding ethyl alcohol in the etching solution for resin combination
Amine compounds do not lead to the problem of the practical upper horizontal resin residue become, undercut, can shorten etching period.
In embodiment 4 and 5, the content of fused silica is few compared with Example 1, therefore etching period is elongated, but not
Lead to the problem of the practical upper horizontal undercut become.
The fused silica of alternate embodiment 5 and use in the embodiment 6 ~ 8 of glass, clay, aluminium hydroxide, although energy
Enough etchings, but etching period is elongated compared with fused silica.However, not leading to the problem of stinging for the practical upper level become
Side.
The potassium hydroxide of alternate embodiment 1 and use in the embodiment 17 and 18 of sodium hydroxide, lithium hydroxide, also do not generate
The practical upper horizontal undercut as problem.
In embodiment 19, compared with Example 10, the temperature of etching solution is improved, therefore etching period shortens, but in ring
The practical upper horizontal resin combination as problem is not remained on oxygen plexiglas cloth base material, can to resin composition layer into
Row etching and processing.In embodiment 20 and 21, compared with Example 10, the temperature of etching solution is low, therefore etching period is elongated, but not
Lead to the problem of the practical upper horizontal undercut become.
(embodiment 22 ~ 28)
As etching solution, using etching solution described in table 3, in addition to this, by method same as Example 1, it is etched
Processing.
(embodiment 29)
The content of fused silica is set as 50 mass %, the content of biphenyl aralkyl-type epoxy resin is set as 38 mass %,
In addition to this, it by method identical with embodiment 22, is etched.
(embodiment 30 ~ 32)
As inorganic filling material, substitute fused silica, using glass, clay, aluminium hydroxide, in addition to this, by with
The identical method of embodiment 29, is etched.
(embodiment 33 and 34)
As etching solution, using etching solution described in table 3, in addition to this, by method identical with embodiment 22, it is etched
Processing.
In embodiment 22 ~ 34, compared with comparative example 5 or comparative example 6, it is not deformed, goes bad in resin composition layer
Etc defect, scar is not generated on connection gasket, in addition, will not be by conductive pattern together in the etching of resin composition layer
Removal does not remain the practical upper horizontal resin combination as problem on glass fabric of epoxy resin substrate, can be to resin
Composition layer is etched processing.
By embodiment 22 ~ 34 compared with embodiment 9 ~ 16, resin is used for using containing ethanolamine compound of more than two kinds
In the embodiment 22 ~ 34 of the etching solution of composition, it is difficult to generate undercut.
According to the comparison of embodiment 22,25 ~ 28, the etching solution for resin combination contains N- (beta-aminoethyl) ethyl alcohol
For amine as in the embodiment 22,25 and 26 of ethanolamine compound, etching period is short, also without generating undercut.For resin combination
The etching solution of object, as in the embodiment 27 of ethanolamine compound, generates small undercut without N- (beta-aminoethyl) ethanol amine,
Etching solution for resin combination, as in the embodiment 28 of ethanolamine compound, is use up without N- (beta-aminoethyl) ethanol amine
Pipe is without generating undercut, but etching period is elongated.
In embodiment 29, the content of fused silica is few compared with embodiment 22, therefore etching period is elongated, but does not produce
Raw undercut.
The fused silica of alternate embodiment 29 and use in the embodiment 30 ~ 32 of glass, clay, aluminium hydroxide, though
It can so etch, but etching period is elongated compared with fused silica.However, not generating undercut.
The potassium hydroxide of alternate embodiment 22 and use in the embodiment 33 and 34 of sodium hydroxide or lithium hydroxide, also do not produce
Raw undercut.
(embodiment 35)
In embodiment 1, via metal mask, by the inclusion of 30 matter of potassium hydroxide 30 mass % and N- (beta-aminoethyl) ethanol amine
The etching solution (80 DEG C for the treatment of temperature) of % is measured, a part (step (A)) in resin composition layer is removed.Thereafter, by the inclusion of hydrogen
The washing of 0.3 mass % of potassium oxide 0.3 mass % and N- (beta-aminoethyl) ethanol amine removes liquid (20 DEG C for the treatment of temperature), goes completely
Except remaining resin composition layer (step (B)).After step (B), by the erosion of the remaining attachment on the surface of resin composition layer
Liquid is carved by being washed using the spraying treatment of pure water.Step (A) and step (B) are carried out by impregnation.With not
Embodiment 10 containing step (B) is compared, it is thus identified that is included conductive pattern surface, is not remained tree on glass fabric of epoxy resin substrate
Oil/fat composition layer has carried out etching removal.In addition, not confirming the practical upper horizontal undercut as problem.The temperature of etching solution
Time required for degree and etching process is shown in table 4 and table 5.
(embodiment 36 ~ 46)
The cooperation of washing removal liquid in etching solution and/or step (B) in step (A) is changed to match described in table 4 and table 5
It closes, in addition to this, by method identical with embodiment 35, is etched.By embodiment 36 ~ 39 and 35 phase of embodiment
Than the content of the potassium hydroxide in etching solution is bigger, then the required time gets over until resin composition layer is etched removal
It is short.In addition, passing through the ethanolamine compound and alkali metal hydrogen in change etching solution by embodiment 40 ~ 46 compared with embodiment 35
The type of oxide, the time until etching removal change, but do not remain on glass fabric of epoxy resin substrate practical
The upper horizontal resin combination as problem, does not generate undercut.On the other hand, by embodiment 37 and 39 and 35 phase of embodiment
Than, it is found that the content of potassium hydroxide or ethanolamine compound is more, then generate the tendency of small undercut in bottom surface, but it is practical on
The level that there is no problem.
(embodiment 47 and 48)
The content of fused silica is set as 65 mass %, 50 mass %, the content of biphenyl aralkyl-type epoxy resin is set as
In addition to this 23 mass %, 38 mass % by method identical with embodiment 35, are etched.Fused silica
Content is fewer, then the time required until resin composition layer is all etched removal is longer, but in glass epoxy
Not cull composition on cloth base material, does not occur undercut.
(embodiment 49 ~ 51)
As inorganic filling material, substitute fused silica, using glass, clay, aluminium hydroxide, in addition to this, by with
The identical method of embodiment 35, is etched.Time needed for until resin composition layer is all etched removal becomes
It is long, but the not cull composition on glass fabric of epoxy resin substrate, undercut does not occur.
(embodiment 52 ~ 58)
Treatment temperature in step (A) or step (B) is changed to the temperature that table 4 or table 5 are recorded, in addition to this, by with reality
The identical method of example 35 is applied, is etched.Embodiment 52 ~ 54 and embodiment 35 are compared, the processing of step (A) is confirmed
Temperature is lower, then the time needed for being etched removal to resin composition layer is longer, but on glass fabric of epoxy resin substrate not
The practical upper horizontal resin combination as problem is remained, etching removal has been carried out.It is asked in addition, not confirming practical upper become
The horizontal undercut of topic.If in addition, having carried out the processing temperature of the cross sectional shape step (A) of the resin composition layer of etching removal
Degree is got higher, then finds small undercut in bottom surface, be the level that there is no problem in practical.By embodiment 55 ~ 58 and embodiment 35
Comparison, that there are the treatment temperatures in step (B) is higher, then easier cull inclines on glass fabric of epoxy resin substrate
To.In addition, not generating undercut in the cross sectional shape of resin composition layer for having carried out etching removal.
(embodiment 59)
As etching solution, using etching solution described in table 6 or table 7, in addition to this, by method identical with embodiment 35, into
Row etching process.Compared with the embodiment 22 without step (B), it is thus identified that include conductive pattern surface, in glass epoxy
Not cull composition layer on cloth base material has carried out etching removal.In addition, not confirming the practical upper level as problem
Undercut.Time required for the temperature and etching process of etching solution is shown in table 6 and table 7.
(embodiment 60 ~ 65)
The cooperation of washing removal liquid in etching solution and/or step (B) in step (A) is changed to match described in table 6 and table 7
It closes, in addition to this, by method identical with embodiment 59, is etched.According to the comparison of embodiment 59,62 ~ 65, use
Contain embodiment 59,62 and 63 of N- (beta-aminoethyl) ethanol amine as ethanolamine compound in the etching solution of resin combination
In, etching period is short, also without generating undercut.Etching solution for resin combination is made without N- (beta-aminoethyl) ethanol amine
To generate small undercut in the embodiment 64 of ethanolamine compound, the etching solution for resin combination is free of N- (beta-amino second
Base) ethanol amine is as in the embodiment 65 of ethanolamine compound, although not generating undercut, etching period is elongated.
(embodiment 66)
The content of fused silica is set as 50 mass %, the content of biphenyl aralkyl-type epoxy resin is set as 38 mass %,
In addition to this, it by method identical with embodiment 59, is etched.Fused silica contains compared with embodiment 59
Amount is few, therefore etching period is elongated, but does not generate undercut.
(embodiment 67 ~ 69)
As inorganic filling material, substitute fused silica, using glass, clay, aluminium hydroxide, in addition to this, by with
The identical method of embodiment 59, is etched.Although can etch, etching period becomes compared with fused silica
It is long.Do not generate undercut.
(embodiment 70 ~ 71)
As etching solution, using etching solution described in table 6 or table 7, in addition to this, by method identical with embodiment 59, into
Row etching process.Even if also not generating undercut in the case where substituting potassium hydroxide and using sodium hydroxide, lithium hydroxide.
Industrial applicibility
Etching solution of the invention can be to heat resistance that inorganic filling material is filled with high-content, dielectric property, mechanical strength, resistance to
The excellent insualtion resin composition layer such as chemicals is etched processing, can be applied to such as multilayer increasing layer distributing board,
The microfabrication of insulating resin in component built-in module substrate, flip chip package substrate, package substrate carrying mainboard etc..
Description of symbols
1 circuit substrate
2 insulating layers
3 are welded to connect pad, connection gasket
4 resin composition layers
5 metal masks
6 copper foils.
Claims (10)
1. etching solution, which is characterized in that in the resin to contain alkali-insoluble resin and the inorganic filler of 50 ~ 80 mass %
In the etching solution of composition, which contains the alkali metal hydroxide of 15 ~ 45 mass %.
2. the etching solution according to claim 1 for resin combination, which is characterized in that alkali metal hydroxide is choosing
From at least one kind of compound in potassium hydroxide, sodium hydroxide and lithium hydroxide.
3. the etching solution according to claim 1 or 2 for resin combination, which is characterized in that inorganic filling material is
It is at least one kind of in silica, glass, clay and aluminium hydroxide.
4. etching solution described according to claim 1 ~ any one of 3, which is characterized in that aforementioned etching solution contains 5 ~ 40 mass %
Ethanolamine compound.
5. etching solution according to claim 4, which is characterized in that ethanolamine compound is selected from ethanol amine, N- (beta-amino
Ethyl) in ethanol amine, N- methylethanolamine, N- ehtylethanolamine, N methyldiethanol amine and N- ethyldiethanolamine at least 1
Kind compound.
6. the etching solution according to claim 4 for resin combination, which is characterized in that ethanolamine compound is to be selected from
Ethanol amine, N- (beta-aminoethyl) ethanol amine, N- methylethanolamine, N- ehtylethanolamine, N methyldiethanol amine and N- ethyl
At least two kinds of compounds in diethanol amine.
7. the etching solution according to claim 6 for resin combination, wherein as ethanolamine compound, at least contain
There is N- (beta-aminoethyl) ethanol amine.
8. engraving method, which is characterized in that in the resin group of the inorganic filler comprising alkali-insoluble resin and 50 ~ 80 mass %
In the engraving method for closing nitride layer, including removing the resin combination by etching solution described in any one of claim 1 ~ 7
The step of layer.
9. engraving method, which is characterized in that the resin combination of the inorganic filler comprising alkali-insoluble resin and 50 ~ 80 mass %
In the engraving method of nitride layer, include: in order
(A) step of a part in the resin composition layer is removed by etching solution described in any one of claim 4 ~ 7
Suddenly；
(B) by the inclusion of the alkali gold in alkali metal hydroxide and ethanolamine compound and its content and respective aforementioned etching solution
Belong to hydroxide to compare few washing removal liquid with the content of ethanolamine compound and completely remove remaining resin composition layer
The step of.
10. engraving method according to claim 8 or claim 9, wherein the step of removing resin composition layer is impregnation.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2017-076148 | 2017-04-06 | ||
| JP2017076148 | 2017-04-06 | ||
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| JP2018-026675 | 2018-02-19 | ||
| JP2018026675 | 2018-02-19 | ||
| PCT/JP2018/014156 WO2018186362A1 (en) | 2017-04-06 | 2018-04-02 | Etchant for resin composition and etching method |
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| JP (1) | JP6929936B2 (en) |
| KR (1) | KR102340959B1 (en) |
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| CN115011348A (en) * | 2022-06-30 | 2022-09-06 | 湖北兴福电子材料有限公司 | Aluminum nitride etching solution and application thereof |
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| JP6674075B1 (en) * | 2018-10-24 | 2020-04-01 | 三菱製紙株式会社 | Etching solution for resin composition and etching method |
| KR102327244B1 (en) | 2018-10-24 | 2021-11-16 | 미쓰비시 세이시 가부시키가이샤 | Etching liquid and etching method of resin composition |
| JP6774589B1 (en) * | 2019-01-28 | 2020-10-28 | 三菱製紙株式会社 | Etching solution and etching method for resin composition |
| KR102364004B1 (en) * | 2019-04-03 | 2022-02-16 | 미쓰비시 세이시 가부시키가이샤 | Liquid crystal polymer etching solution and liquid crystal polymer etching method |
| JP7341766B2 (en) * | 2019-07-19 | 2023-09-11 | 三菱製紙株式会社 | Etching method for resin compositions |
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| JPWO2018186362A1 (en) | 2020-01-16 |
| TW201842165A (en) | 2018-12-01 |
| JP6929936B2 (en) | 2021-09-01 |
| WO2018186362A1 (en) | 2018-10-11 |
| KR20190120771A (en) | 2019-10-24 |
| KR102340959B1 (en) | 2021-12-17 |
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