WO2020085447A1 - 樹脂組成物のエッチング液及びエッチング方法 - Google Patents
樹脂組成物のエッチング液及びエッチング方法 Download PDFInfo
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- WO2020085447A1 WO2020085447A1 PCT/JP2019/041765 JP2019041765W WO2020085447A1 WO 2020085447 A1 WO2020085447 A1 WO 2020085447A1 JP 2019041765 W JP2019041765 W JP 2019041765W WO 2020085447 A1 WO2020085447 A1 WO 2020085447A1
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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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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- 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
-
- 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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/002—Etching of the substrate by chemical or physical means by liquid chemical etching
Definitions
- the present invention relates to an etching solution and an etching method for a resin composition containing an alkali-insoluble resin and 50 to 80% by mass of an inorganic filler.
- Insulating resin compositions containing these inorganic fillers and alkali-insoluble resins have excellent physical properties such as heat resistance, dielectric properties, mechanical strength, and chemical resistance, and are used for the outer surface of circuit boards. It is widely used as an interlayer insulating material for resists and multilayer build-up wiring boards.
- FIG. 1 is a schematic cross-sectional structural diagram of a solder resist pattern in which the resin composition layer 4 is covered except for the connection pads 3 to be soldered on a circuit board.
- the structure shown in FIG. 1 is called an SMD (Solder Masked Defined) structure, and is characterized in that the opening of the resin composition layer 4 is smaller than the connection pad 3.
- the structure shown in FIG. 2 is called an NSMD (Non Solder Masked Defined) structure, and is characterized in that the opening of the resin composition layer 4 is larger than the connection pad 3.
- the opening of the resin composition layer 4 in FIG. 1 is formed by removing a part of the resin composition layer.
- known methods such as drilling, laser, plasma, blasting and the like can be used. Moreover, these methods can be combined as needed. Among these, processing by a laser such as a carbon dioxide gas laser, an excimer laser, a UV laser, a YAG laser is the most general, and a part of the resin composition layer 4 is removed by laser light irradiation to form a through hole for forming a through hole.
- Through holes and non-through holes such as openings for forming via holes and openings for forming connection pads 3 can be formed (see, for example, Patent Documents 1 and 2).
- thermosetting resin in the resin composition layer, but when the thermosetting resin is used, a crack may easily occur in the resin composition layer. .
- a method of removing the resin composition layer by a wet blast method As a method other than laser light irradiation, there is a method of removing the resin composition layer by a wet blast method. After forming a resin composition layer on the circuit board having a connection pad on the insulating substrate, subjected to a curing treatment, on the resin composition layer, after providing a resin layer for forming a wet blasting mask, By exposing and developing, a patterned wet blast mask is formed. Next, wet blasting is performed to remove the resin composition layer, form an opening, and subsequently remove the wet blasting mask (see, for example, Patent Document 3).
- the thickness that can be polished by one blast treatment is small, and it is necessary to repeat the blast treatment multiple times. Therefore, not only the time required for polishing becomes very long, but also the portion where the resin composition layer is adhered is on the connection pad or on the insulating substrate, and due to the difference in the material, it is uniform. It has been extremely difficult to perform highly accurate processing, such as inability to perform various polishing operations and the occurrence of residues.
- a processing method for removing a resin composition layer containing a resin composition containing an inorganic filler and an alkali-insoluble resin an etching method performed by dipping treatment using a hydrazine-based chemical solution at 40 ° C. as an etching solution is disclosed.
- hydrazine is a poisonous substance, which is not preferable because it has a large impact on the human body and a large environmental load.
- Patent Document 5 discloses, as a more preferred embodiment, an etching solution further containing an ethanolamine compound.
- Patent Document 5 has a small effect on the human body and environmental load, but in some cases, residues were left on the surface after etching. In addition, an undercut may be observed in the resin composition layer after etching. Also, in highly productive etching processing, it is important that several patterns are arranged in the surface and that each pattern is processed uniformly. Fine processing has been demanded, and its uniformity has also been required at the same time, which is not sufficient in some cases.
- the opening diameter of the opening in the resin composition layer is ⁇ 100 ⁇ m due to lack of affinity between the etching solution and the resin composition layer. In the small-diameter opening process as described below, an unetched portion may occur. Therefore, there has been a demand for an etching method that does not generate unetched portions.
- a resin composition layer containing the resin composition can be stably removed without residue, It is an object of the present invention to provide an etching solution for a resin composition and an etching method which are less likely to cause an undercut in the subsequent resin composition layer and have high in-plane uniformity. Further, it is an object of the present invention to provide an etching method capable of suppressing the generation of unetched portions even in a small-diameter opening process in which the opening diameter is ⁇ 100 ⁇ m or less.
- An etching solution of a resin composition containing an alkali-insoluble resin and 50 to 80% by mass of an inorganic filler wherein the etching solution comprises 15 to 45% by mass of an alkali metal hydroxide as a first component and a second 3 to 60% by mass of a polyol compound as a third component, containing 1 to 40% by mass of an ethanolamine compound as a component, 2 to 20% by mass of a polycarboxylic acid or 2 to 20% by mass of a hydroxy acid
- An etching solution for a resin composition which comprises: ⁇ 2> The etching solution for a resin composition according to ⁇ 1>, wherein the third component is a polyol compound in an amount of 3 to 60% by mass.
- ⁇ 3> The etching solution for a resin composition according to ⁇ 1> or ⁇ 2>, wherein the polyol compound has a molecular weight of 80 or more and 200 or less.
- ⁇ 4> The etching solution for a resin composition according to any one of ⁇ 1> to ⁇ 3>, in which the polyol compound has three or more hydroxyl groups.
- ⁇ 5> The etching solution for a resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polyol compound is glycerin.
- ⁇ 6> The etching solution for a resin composition according to ⁇ 1>, wherein the third component is 2 to 20% by mass of a polycarboxylic acid.
- a method for etching a resin composition which comprises: ⁇ 9> The method for etching a resin composition according to ⁇ 8>, further including a step of applying ultrasonic waves after the etching treatment step.
- etching treatment step Prior to the etching treatment step, there is further provided a step of pretreatment with a pretreatment liquid consisting of an acidic aqueous solution containing 2.5 to 7.5% by mass of anionic surfactant.
- a pretreatment liquid consisting of an acidic aqueous solution containing 2.5 to 7.5% by mass of anionic surfactant.
- etching resist is used in the etching treatment step, and the etching resist is a metal mask or a dry film resist.
- a resin composition layer containing the resin composition is stably removed without residue. It is possible to provide an etching solution for a resin composition and an etching method in which an undercut hardly occurs in the resin composition layer after etching and the in-plane uniformity is high. Furthermore, it is possible to provide an etching method capable of suppressing the generation of unetched portions even in a small-diameter opening process in which the opening diameter is 100 ⁇ m or less.
- FIG. 3 is a schematic cross-sectional structure diagram of a solder resist pattern.
- FIG. 3 is a schematic cross-sectional structure diagram of a solder resist pattern.
- FIG. 4 is a cross-sectional process diagram showing an example of a process of etching the resin composition layer 4 by the etching method of the present invention.
- etching solution of the resin composition may be abbreviated as “etching solution”
- etching method of the resin composition may be abbreviated as “etching method”.
- the etching method of the present invention is characterized by including a step of etching a resin composition containing an alkali-insoluble resin and 50 to 80% by mass of an inorganic filler using the etching liquid of the present invention.
- the etching solution of the present invention contains 15 to 45 mass% of alkali metal hydroxide as the first component. Since the alkali-insoluble resin has the property of not being dissolved in the alkaline aqueous solution, it cannot be removed by the alkaline aqueous solution. However, by using the etching solution of the present invention, the resin composition containing the alkali-insoluble resin can be removed. This is because the inorganic filler in the highly filled resin composition, that is, the inorganic filler filled in the resin composition at a high content of 50 to 80 mass% has a high concentration of alkali metal hydroxide. This is because the solution is dispersed and removed by an aqueous solution containing.
- the content of the alkali metal hydroxide is 15 mass% or more, the solubility of the inorganic filler is excellent, and when the content of the alkali metal hydroxide is 45 mass% or less, the precipitation of the alkali metal hydroxide is performed. Is less likely to occur, the stability of the liquid over time is excellent.
- the content of the alkali metal hydroxide is more preferably 20 to 45% by mass.
- alkali metal hydroxide at least one compound selected from the group consisting of potassium hydroxide, sodium hydroxide and lithium hydroxide is preferably used.
- the alkali metal hydroxide one of these may be used alone, or two or more of them may be used in combination.
- the etching solution of the present invention contains 1 to 40% by mass of an ethanolamine compound as a second component.
- the ethanolamine compound penetrates into the resin composition, swells the resin composition, and the inorganic filler can be uniformly dissolved.
- the content of the ethanolamine compound is 1% by mass or more, the swelling property of the alkali-insoluble resin is excellent, and when it is 40% by mass or less, the compatibility with water becomes high, phase separation hardly occurs, and the stability with time is high. Excellent in.
- the content of the ethanolamine compound is more preferably 3 to 35% by mass.
- the ethanolamine compound may be any type such as primary amine, secondary amine, and tertiary amine, and may be used alone or in combination of two or more. Good.
- An example of a typical amine compound is 2-aminoethanol which is a primary amine; a mixture of a primary amine and a secondary amine (that is, a primary amino group and a secondary amino group in one molecule).
- 2- (2-aminoethylamino) ethanol which is a compound having a group; 2- (methylamino) ethanol and 2- (ethylamino) ethanol which are secondary amines; and 2,2 which is a tertiary amine Examples include'-methyliminodiethanol and N, N-dimethylaminoethanol. Among them, 2- (methylamino) ethanol and 2- (2-aminoethylamino) ethanol are more preferable.
- the etching solution of the present invention contains 3 to 60% by mass of a polyol compound, 2 to 20% by mass of a polycarboxylic acid or 2 to 20% by mass of a hydroxy acid as a third component.
- the etching solution of the present invention contains a polyol compound, a polyvalent carboxylic acid or a hydroxy acid, the alkali-insoluble resin and the dissolved inorganic filler can be simultaneously dispersed and removed.
- the etching liquid contains a polyol compound, a polycarboxylic acid or a hydroxy acid, and thus has a function of collecting components that cannot maintain the film shape, and at the same time improves the removal performance. It is considered that this effect increases the margin of the processing time in which the residue does not remain, and the resin composition containing the alkali-insoluble resin and many inorganic fillers can be stably removed.
- the content of the polyol compound used in the etching liquid of the present invention is less than 3% by mass, the performance of collectively dispersing becomes insufficient, and if it exceeds 60% by mass, it becomes too cohesive and the removability is insufficient. Becomes The content of the polyol compound is more preferably 10 to 40% by mass.
- the polyol compound used in the etching solution of the present invention has a preferable molecular weight range, preferably 80 or more and 200 or less.
- a compound having three or more hydroxyl groups is preferable.
- Specific examples include glycerin, pentaerythritol, sorbitol, xylitol, boremitol, diethylene glycol, ethylene glycol and the like. Among these, glycerin is particularly preferable.
- the polyol compound one kind may be used alone, or two or more kinds may be used in combination.
- the content of the polycarboxylic acid used in the etching solution of the present invention is less than 2% by mass, the ability to disperse them in a lump will be insufficient, and if it exceeds 20% by mass, they will be too cohesive and the removability will be poor. Will be enough.
- the content of polyvalent carboxylic acid is more preferably 3 to 15% by mass.
- the polyvalent carboxylic acid used in the etching solution of the present invention also includes salts of polyvalent carboxylic acids.
- polycarboxylic acid used in the etching solution of the present invention examples include oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), L-aspartic acid- Examples are N, N-2 acetic acid (ADSA), diethylenetriamine pentaacetic acid (DTPA) and salts thereof.
- polyvalent carboxylic acids malonic acid, maleic acid, ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA) and salts thereof in a process for removing a resin composition containing an alkali-insoluble resin and an inorganic filler
- EDTA ethylenediamine tetraacetic acid
- DTPA diethylenetriamine pentaacetic acid
- salts thereof in a process for removing a resin composition containing an alkali-insoluble resin and an inorganic filler
- EDTA ethylenediaminetetraacetic acid
- EDTA ethylenediaminetetraacetic acid
- its salts are preferred.
- the polycarboxylic acid one kind may be used alone, or two or more kinds may be used in combination.
- the content of the hydroxy acid used in the etching solution of the present invention is less than 2% by mass, the performance of collectively dispersing becomes insufficient, and if it exceeds 20% by mass, it becomes too cohesive and the removability becomes insufficient. Become.
- the content of hydroxy acid is more preferably 3 to 15% by mass.
- Hydroxy acids used in the etching solution of the present invention also include salts of hydroxy acids. Further, the salt of hydroxy acid may be a hydrate.
- the hydroxy acid used in the etching solution of the present invention includes glycolic acid, lactic acid, tartronic acid, glyceric acid, leucic acid, malic acid, tartaric acid, gluconic acid, citric acid, isocitric acid, mevalonic acid, pantoic acid, and hydroxyethyl.
- Iminodiacetic acid hydroxyiminodisuccinic acid, quinic acid, salicylic acid, 4-hydroxyphthalic acid, 4-hydroxyisophthalic acid, creosoteic acid (homosalicylic acid, hydroxy (methyl) benzoic acid), vanillic acid, syringic acid, hydroxypentane
- acids hydroxyhexanoic acid, resorcylic acid, protocatechuic acid, gentisic acid, orseric acid, gallic acid, mandelic acid, atrolactic acid, melilotic acid, phloretic acid, coumaric acid, umbellic acid, caffeic acid, and salts thereof. To be done.
- hydroxy acids malic acid, tartaric acid, gallic acid, 4-hydroxyisophthalic acid and salts thereof
- the resin composition in the process of removing the resin composition containing the alkali-insoluble resin and the inorganic filler, the resin composition is contained. It is more preferable in order to stably remove the resulting resin composition layer without a residue, tartaric acid and 4-hydroxyphthalic acid and salts thereof are more preferable, and tartaric acid and salts thereof are particularly preferable.
- the hydroxy acid one kind may be used alone, or two or more kinds may be used in combination.
- a coupling agent, a leveling agent, a coloring agent, a surfactant, an antifoaming agent, an organic solvent and the like can be appropriately added to the etching liquid of the present invention, if necessary.
- the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
- the etching solution of the present invention is preferably an alkaline aqueous solution.
- water used in the etching solution of the present invention tap water, industrial water, pure water or the like can be used. Of these, pure water is preferably used, and pure water generally used for industry can be used.
- the etching solution of the present invention is an etching solution of a resin composition containing an alkali-insoluble resin and an inorganic filler.
- the content of the inorganic filler in the resin composition is 50 to 80% by mass based on 100% by mass of the nonvolatile content in the resin composition.
- the content of the inorganic filler is less than 50% by mass, the amount of the inorganic filler serving as the sites dissolved by the etching solution is too small in the entire resin composition, so that the etching does not proceed. If the content of the inorganic filler exceeds 80% by mass, the fluidity of the resin composition is lowered, so that the flexibility tends to be lowered, resulting in poor practicality.
- examples of the inorganic filler include silicates such as silica, glass, clay and mica; oxides such as alumina, magnesium oxide, titanium oxide and silica; carbonates such as magnesium carbonate and calcium carbonate; water.
- examples thereof include hydroxides such as aluminum oxide, magnesium hydroxide and calcium hydroxide; sulfates such as barium sulfate and calcium sulfate.
- examples of the inorganic filler include aluminum borate, aluminum nitride, boron nitride, strontium titanate, barium titanate and the like.
- At least one compound selected from the group consisting of silica, glass, clay and aluminum hydroxide is more preferably used because it dissolves in an aqueous solution containing an alkali metal hydroxide.
- Silica is more preferable because of its excellent low thermal expansion property, and spherical fused silica is particularly preferable.
- the inorganic filler one kind among these may be used alone, or two or more kinds may be used in combination.
- the alkali-insoluble resin in the present invention will be described.
- the alkali-insoluble resin is not particularly limited, except that it is not dissolved in an alkaline aqueous solution. Specifically, it is a resin having a very small content of a carboxyl group-containing resin or the like necessary for dissolving in an alkaline aqueous solution, and has an acid value (JIS K2501) as an index of the content of a free carboxyl group in the resin. : 2003) is less than 40 mg KOH / g. More specifically, the alkali-insoluble resin is, for example, a resin containing an epoxy resin and a thermosetting agent that cures the epoxy resin.
- An aqueous solution containing the organic alkaline compound of is mentioned.
- Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins and other bisphenol type epoxy resins; phenol novolac type epoxy resins, cresol novolac type epoxy resins and other novolac type epoxy resins. Can be mentioned. Further, examples of the epoxy resin include biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, fluorene type epoxy resin and the like. As the epoxy resin, one kind among these may be used alone, or two or more kinds may be used in combination.
- thermosetting agent is not particularly limited as long as it has a function of curing an epoxy resin, but preferable examples include a phenol type curing agent, a naphthol type curing agent, an active ester type curing agent, a benzoxazine type curing agent, Cyanate ester resin etc. are mentioned.
- a phenol type curing agent a naphthol type curing agent
- an active ester type curing agent a benzoxazine type curing agent
- Cyanate ester resin etc. are mentioned.
- thermosetting agent one kind among these may be used alone, or two or more kinds may be used in combination.
- a curing accelerator can be further contained.
- the curing accelerator include organic phosphine compounds, organic phosphonium salt compounds, imidazole compounds, amine adduct compounds and tertiary amine compounds.
- the curing accelerator one of these may be used alone, or two or more of them may be used in combination.
- an organometallic compound used as a curing catalyst may be added for the purpose of shortening the curing time.
- the organic metal compound include organic copper compounds, organic zinc compounds, organic cobalt compounds and the like.
- a resin composition containing an alkali-insoluble resin and an inorganic filler can be thermally cured to form an insulating resin composition layer.
- the etching in the etching method of the present invention can be performed at the A stage (before the initiation of the curing reaction) or It proceeds in the state of B stage (intermediate stage of curing reaction).
- the alkali-insoluble resin does not dissolve in the etching solution of the present invention, but the inorganic filler is partially or wholly dissolved in the etching solution of the present invention, whereby the resin composition is dispersed and removed.
- the stage C is reached and the resin is completely cured, it becomes difficult for the etching solution of the present invention to swell the resin composition layer and to penetrate into the resin composition layer, which makes uniform etching difficult.
- the heat curing condition from the A stage to the B stage is preferably 100 to 160 ° C. for 10 to 60 minutes, more preferably 100 to 130 ° C. for 10 to 60 minutes, but is not limited thereto. Not a thing.
- thermosetting proceeds further, and the etching treatment using the etching solution of the present invention becomes difficult.
- FIG. 3 is a sectional process drawing showing an example of a process of etching the resin composition layer 4 by the etching method of the present invention.
- a solder resist pattern in which a part or all of the solder connection pads 3 on the circuit board are exposed from the resin composition layer 4 can be formed.
- the copper foil 3'on the surface of the copper clad laminate 1'composed of the insulating layer 2 and the copper foil 3' is patterned by etching to form the conductor pattern A, and the solder connection pads 3 are formed.
- the circuit board 1 having is formed.
- step (II) the resin composition layer 4 with the copper foil 6 is formed on the surface of the circuit board 1 so as to cover the entire surface.
- step (III) the copper foil 6 on the resin composition layer 4 is patterned by etching to form a metal mask as an etching resist 5.
- step (IV) the resin composition layer 4 is etched through the etching resist 5 (metal mask) with an etching solution for the resin composition layer until a part or all of the solder connection pad 3 is exposed.
- the etching resist 5 metal mask
- the etching resist 5 is removed by etching to form a solder resist pattern in which a part or all of the solder connection pad 3 is exposed from the resin composition layer 4.
- the temperature of the etching solution is preferably 60 to 90 ° C.
- the optimum temperature varies depending on the type of the resin composition, the thickness of the resin composition layer containing the resin composition, the shape of the pattern obtained by the process of removing the resin composition, etc., but the temperature of the etching solution is The temperature is preferably 60 to 85 ° C, more preferably 70 to 85 ° C.
- part or all of the highly filled inorganic filler is gradually dissolved from the surface layer of the resin composition and dispersed with the alkali-insoluble resin. Thereby, the removal of the resin composition proceeds.
- the treatment for etching the resin composition methods such as dipping treatment, paddle treatment, spraying treatment, brushing, scraping and the like can be used. Among these, the dipping treatment is preferable.
- the etching liquid remaining on the surface of the resin composition is washed by a water washing treatment.
- a spray method is preferable from the viewpoint of diffusion rate and uniformity of liquid supply.
- the washing water tap water, industrial water, pure water or the like can be used. Of these, it is preferable to use pure water. As the pure water, those generally used for industry can be used.
- the temperature of the washing water is equal to or lower than the temperature of the etching solution, and preferably the temperature difference is 40 to 50 ° C.
- the etching method of the present invention preferably has a step of irradiating ultrasonic waves after the etching step using the above-mentioned etching solution.
- the step of irradiating with ultrasonic waves may be performed during the water washing step immediately after the etching treatment step, or after the etching treatment step, through the water washing step and after the drying step, during the step of removing the etching resist 5. You may perform an ultrasonic irradiation process. Further, in the water washing step after removing the etching resist 5, the ultrasonic irradiation is effective. However, even if ultrasonic waves are applied during the etching process, the desired effect cannot be obtained.
- the etching method of the present invention refers to the next step after (III) to (V) are completed.
- wet ultrasonic wave irradiation is performed after the etching process using the etching solution (IV) is completed and before (V) is completed and the next step is started. Refers to a process.
- the etching mechanism of the present invention is to dissolve a part or all of an inorganic filler highly filled in a resin composition insoluble in an etching solution, in an etching solution containing a high concentration of an alkali metal hydroxide, This is an etching method in which a state in which the film shape of the resin composition cannot be maintained is formed, and in a subsequent step, a portion where the film cannot be formed is removed. Therefore, it is considered that the irradiation of ultrasonic waves in the etching solution causes the disorder of the shape after etching and the in-plane uniformity cannot be maintained, which causes the desired effect to be not obtained.
- the conditions for ultrasonic irradiation vary depending on the composition of the resin composition containing the alkali-insoluble resin and 50 to 80% by mass of the inorganic filler, the curing state, the composition of the etching solution, etc., but a frequency of 15 kHz or higher is preferable. , 50 kHz or more is more preferable.
- the liquid temperature when irradiating with ultrasonic waves is preferably 70 ° C. or lower, more preferably 60 ° C. or lower.
- the etching method of the present invention comprises a step of pretreating the resin composition with a pretreatment liquid consisting of an acidic aqueous solution containing 2.5 to 7.5% by mass of an anionic surfactant before the etching treatment step. It is preferable to have.
- the pretreatment liquid according to the present invention is an acidic aqueous solution containing 2.5 to 7.5% by mass of anionic surfactant.
- anionic surfactant contained in the pretreatment liquid according to the present invention include lauryl sulfate, polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, and alkylbenzene sulfonate.
- anionic surfactants polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl ether sulfate, and alkylnaphthalene sulfonate have a small diameter so that the opening diameter of the openings in the resin composition layer is ⁇ 100 ⁇ m or less.
- alkylnaphthalene sulfonate is particularly preferable.
- alkali metal ions and alkanolamine salt ion are preferable.
- these anionic surfactants may be used alone or in combination of two or more.
- the content of the anionic surfactant contained in the pretreatment liquid is It is preferably 2.5% by mass or more, and more preferably 3% by mass or more.
- the obtained effect does not increase, it is uneconomical, and it takes time to wash with water after pretreatment, and in the case of insufficient washing with water, aggregation of anionic surfactants leads to the generation of unetched portions. From the viewpoint of fear, etc., it is preferably 7.5% by mass or less, and more preferably 6% by mass or less.
- the pretreatment liquid according to the present invention is acidic, and the pH is 6 or less from the viewpoint of suppressing the generation of unetched portions even in the small-diameter opening treatment such that the opening diameter of the opening in the resin composition layer is ⁇ 100 ⁇ m or less. Preferably there is.
- the pH is preferably 1 or more from the viewpoint that the obtained effect does not increase, it is uneconomical, and that it takes time to mix the pH adjuster.
- the pH adjuster hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, hydroxide salt, carbonate or the like can be used.
- the pretreatment liquid according to the present invention may contain known additives such as an antifoaming agent, a foam suppressor, a thickener, and a preservative.
- water used in the pretreatment liquid according to the present invention tap water, industrial water, pure water, etc. can be used. Of these, it is preferable to use pure water. In the present invention, pure water generally used for industry can be used.
- the pretreatment time is not particularly limited, but even in a small-diameter opening treatment such that the opening diameter of the opening in the resin composition layer is ⁇ 100 ⁇ m or less, it is 1 minute or more in order to suppress the generation of unetched portions. It is preferable that it is for 3 minutes or more.
- the pretreatment time is preferably 10 minutes or less.
- the temperature of the pretreatment liquid according to the present invention is not particularly limited, but even in a small-diameter opening treatment such that the opening diameter of the opening in the resin composition layer is ⁇ 100 ⁇ m or less, in order to suppress the generation of unetched portions, 10 ° C. It is preferably at least 30 ° C., more preferably at 30 ° C. or higher.
- the temperature of the pretreatment liquid is preferably 70 ° C. or lower.
- the pretreatment liquid is brought into contact with the resin composition layer 4 and the etching resist 5 to improve the affinity between the etching liquid and the resin composition layer 4, and then the etching is performed.
- the resin composition layer 4 is etched through the resist 5 with the etching solution of the present invention until a part or all of the solder connection pad 3 is exposed.
- the pretreatment liquid adhering to the surface of the resin composition layer 4 is preferably washed with water.
- a spray method is preferable from the viewpoint of diffusion rate and uniformity of liquid supply.
- the washing water tap water, industrial water, pure water or the like can be used. Of these, it is preferable to use pure water.
- the pure water those generally used for industry can be used.
- the temperature of the washing water is preferably 10 to 30 ° C.
- etching resist 5 When the etching resist 5 is used in the etching process, a dry film resist pattern can be used as the etching resist 5 in addition to the metal mask described above.
- the dry film resist according to the present invention contains at least a photocrosslinkable resin composition and is coated with a photocrosslinkable resin on a carrier film such as polyester to form a photocrosslinkable resin layer. It is configured such that the film covers the photocrosslinkable resin layer.
- the photocrosslinkable resin layer contains, for example, a binder polymer containing a carboxyl group, a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, a photopolymerization initiator, a solvent, and other additives. To do. The blending ratio thereof is determined by the balance of required properties such as sensitivity, resolution, and degree of crosslinking.
- photo-crosslinkable resin composition examples include "Photopolymer Handbook” (edited by Photopolymer Association, published in 1989, published by Kogyo Kenkyukai) and “Photopolymer Technology” (edited by Ao Yamamoto, Mototaro Nagamatsu, 1988). Published, published by Nikkan Kogyo Shimbun, etc., and a desired photocrosslinkable resin composition can be used.
- the thickness of the photocrosslinkable resin layer is preferably 15 to 100 ⁇ m, more preferably 20 to 50 ⁇ m.
- the method for exposing the dry film resist according to the present invention includes a xenon lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high pressure mercury lamp, a reflective image exposure using a UV fluorescent lamp as a light source, a single-sided and double-sided contact exposure using a photomask, and a proxy.
- Examples include the mitigation method, projection method, and laser scanning exposure.
- a laser light source such as a He-Ne laser, a He-Cd laser, an argon laser, a krypton ion laser, a ruby laser, a YAG laser, a nitrogen laser, a dye laser, and an excimer laser is used depending on the emission wavelength.
- the exposure can be performed by wavelength conversion and scanning exposure, or by scanning exposure using a liquid crystal shutter or a micromirror array shutter.
- a developer suitable for the photo-crosslinkable resin layer used is sprayed from the vertical direction of the substrate toward the substrate surface to remove unnecessary dry film resist (unexposed film). Part) is removed and an etching resist 5 having a dry film resist pattern is formed.
- the developing solution generally, a 1 to 3 mass% sodium carbonate aqueous solution is used, and more preferably a 1 mass% sodium carbonate aqueous solution is used.
- a peeling liquid suitable for the photocrosslinkable resin layer to be used is sprayed from the vertical direction of the substrate toward the substrate surface to form the dry film resist pattern. Remove.
- the stripping solution 2 to 4 mass% sodium hydroxide aqueous solution is generally used, and more preferably 3 mass% sodium hydroxide aqueous solution is used.
- Examples 1-1 to 1-15 and 1-17, Comparative Examples 1-2 to 1-7) 78% by mass of spherical fused silica as an inorganic filler, 10% by mass of a biphenylaralkyl type epoxy resin as an epoxy resin, 10% by mass of a phenol novolac type cyanate resin as a thermosetting agent, and 1% by mass of triphenylphosphine as a curing accelerator.
- a coupling agent and a leveling agent were added to make the total amount 100% by mass, and methyl ethyl ketone and cyclohexanone were mixed as a medium to obtain a liquid resin composition.
- the liquid resin composition was applied on a polyethylene terephthalate film (thickness 38 ⁇ m), and then dried at 100 ° C. for 5 minutes to remove the medium.
- an A-stage resin composition layer having a film thickness of 20 ⁇ m and made of a resin composition containing an alkali-insoluble resin and an inorganic filler was formed.
- a peelable metal foil in which a copper foil 6 having a thickness of 3 ⁇ m, a peeling layer, and a carrier foil are laminated in this order is prepared, and the copper foil 6 and the resin composition layer 4 are thermocompression bonded to each other. After that, the peeling layer and the carrier foil were peeled off to obtain a resin composition layer 4 with a copper foil 6.
- Epoxy resin glass cloth base material copper clad laminate 1 '(area 170 mm x 255 mm, copper foil thickness 12 ⁇ m, base material thickness 0.1 mm) copper foil 3'on one surface is patterned by etching to form a conductor pattern A.
- the formed epoxy resin glass cloth base material (circuit board 1) was obtained.
- the polyethylene terephthalate film is peeled off from the resin composition layer 4 with the copper foil 6, and the epoxy resin glass cloth base material on which the conductor pattern A is formed is heated at a temperature of 100 ° C. using a vacuum heat-bonding laminator. After vacuum thermocompression bonding at 1.0 MPa, it was heated at 130 ° C. for 45 minutes to form a B-stage resin composition layer 4.
- the copper foil 6 on the resin composition layer 4 was patterned by etching to form an opening in a predetermined region of the copper foil, and a resin composition layer 4 with an etching resist 5 (metal mask) was prepared.
- the resin composition layer 4 was subjected to an etching treatment by immersion treatment at 80 ° C. with the etching liquid described in Table 1 or 2 through the etching resist 5. After the etching treatment, the etching liquid remaining on the surface of the resin composition layer 4 was washed by a spray treatment with pure water.
- the opening length a of the etching resist 5 is 270 ⁇ m and the film thickness b of the resin composition layer 4 is 20 ⁇ m
- the bottom length c of the opening of the resin composition layer 4 is 310 ⁇ m ⁇ 5 ⁇ m.
- Table 1 and Table 2 show the different processing times as "standard processing time”.
- the presence / absence of resin residue was evaluated as to whether or not the resin composition layer 4 was reliably removed from the opening of the etching resist 5. Further, whether or not the resin composition layer 4 can be stably removed was evaluated by the residue of the evaluation portion 7 shown in FIG. Further, "presence or absence of undercut” was evaluated as the evaluation of the deformation in the opening shape of the resin composition layer 4. The results are shown in Tables 1 and 2. The criteria for each evaluation are shown below.
- Undercut is not seen in the resin composition layer.
- ⁇ A small undercut is seen on the bottom surface of the resin composition layer.
- X A large undercut, which is a practical problem, is seen on the bottom surface of the resin composition layer.
- Example 1-16 An etching treatment was performed in the same manner as in Example 1-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 2.
- Example 1-1 An etching treatment was performed in the same manner as in Example 1-3, except that the content of the spherical fused silica was 45% by mass and the content of the biphenylaralkyl type epoxy resin was 43% by mass. Although the etching time was extended to 30 minutes, a large amount of resin remained on the surface of the conductor pattern and the epoxy resin glass cloth substrate, and the resin composition layer could not be etched. The results are shown in Table 2.
- the etching liquid of the present invention causes less undercut, less residue of the resin composition, an alkali-insoluble resin and an inorganic filler as compared with Comparative Examples.
- the contained resin composition can be stably removed.
- Example 2-13 Etching treatment was performed in the same manner as in Example 2-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 4.
- the etching liquid of the present invention causes less undercut, less residue of the resin composition, an alkali-insoluble resin and an inorganic filler as compared with Comparative Examples.
- the contained resin composition can be stably removed.
- Example 3-13 Etching treatment was performed in the same manner as in Example 3-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 6.
- the etching solution of the present invention causes less undercut, less residue of the resin composition, an alkali-insoluble resin and an inorganic filler as compared with Comparative Examples.
- the contained resin composition can be stably removed.
- Examples 4-1 to 4-7 Comparative Examples 4-2 to 4-3 78% by mass of spherical fused silica as an inorganic filler, 10% by mass of a biphenylaralkyl type epoxy resin as an epoxy resin, 10% by mass of a phenol novolac type cyanate resin as a thermosetting agent, and 1% by mass of triphenylphosphine as a curing accelerator.
- a coupling agent and a leveling agent were added to make the total amount 100% by mass, and methyl ethyl ketone and cyclohexanone were mixed as a medium to obtain a liquid resin composition.
- the liquid resin composition was applied on a polyethylene terephthalate film (thickness 38 ⁇ m), and then dried at 100 ° C. for 5 minutes to remove the medium.
- an A-stage resin composition layer having a film thickness of 20 ⁇ m and made of a resin composition containing an alkali-insoluble resin and an inorganic filler was formed.
- a peelable metal foil in which a copper foil 6 having a thickness of 3 ⁇ m, a peeling layer, and a carrier foil were laminated in this order was prepared, and both were thermocompression bonded so that the copper foil and the resin composition layer were in contact with each other. After that, the peeling layer and the carrier foil were peeled off to obtain a resin composition layer 4 with a copper foil 6.
- Epoxy resin glass cloth base material copper clad laminate 1 '(area horizontal 400mm x 500mm, copper foil thickness 12 ⁇ m, base material thickness 0.1mm) copper foil 3'on one surface is patterned by etching, and conductor pattern A
- an epoxy resin glass cloth base material (circuit board 1) was obtained in which 10 pieces were evenly arranged in the horizontal direction and 12 pieces were arranged in the longitudinal direction.
- the polyethylene terephthalate film is peeled off from the resin composition layer 4 with the copper foil 6, and the epoxy resin glass cloth base material on which the conductor pattern A is formed is heated at a temperature of 100 ° C. using a vacuum heat-bonding laminator. After vacuum thermocompression bonding at 1.0 MPa, it was heated at 130 ° C. for 45 minutes to form a B-stage resin composition layer 4.
- the copper foil 6 on the resin composition layer 4 was patterned by etching to form an opening in a predetermined region of the copper foil, and a resin composition layer 4 with an etching resist 5 (metal mask) 5 was prepared. .
- the resin composition layer 4 was dipped at 80 ° C. through the etching resist 5 with the etching solution shown in Table 7, and subsequently, at the temperature of 25 ° C. for the purpose of removing the resin composition layer 4.
- Immersion treatment was performed in a tank filled with tap water. During the immersion treatment with tap water, the presence or absence of ultrasonic irradiation was changed. Then, the surface was washed by spraying with pure water. Table 7 shows the composition of the etching solution and the presence or absence of ultrasonic irradiation.
- the presence / absence of resin residue was evaluated as to whether or not the resin composition layer 4 was reliably removed from the opening of the etching resist 5. Moreover, "undercut” was evaluated as an evaluation of the deformation in the opening shape of the resin composition layer 4. Further, the target opening diameters (target opening diameters) are the same, and 120 openings d in the plane are observed, and the opening diameter of the opening having the maximum opening diameter is the "maximum value”. The opening diameter of the opening having the smallest value was taken as the "minimum value”, and the variation value (%) was calculated by "(maximum value-minimum value) / opening target value x 100", and "in-plane uniformity" was evaluated. The results are shown in Table 7. The criteria for each evaluation are shown below.
- undercut Undercut is not seen in the resin composition layer.
- B A very small undercut is seen on the bottom surface of the resin composition layer.
- ⁇ A small undercut is observed on the bottom surface of the resin composition layer, but this is not a problem.
- X A large undercut, which is a practical problem, is seen on the bottom surface of the resin composition layer.
- Example 4-8 Etching treatment was performed in the same manner as in Example 4-2, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 7.
- Example 4-1 An etching treatment was performed in the same manner as in Example 4-2, except that the content of the spherical fused silica was 45% by mass and the content of the biphenylaralkyl type epoxy resin was 43% by mass. Although the etching time was extended to 30 minutes, a large amount of resin remained on the surface of the conductor pattern and the epoxy resin glass cloth substrate, and the resin composition layer could not be etched. The results are shown in Table 7.
- Examples 4-9 to 4-13 By the same method as in Examples 4-1, 4-2, 4-4, 4-6 and 4-7, except that ultrasonic irradiation is not performed during the immersion treatment for removing the resin composition layer 4. An etching process was performed. The results are shown in Table 7.
- Example 4-14 After the etching treatment (IV), the etching resist 5 (metal mask) obtained by the same method as in Example 4-10 was removed using a ferric chloride solution, and ultrasonic irradiation was performed in the subsequent water washing step. .
- the results are shown in Table 7.
- the resin composition containing the alkali-insoluble resin and the inorganic filler is undercut by having a step of ultrasonic irradiation after the etching treatment step using the etching solution of the resin composition. It can be seen that there is little generation of the resin composition, the resin composition can be stably removed without residue, and the in-plane uniformity is high.
- Examples 5-1 to 5-7 Comparative examples 5-2 to 5-3
- Etching treatment was performed in the same manner as in Example 4-1, except that the etching solutions shown in Table 8 or Table 9 were used. The results are shown in Tables 8 and 9.
- Example 5-8 By the same method as in Example 4-1, except that the content of the spherical fused silica was 55% by mass, the content of the biphenylaralkyl type epoxy resin was 33% by mass, and the etching solution shown in Table 9 was used. An etching process was performed. The results are shown in Table 9.
- Examples 5-9 to 5-13 By the same method as in Examples 5-1, 5-3, 5-4, 5-5 and 5-7, except that ultrasonic irradiation is not performed during the dipping treatment for removing the resin composition layer 4. An etching process was performed. The results are shown in Table 9.
- Example 5-14 After performing the etching treatment in the same manner as in Example 5-12, the etching resist 5 (metal mask) was removed using a ferric chloride solution, and ultrasonic irradiation was performed in the subsequent step of washing with water. The results are shown in Table 9.
- the resin composition containing the alkali-insoluble resin and the inorganic filler can be obtained by the step of ultrasonic irradiation after the etching treatment step using the etching solution of the resin composition. It can be seen that the occurrence of undercut is small, the resin composition can be stably removed without residue, and the in-plane uniformity is high.
- Example 6-12 An etching treatment was performed in the same manner as in Example 6-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 11.
- Example 6-1 An etching treatment was performed in the same manner as in Example 6-3, except that the content of the spherical fused silica was 45% by mass and the content of the biphenylaralkyl type epoxy resin was 43% by mass. Although the etching time was extended to 30 minutes, a large amount of resin remained on the surface of the conductor pattern and the epoxy resin glass cloth substrate, and the resin composition layer could not be etched. The results are shown in Table 11.
- Example 6-21 After performing the etching treatment in the same manner as in Example 6-15, the etching resist 5 (metal mask) was removed using a ferric chloride solution, and ultrasonic irradiation was performed in the subsequent step of washing with water. The results are shown in Table 11.
- the resin composition containing the alkali-insoluble resin and the inorganic filler can be obtained by the step of irradiating ultrasonic waves after the etching treatment step using the etching solution of the resin composition. It can be seen that the occurrence of undercut is small, the resin composition can be stably removed without residue, and the in-plane uniformity is high.
- the liquid resin composition was applied on a polyethylene terephthalate film (thickness 38 ⁇ m), and then dried at 100 ° C. for 5 minutes to remove the medium.
- an A-stage resin composition layer having a film thickness of 20 ⁇ m and made of a resin composition containing an alkali-insoluble resin and an inorganic filler was formed.
- a peelable metal foil in which a copper foil 6 having a thickness of 3 ⁇ m, a peeling layer, and a carrier foil were laminated in this order was prepared, and both were thermocompression bonded so that the copper foil and the resin composition layer were in contact with each other. After that, the peeling layer and the carrier foil were peeled off to obtain a resin composition layer 4 with a copper foil 6.
- Epoxy resin glass cloth base material copper clad laminate 1 '(area 170 mm x 255 mm, copper foil thickness 12 ⁇ m, base material thickness 0.1 mm) copper foil 3'on one surface is patterned by etching to form a conductor pattern A.
- the formed epoxy resin glass cloth base material (circuit board 1) was obtained.
- the polyethylene terephthalate film is peeled off from the resin composition layer 4 with the copper foil 6, and the epoxy resin glass cloth base material on which the conductor pattern A is formed is heated at a temperature of 100 ° C. using a vacuum heat-bonding laminator. After vacuum thermocompression bonding at 1.0 MPa, it was heated at 130 ° C. for 45 minutes to form a B-stage resin composition layer 4.
- the copper foil 6 on the resin composition layer 4 was patterned by etching to form an opening in a predetermined region of the copper foil 6, and a resin composition layer 4 with an etching resist 5 (metal mask) was prepared. .
- a spray-type water washing treatment with pure water is performed for 1 minute to perform etching.
- the resin composition layer 4 is subjected to an etching treatment by immersion treatment at 80 ° C. with the etching liquid described in Table 13 through the etching resist 5. went.
- the pH of each pretreatment liquid was adjusted using sulfuric acid or potassium hydroxide. After the etching treatment, the etching liquid remaining on the surface of the resin composition layer 4 was washed by a spray treatment with pure water.
- the film thickness b of the resin composition layer 4 and the bottom length c of the opening of the resin composition layer 4 shown in FIG. It was defined as "standard processing time”. Specifically, since the opening length a of the etching resist 5 is 160 ⁇ m and the film thickness b of the resin composition layer 4 is 20 ⁇ m, the bottom length c of the opening of the resin composition layer 4 is 200 ⁇ m ⁇ 5 ⁇ m.
- the treatment time was defined as "standard treatment time”.
- the opening length a of the etching resist 5 is 50 ⁇ m and the film thickness b of the resin composition layer 4 is 20 ⁇ m
- the bottom length of the opening of the resin composition layer 4 is confirmed from the confirmation of 100 openings of the etching resist 5. It was evaluated by "small-diameter opening" whether or not the small-diameter opening treatment was performed when the thickness c was 90 ⁇ m ⁇ 5 ⁇ m. The results are shown in Table 14.
- etching was performed using an etching liquid of the resin composition.
- the etching treatment can be performed while suppressing the unetched portion even in the small-diameter opening treatment in which the opening diameter of the opening portion in the resin composition layer containing the alkali-insoluble resin and the inorganic filler becomes ⁇ 100 ⁇ m or less.
- Examples 7-1 to 7-15 and 7-17, Comparative Examples 7-2 to 7-7) 78% by mass of spherical fused silica as an inorganic filler, 10% by mass of a biphenylaralkyl type epoxy resin as an epoxy resin, 10% by mass of a phenol novolac type cyanate resin as a thermosetting agent, and 1% by mass of triphenylphosphine as a curing accelerator.
- a coupling agent and a leveling agent were added to make the total amount 100% by mass, and methyl ethyl ketone and cyclohexanone were mixed as a medium to obtain a liquid resin composition.
- the liquid resin composition was applied on a polyethylene terephthalate film (thickness 38 ⁇ m), and then dried at 100 ° C. for 5 minutes to remove the medium.
- an A-stage resin composition layer having a film thickness of 20 ⁇ m and made of a resin composition containing an alkali-insoluble resin and an inorganic filler was formed.
- Epoxy resin glass cloth base material copper clad laminate 1 '(area 170 mm x 255 mm, copper foil thickness 12 ⁇ m, base material thickness 0.1 mm) copper foil 3'on one surface is patterned by etching to form a conductor pattern A.
- the formed epoxy resin glass cloth base material (circuit board 1) was obtained.
- the resin composition layer 4 was vacuum thermocompression-bonded at a temperature of 100 ° C. and a pressure of 1.0 MPa on the epoxy resin glass cloth substrate on which the conductor pattern A was formed, using a vacuum thermocompression-bonding type laminator, 130 It heated at 45 degreeC for 45 minutes, and formed the resin composition layer 4 of B stage.
- a dry film resist 6 (manufactured by Asahi Kasei Co., Ltd., trade name: ASG-302) was thermocompression-bonded on the resin composition layer 4, and then an energy of 50 mJ / cm 2 was applied through a photomask by a contact exposure machine.
- the dry film resist 6 is subjected to pattern exposure, and then developed with a 1% by mass aqueous solution of sodium carbonate at 25 ° C. to form an opening in a predetermined region of the dry film resist 6, and the etching resist 5 (dry A resin composition layer 4 having a film resist pattern) was prepared.
- the opening length a of the etching resist 5 was 270 ⁇ m and the film thickness b of the resin composition layer 4 was 20 ⁇ m
- the bottom length c of the opening of the resin composition layer 4 was 310 ⁇ m ⁇ 5 ⁇ m. Tables 15 and 16 show the different processing times as "standard processing time”.
- the presence / absence of resin residue was evaluated as to whether or not the resin composition layer 4 was reliably removed from the opening of the etching resist 5. Further, whether or not the resin composition layer 4 can be stably removed was evaluated by the residue of the evaluation portion 7 shown in FIG. Further, "presence or absence of undercut” was evaluated as the evaluation of the deformation in the opening shape of the resin composition layer 4. The results are shown in Tables 15 and 16. The criteria for each evaluation are shown below.
- Undercut is not seen in the resin composition layer.
- ⁇ A small undercut is seen on the bottom surface of the resin composition layer.
- X A large undercut, which is a practical problem, is seen on the bottom surface of the resin composition layer.
- Example 7-16 An etching treatment was performed in the same manner as in Example 7-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 16.
- the resin composition containing the alkali-insoluble resin and the inorganic filler is less likely to cause undercut and has no residue of the resin composition, as compared with Comparative Examples. It can be removed stably.
- Example 8-13 An etching treatment was performed in the same manner as in Example 8-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 18.
- the resin composition containing the alkali-insoluble resin and the inorganic filler is less likely to cause undercut and has less residue in the resin composition, as compared with Comparative Examples. , Can be removed stably.
- Example 9-13 Etching treatment was performed in the same manner as in Example 9-3, except that the content of the spherical fused silica was 55 mass% and the content of the biphenylaralkyl-type epoxy resin was 33 mass%. The results are shown in Table 20.
- the present invention provides a resin composition containing an alkali-insoluble resin and an inorganic filler with less undercut and no residue of the resin composition, as compared with Comparative Examples. It can be removed stably.
- the etching liquid and the etching method of the present invention are capable of etching an insulating resin composition layer filled with a high content of an inorganic filler and having excellent heat resistance, dielectric properties, mechanical strength, chemical resistance, etc.
- it can be applied to fine processing of an insulating resin in a multilayer build-up wiring board, a component built-in module board, a flip chip package board, a package board mounting motherboard, and the like.
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Abstract
Description
<2>第3成分が、3~60質量%のポリオール化合物である<1>に記載の樹脂組成物のエッチング液。
<3>上記ポリオール化合物の分子量が80以上200以下である<1>又は<2>に記載の樹脂組成物のエッチング液。
<4>上記ポリオール化合物が3つ以上のヒドロキシル基を有する<1>~<3>のいずれかに記載の樹脂組成物のエッチング液。
<5>上記ポリオール化合物が、グリセリンである<1>~<4>のいずれかに記載の樹脂組成物のエッチング液。
<6>第3成分が、2~20質量%の多価カルボン酸である<1>に記載の樹脂組成物のエッチング液。
<7>第3成分が、2~20質量%のヒドロキシ酸である<1>に記載の樹脂組成物のエッチング液。
<8><1>~<7>のいずれかに記載の樹脂組成物のエッチング液を用いて、アルカリ不溶性樹脂及び50~80質量%の無機充填剤を含む樹脂組成物をエッチング処理する工程を有することを特徴とする樹脂組成物のエッチング方法。
<9>エッチング処理工程後に、超音波照射する工程をさらに有する<8>に記載の樹脂組成物のエッチング方法。
<10>エッチング処理工程前に、2.5~7.5質量%の陰イオン界面活性剤を含有する酸性水溶液からなる前処理液で前処理する工程をさらに有する<8>又は<9>に記載の樹脂組成物のエッチング方法。
<11>エッチング処理工程において、エッチングレジストを使用し、このエッチングレジストが、金属マスク又はドライフィルムレジストである<8>~<10>のいずれかに記載の樹脂組成物のエッチング方法。
無機充填剤として、球状溶融シリカ78質量%、エポキシ樹脂として、ビフェニルアラルキル型エポキシ樹脂10質量%、熱硬化剤として、フェノールノボラック型シアネート樹脂10質量%、硬化促進剤として、トリフェニルホスフィン1質量%、その他、カップリング剤、レベリング剤を加え、全量を100質量%としたものに、メチルエチルケトンとシクロヘキサノンを媒体として混合し、液状樹脂組成物を得た。
○:樹脂組成物が残っていない。
△:極微量の樹脂組成物が残っているが、プラズマ洗浄処理等の後処理で容易に除去できるレベル。
×:多くの樹脂組成物が残り、後処理で除去されないレベル。
○:エッチング処理時間が「標準処理時間±30%」でも、エッチング後の表面に樹脂組成物が残っていない。
△:エッチング処理時間が「標準処理時間±30%」でも、エッチング後の表面に極微量の樹脂組成物が残っているが、プラズマ洗浄処理等の後処理で容易に除去できるレベルである。
×:エッチング処理時間が「標準処理時間±30%」で、エッチング後の表面に多くの樹脂組成物が残り、後処理で除去されないレベル。
〇:樹脂組成物層にアンダーカットが見られない。
△:樹脂組成物層の底面に小さなアンダーカットが見られる。
×:樹脂組成物層の底面に実用上問題となる大きなアンダーカットが見られる。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例1-3と同様の方法により、エッチング処理を行った。結果を表2に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とした以外は、実施例1-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表2に示す。
実施例1-1と同様の方法により得られたエッチングレジスト5付きの樹脂組成物層4をウェットブラストによりエッチング処理し、その後、エッチングレジスト5を除去した。これを光学顕微鏡で観察した結果、樹脂組成物層4のエッチング量にばらつきがあり、エポキシ樹脂ガラス布基材上に樹脂組成物が残っている箇所があった。また、表面の一部又は全部が露出された導体パターンにはブラスト処理によって付けられた傷が多数確認された。
表3又は表4に記載したエッチング液を使用した以外は、実施例1-1と同様の方法により、エッチング処理を行った。結果を表3及び表4に示す。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例2-3と同様の方法により、エッチング処理を行った。結果を表4に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とし、エッチング時間を30分まで延長した以外は、実施例2-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表4に示す。
表5又は表6に記載したエッチング液を使用した以外は、実施例1-1と同様の方法により、エッチング処理を行った。結果を表5及び表6に示す。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例3-3と同様の方法により、エッチング処理を行った。結果を表6に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とし、エッチング時間を30分まで延長した以外は、実施例3-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表6に示す。
無機充填剤として、球状溶融シリカ78質量%、エポキシ樹脂として、ビフェニルアラルキル型エポキシ樹脂10質量%、熱硬化剤として、フェノールノボラック型シアネート樹脂10質量%、硬化促進剤として、トリフェニルホスフィン1質量%、その他、カップリング剤、レベリング剤を加え、全量を100質量%としたものに、メチルエチルケトンとシクロヘキサノンを媒体として混合し、液状樹脂組成物を得た。
○:樹脂組成物が残っていない。
○△:極微量の樹脂組成物が残っているが、問題とならないレベル。
△:微量の樹脂組成物が残っているが、プラズマ洗浄処理で容易に除去できるレベル。
×:多くの樹脂組成物が残り、プラズマ洗浄処理で除去されないレベル。
○:樹脂組成物層にアンダーカットが見られない。
○△:樹脂組成物層の底面に極小さなアンダーカットが見られる。
△:樹脂組成物層の底面に小さなアンダーカットが見られるが問題とならないレベル。
×:樹脂組成物層の底面に実用上問題となる大きなアンダーカットが見られる。
○:非常に均一性が高い。変動値が3%未満。
○△:均一性が高い。変動値が3%以上5%未満。
△:均一。変動値が5%以上6%未満。
×:均一とは言えない。変動値が6%以上。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例4-2と同様の方法により、エッチング処理を行った。結果を表7に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とした以外は、実施例4-2と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表7に示す。
樹脂組成物層4を除去する浸漬処理の際に、超音波照射を行わない以外は、実施例4-1、4-2、4-4、4-6及び4-7と同様の方法により、エッチング処理を行った。結果を表7に示す。
実施例4-10と同様の方法により得られたエッチング処理後(IV)のエッチングレジスト5(金属マスク)を、塩化第二鉄溶液を用いて除去し、その後の水洗する工程で超音波照射した。結果を表7に示す。
表8又は表9に記載したエッチング液を使用した以外は、実施例4-1と同様の方法により、エッチング処理を行った。結果を表8及び表9に示す。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とし、表9に記載したエッチング液を使用した以外は、実施例4-1と同様の方法により、エッチング処理を行った。結果を表9に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とした以外は、実施例5-8と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表9に示す。
樹脂組成物層4を除去する浸漬処理の際に、超音波照射を行わない以外は、実施例5-1、5-3、5-4、5-5、5-7と同様の方法により、エッチング処理を行った。結果を表9に示す。
実施例5-12と同様の方法により、エッチング処理を行った後、エッチングレジスト5(金属マスク)を、塩化第二鉄溶液を用いて除去し、その後の水洗する工程で超音波照射した。結果を表9に示す。
表10又は表11に記載したエッチング液を使用した以外は、実施例4-1と同様の方法により、エッチング処理を行った。結果を表10及び表11に示す。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例6-3と同様の方法により、エッチング処理を行った。結果を表11に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とした以外は、実施例6-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表11に示す。
樹脂組成物層4を除去する浸漬処理の際に、超音波照射を行わない以外は、実施例6-1~6-8と同様の方法により、エッチング処理を行った。
実施例6-15と同様の方法により、エッチング処理を行った後、エッチングレジスト5(金属マスク)を、塩化第二鉄溶液を用いて除去し、その後の水洗する工程で超音波照射した。結果を表11に示す。
無機充填剤として、球状溶融シリカ78質量%、エポキシ樹脂として、ビフェニルアラルキル型エポキシ樹脂10質量%、熱硬化剤として、フェノールノボラック型シアネート樹脂10質量%、硬化促進剤として、トリフェニルホスフィン1質量%、その他、カップリング剤、レベリング剤を加え、全量を100質量%としたものに、メチルエチルケトンとシクロヘキサノンを媒体として混合し、液状樹脂組成物を得た。
○:標準処理時間で小径開口100箇所の内、樹脂開口箇所が95箇所以上である。
△:標準処理時間で小径開口100箇所の内、樹脂開口箇所が85箇所以上95箇所未満である。
×:標準処理時間で小径開口100箇所の内、樹脂開口箇所が85箇所未満である。
無機充填剤として、球状溶融シリカ78質量%、エポキシ樹脂として、ビフェニルアラルキル型エポキシ樹脂10質量%、熱硬化剤として、フェノールノボラック型シアネート樹脂10質量%、硬化促進剤として、トリフェニルホスフィン1質量%、その他、カップリング剤、レベリング剤を加え、全量を100質量%としたものに、メチルエチルケトンとシクロヘキサノンを媒体として混合し、液状樹脂組成物を得た。
○:樹脂組成物が残っていない。
△:極微量の樹脂組成物が残っているが、プラズマ洗浄処理等の後処理で容易に除去できるレベル。
×:多くの樹脂組成物が残り、後処理で除去されないレベル。
○:エッチング処理時間が「標準処理時間±30%」でも、エッチング後の表面に樹脂組成物が残っていない。
△:エッチング処理時間が「標準処理時間±30%」でも、エッチング後の表面に極微量の樹脂組成物が残っているが、プラズマ洗浄処理等の後処理で容易に除去できるレベルである。
×:エッチング処理時間が「標準処理時間±30%」で、エッチング後の表面に多くの樹脂組成物が残り、後処理で除去されないレベル。
〇:樹脂組成物層にアンダーカットが見られない。
△:樹脂組成物層の底面に小さなアンダーカットが見られる。
×:樹脂組成物層の底面に実用上問題となる大きなアンダーカットが見られる。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例7-3と同様の方法により、エッチング処理を行った。結果を表16に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とし、エッチング時間を30分まで延長した以外は、実施例7-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表16に示す。
実施例7-1と同様の方法により得られたエッチングレジスト5(ドライフィルムレジストパターン)付きの樹脂組成物層4をウェットブラストによりエッチング処理し、その後、エッチングレジスト5を除去した。これを光学顕微鏡で観察した結果、樹脂組成物層4のエッチング量にばらつきがあり、エポキシ樹脂ガラス布基材上に樹脂組成物が残っている箇所があった。また、表面の一部又は全部が露出された導体パターンにはウェットブラスト処理によって付けられた傷が多数確認された。
表17又は表18に記載したエッチング液を使用した以外は、実施例7-1と同様の方法により、エッチング処理を行った。結果を表17及び表18に示す。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例8-3と同様の方法により、エッチング処理を行った。結果を表18に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とし、エッチング時間を30分まで延長した以外は、実施例8-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表18に示す。
表19又は表20に記載したエッチング液を使用した以外は、実施例7-1と同様の方法により、エッチング処理を行った。結果を表19及び表20に示す。
球状溶融シリカの含有量を55質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を33質量%とした以外は、実施例9-3と同様の方法により、エッチング処理を行った。結果を表20に示す。
球状溶融シリカの含有量を45質量%とし、ビフェニルアラルキル型エポキシ樹脂の含有量を43質量%とし、エッチング時間を30分まで延長した以外は、実施例9-3と同様の方法により、エッチング処理を行った。エッチング時間を30分まで延長したが、導体パターン表面上及びエポキシ樹脂ガラス布基材上に大量の樹脂残りがあり、樹脂組成物層をエッチング加工することができなかった。結果を表20に示す。
1’ 銅張積層板
2 絶縁層
3 半田接続パッド、接続パッド
3’ 銅箔
4 樹脂組成物層
5 エッチングレジスト(金属マスク、ドライフィルムレジストパターン)
6 銅箔、ドライフィルムレジスト
7 評価部分
A 導体パターン
a エッチングレジスト5の開口長さ
b 樹枝組成物層4の膜厚
c 樹枝組成物層4の底部長さ
d 開口部
Claims (11)
- アルカリ不溶性樹脂及び50~80質量%の無機充填剤を含む樹脂組成物のエッチング液において、該エッチング液が、第1成分としての15~45質量%のアルカリ金属水酸化物及び第2成分としての1~40質量%のエタノールアミン化合物を含有し、且つ第3成分としての3~60質量%のポリオール化合物、2~20質量%の多価カルボン酸又は2~20質量%のヒドロキシ酸を含有することを特徴とする樹脂組成物のエッチング液。
- 第3成分が、3~60質量%のポリオール化合物である請求項1に記載の樹脂組成物のエッチング液。
- 上記ポリオール化合物の分子量が80以上200以下である請求項1又は2に記載の樹脂組成物のエッチング液。
- 上記ポリオール化合物が3つ以上のヒドロキシル基を有する請求項1~3のいずれかに記載の樹脂組成物のエッチング液。
- 上記ポリオール化合物が、グリセリンである請求項1~4のいずれかに記載の樹脂組成物のエッチング液。
- 第3成分が、2~20質量%の多価カルボン酸である請求項1に記載の樹脂組成物のエッチング液。
- 第3成分が、2~20質量%のヒドロキシ酸である請求項1に記載の樹脂組成物のエッチング液。
- 請求項1~7のいずれかに記載の樹脂組成物のエッチング液を用いて、アルカリ不溶性樹脂及び50~80質量%の無機充填剤を含む樹脂組成物をエッチング処理する工程を有することを特徴とする樹脂組成物のエッチング方法。
- エッチング処理工程後に、超音波照射する工程をさらに有する請求項8に記載の樹脂組成物のエッチング方法。
- エッチング処理工程前に、2.5~7.5質量%の陰イオン界面活性剤を含有する酸性水溶液からなる前処理液で前処理する工程をさらに有する請求項8又は9に記載の樹脂組成物のエッチング方法。
- エッチング処理工程において、エッチングレジストを使用し、このエッチングレジストが、金属マスク又はドライフィルムレジストである請求項8~10のいずれかに記載の樹脂組成物のエッチング方法。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001310959A (ja) * | 2000-02-23 | 2001-11-06 | Toray Ind Inc | 樹脂膜のウエットエッチング用エッチング液及びそれを用いて成るエッチング方法 |
JP2001358428A (ja) * | 2000-06-14 | 2001-12-26 | Toray Ind Inc | エッチング方法 |
JP2006324452A (ja) * | 2005-05-19 | 2006-11-30 | Wako Pure Chem Ind Ltd | 半導体基板表面処理剤及び処理方法 |
US20070120089A1 (en) * | 2005-11-28 | 2007-05-31 | 3M Innovative Properties Company | Polymer etchant and method of using same |
JP2010524266A (ja) * | 2007-04-13 | 2010-07-15 | スリーエム イノベイティブ プロパティズ カンパニー | カバー層を有するフレキシブル回路 |
JP2010539705A (ja) * | 2007-09-13 | 2010-12-16 | スリーエム イノベイティブ プロパティズ カンパニー | 部分的に剛性のフレキシブル回路及びそれらの作製方法 |
WO2015002272A1 (ja) * | 2013-07-05 | 2015-01-08 | 和光純薬工業株式会社 | エッチング剤、エッチング方法およびエッチング剤調製液 |
WO2018186362A1 (ja) * | 2017-04-06 | 2018-10-11 | 三菱製紙株式会社 | 樹脂組成物用のエッチング液及びエッチング方法 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3481877A (en) * | 1967-02-27 | 1969-12-02 | Amchem Prod | Cleaning solution concentrate and method of preparing same |
JP3765970B2 (ja) * | 2000-07-12 | 2006-04-12 | ソニーケミカル株式会社 | エッチング液及びフレキシブル配線板の製造方法 |
US20040247921A1 (en) * | 2000-07-18 | 2004-12-09 | Dodsworth Robert S. | Etched dielectric film in hard disk drives |
US6403211B1 (en) * | 2000-07-18 | 2002-06-11 | 3M Innovative Properties Company | Liquid crystal polymer for flexible circuits |
US6923919B2 (en) * | 2000-07-18 | 2005-08-02 | 3M Innovative Properties Company | Liquid crystal polymers for flexible circuits |
JP2002180044A (ja) * | 2000-12-07 | 2002-06-26 | Toray Eng Co Ltd | 熱可塑性ポリイミド樹脂用エッチング液 |
CN100416409C (zh) * | 2001-03-29 | 2008-09-03 | 大日本印刷株式会社 | 采用湿蚀刻的电子部件的制造方法 |
JP2003101244A (ja) | 2001-09-27 | 2003-04-04 | Ibiden Co Ltd | 多層プリント配線板の製造方法および多層プリント配線板 |
DE10241300A1 (de) * | 2002-09-04 | 2004-03-18 | Merck Patent Gmbh | Ätzpasten für Siliziumoberflächen und -schichten |
CN1273872C (zh) * | 2003-10-09 | 2006-09-06 | 刘萍 | 一种无肼刻蚀液 |
US7148149B2 (en) * | 2003-12-24 | 2006-12-12 | Matsushita Electric Industrial Co., Ltd. | Method for fabricating nitride-based compound semiconductor element |
US20050186404A1 (en) * | 2004-02-23 | 2005-08-25 | Guoping Mao | Etched polycarbonate films |
JP4339284B2 (ja) * | 2004-06-17 | 2009-10-07 | 三菱製紙株式会社 | 樹脂エッチング液、樹脂エッチング方法、樹脂剥離方法、およびフレキシブルプリント配線板の製造方法 |
JP2006012892A (ja) * | 2004-06-22 | 2006-01-12 | Mitsubishi Paper Mills Ltd | デスミア液、およびデスミア方法 |
JP4519548B2 (ja) * | 2004-07-12 | 2010-08-04 | ポリプラスチックス株式会社 | 液晶性ポリマー成形品のメッキ前処理方法 |
CN100467566C (zh) * | 2005-01-10 | 2009-03-11 | 安捷利(番禺)电子实业有限公司 | 挠性印制电路绝缘薄膜的化学蚀刻法及其蚀刻液 |
JP4104154B2 (ja) * | 2005-03-31 | 2008-06-18 | 東レエンジニアリング株式会社 | 液晶ポリマーのエッチング液及び液晶ポリマーのエッチング方法。 |
JP5138277B2 (ja) | 2007-05-31 | 2013-02-06 | 京セラSlcテクノロジー株式会社 | 配線基板およびその製造方法 |
JP2010111795A (ja) * | 2008-11-07 | 2010-05-20 | Chisso Corp | 剥離液 |
US20120187336A1 (en) * | 2011-01-20 | 2012-07-26 | Surface Chemistry Discoveries, Inc. | Conditioning compositions for solar cells |
TWI521016B (zh) * | 2012-07-18 | 2016-02-11 | 財團法人工業技術研究院 | 蝕刻含聚亞醯胺之膜層的方法 |
WO2017038713A1 (ja) | 2015-08-31 | 2017-03-09 | 住友ベークライト株式会社 | プリント配線板の製造方法、半導体装置の製造方法 |
WO2018088345A1 (ja) | 2016-11-11 | 2018-05-17 | 住友ベークライト株式会社 | 金属箔付き樹脂膜、構造体、配線基板の製造方法、半導体装置の製造方法 |
-
2019
- 2019-10-24 KR KR1020217015488A patent/KR102327244B1/ko active IP Right Grant
- 2019-10-24 WO PCT/JP2019/041765 patent/WO2020085447A1/ja active Application Filing
- 2019-10-24 TW TW108138764A patent/TW202028428A/zh unknown
- 2019-10-24 CN CN201980068941.XA patent/CN112912466A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001310959A (ja) * | 2000-02-23 | 2001-11-06 | Toray Ind Inc | 樹脂膜のウエットエッチング用エッチング液及びそれを用いて成るエッチング方法 |
JP2001358428A (ja) * | 2000-06-14 | 2001-12-26 | Toray Ind Inc | エッチング方法 |
JP2006324452A (ja) * | 2005-05-19 | 2006-11-30 | Wako Pure Chem Ind Ltd | 半導体基板表面処理剤及び処理方法 |
US20070120089A1 (en) * | 2005-11-28 | 2007-05-31 | 3M Innovative Properties Company | Polymer etchant and method of using same |
JP2010524266A (ja) * | 2007-04-13 | 2010-07-15 | スリーエム イノベイティブ プロパティズ カンパニー | カバー層を有するフレキシブル回路 |
JP2010539705A (ja) * | 2007-09-13 | 2010-12-16 | スリーエム イノベイティブ プロパティズ カンパニー | 部分的に剛性のフレキシブル回路及びそれらの作製方法 |
WO2015002272A1 (ja) * | 2013-07-05 | 2015-01-08 | 和光純薬工業株式会社 | エッチング剤、エッチング方法およびエッチング剤調製液 |
WO2018186362A1 (ja) * | 2017-04-06 | 2018-10-11 | 三菱製紙株式会社 | 樹脂組成物用のエッチング液及びエッチング方法 |
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CN112912466A (zh) | 2021-06-04 |
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KR20210068134A (ko) | 2021-06-08 |
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