WO2020158610A1 - 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 PDF

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WO2020158610A1
WO2020158610A1 PCT/JP2020/002551 JP2020002551W WO2020158610A1 WO 2020158610 A1 WO2020158610 A1 WO 2020158610A1 JP 2020002551 W JP2020002551 W JP 2020002551W WO 2020158610 A1 WO2020158610 A1 WO 2020158610A1
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Prior art keywords
etching
resin composition
mass
resin
compound
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PCT/JP2020/002551
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English (en)
French (fr)
Japanese (ja)
Inventor
寛彦 後閑
昌大 田邉
隆 宮崎
豊田　裕二
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三菱製紙株式会社
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Priority to JP2020526634A priority Critical patent/JP6774589B1/ja
Priority to CN202080010796.2A priority patent/CN113348226A/zh
Priority to KR1020217023926A priority patent/KR102376557B1/ko
Publication of WO2020158610A1 publication Critical patent/WO2020158610A1/ja

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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • 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

Definitions

  • the present invention relates to an etching solution (etching solution for a resin composition) and an etching solution for etching a resin composition containing an alkali-insoluble resin, 20 to 40% by mass of an organic filler and 30 to 50% by mass of an inorganic filler. Regarding methods etc.
  • a filler having a low relative dielectric constant for example, it is known to use an organic filler such as fluororesin powder.
  • Insulating resin compositions containing these inorganic fillers, organic fillers and alkali-insoluble resins have excellent physical properties such as heat resistance, dielectric properties, mechanical strength, and chemical resistance, and are the outer surface of the circuit board. It has been widely considered to be used as a solder resist used in the above and as an interlayer insulating material used in a multilayer build-up wiring board.
  • 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 referred to as 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.
  • a processing method for removing the resin composition layer containing the resin composition containing the inorganic filler and the alkali-insoluble resin known methods such as drilling, laser, plasma, and blast can be used. Also, these methods can be combined as necessary. Among them, processing with 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 or 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, cracks 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 a 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 blast mask, By exposing and developing, a patterned wet blast mask is formed. Next, the resin composition layer is removed by performing wet blasting to form an opening, and then the wet blasting mask is removed (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 extremely 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 incomplete polishing or residual residue.
  • 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 a 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 influence 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.
  • a resin composition containing an alkali-insoluble resin, 20 to 40% by mass of an organic filler and 30 to 50% by mass of an inorganic filler is etched by using the etching solution of Patent Document 5, the surface after the etching is organically filled. Sometimes the residue of the agent appeared.
  • An object of the present invention is to provide a novel etching solution suitable for a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler. Efficiently removing the resin composition (resin composition layer containing the resin composition) in a process of removing the resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler using an etching liquid It is another object of the present invention to provide an etching solution for a resin composition and an etching method which can be removed (for example, stably without residue) and have high in-plane uniformity. Furthermore, it is another 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.
  • Etching solution of resin composition containing alkali-insoluble resin, 20 to 40% by mass of organic filler and 30 to 50% by mass of inorganic filler [etching solution for resin composition, etching solution for resin composition, resin In the etching liquid for etching the composition layer (layer formed of the resin composition)]
  • the etching liquid contains 15 to 45% by mass of the alkali metal hydroxide as the first component and the second component as the second component.
  • etching solution according to ⁇ 1> wherein the third component contains at least one selected from a polyol compound, a polycarboxylic acid compound, and a hydroxy acid compound.
  • ⁇ 5> The etching liquid according to any one of ⁇ 2> to ⁇ 4>, in which the polyol compound has three or more hydroxyl groups.
  • ⁇ 6> The etching solution according to any one of ⁇ 2> to ⁇ 5>, in which the polyol compound contains glycerin.
  • ⁇ 7> The etching solution according to any one of ⁇ 1> to ⁇ 6>, in which the third component contains 2 to 20% by mass of a polyvalent carboxylic acid compound.
  • ⁇ 8> The etching solution according to any one of ⁇ 1> to ⁇ 7>, in which the third component contains 2 to 20% by mass of a hydroxy acid compound.
  • etching liquid according to any one of ⁇ 1> to ⁇ 8>, wherein the etching liquid contains 0.1 to 3% by mass of an aromatic alcohol compound.
  • a method for etching a resin composition which comprises the step of:
  • ⁇ 11> Etching treatment of a resin composition containing an alkali-insoluble resin, 20 to 40% by mass of an organic filler and 30 to 50% by mass of an inorganic filler using the etching liquid according to any one of ⁇ 1> to ⁇ 9>. And an ultrasonic wave irradiation step of irradiating ultrasonic waves after the etching step.
  • the resin composition according to ⁇ 10> or ⁇ 11> Prior to the etching step, the resin composition according to ⁇ 10> or ⁇ 11>, further including 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. Method of etching things.
  • etching a resin composition according to any one of ⁇ 10> to ⁇ 13>, wherein an etching resist is used in the etching step, and the etching resist is a metal mask or a dry film resist.
  • the present invention it is possible to provide a novel etching solution suitable for a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler. Further, according to the present invention, in a process of removing a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler using an etching solution, the resin composition (a resin containing the resin composition is used. It is possible to provide an etching solution and an etching method for a resin composition, which can efficiently remove (composition layer)) (for example, stable removal without residue) and have high in-plane uniformity. Furthermore, according to the present invention, it is possible to provide an etching method capable of suppressing the occurrence 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 solution of the present invention is, for example, a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler (in particular, an alkali-insoluble resin, 20 to 40 mass% of organic filler and 30 to 50 mass% of inorganic filler).
  • the resin composition containing the agent) is used for processing.
  • the etching method of the present invention uses the etching solution of the present invention to prepare a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler (particularly, an alkali-insoluble resin, 20 to 40% by mass of an organic filler). And a resin composition containing 30 to 50% by mass of an inorganic filler).
  • the etching solution of the present invention comprises a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler (in particular, an alkali-insoluble resin, 20 to 40% by mass of an organic filler and 30 to 50% by mass of an inorganic filler).
  • etching solution etching solution for resin composition, solution for etching resin composition.
  • the etching solution of the present invention usually contains an alkali metal hydroxide (particularly, 15 to 45% by mass of alkali metal hydroxide) as the first component. Since the alkali-insoluble resin has a 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 30 to 50 mass% has a high concentration of alkali metal hydroxide. This is because it is dissolved and dispersed by the etching liquid containing.
  • an alkali metal hydroxide particularly, 15 to 45% by mass of alkali metal hydroxide
  • the content of the alkali metal hydroxide (ratio to the whole etching solution, the same applies below) is 15% by mass or more, the solubility of the inorganic filler is excellent, and the content of the alkali metal hydroxide is When the content is 45% by mass or less, precipitation of the alkali metal hydroxide is unlikely to occur, and thus 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 usually contains an alkanolamine compound (usually an ethanolamine compound, particularly 1 to 40% by mass of ethanolamine compound) as a second component.
  • an alkanolamine compound usually an ethanolamine compound, particularly 1 to 40% by mass of ethanolamine compound
  • the ethanolamine compound and the like penetrate into the resin composition, swell the resin composition, and the inorganic filler can be uniformly dissolved.
  • the content of the alkanolamine compound for example, ethanolamine compound
  • the content of the alkanolamine compound is more preferably 3 to 35% by mass.
  • alkanolamine compound for example, ethanolamine compound
  • any kind such as primary amine, secondary amine, and tertiary amine may be used, and one kind may be used alone, or two or more kinds may be used. You may use in combination.
  • 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 2-(dimethylamino)ethanol. Among them, 2-(methylamino)ethanol and 2-(2-aminoethylamino)ethanol are more preferable.
  • the etching solution of the present invention contains at least one third component selected from alcohol compounds and carboxylic acid compounds.
  • the etching solution of the present invention may contain 3 to 60% by mass of a polyol compound, 2 to 20% by mass of a polycarboxylic acid compound or 2 to 20% by mass of a hydroxy acid compound as a third component. ..
  • the etching solution of the present invention contains such a third component (for example, a polyol compound, a polyvalent carboxylic acid compound and/or a hydroxy acid compound), whereby an alkali-insoluble resin, an organic filler and a dissolved inorganic filler are included. Can be simultaneously removed by dispersion.
  • the etching solution contains the third component (for example, polyol compound, polycarboxylic acid compound and/or hydroxy acid compound), it has a function to combine the components that can no longer maintain the film shape and improve the removal performance at the same time. It is thought to have been done. It is considered that the effect increases the margin of the processing time in which no residue remains, and the resin composition containing the alkali-insoluble resin, the organic filler and the inorganic filler can be stably removed.
  • the third component for example, polyol compound, polycarboxylic acid compound and/or hydroxy acid compound
  • the content of the third component depends on the components constituting the third component, but is, for example, 0.1% by mass or more, 0.5% by mass or more, and preferably It may be 1 mass% or more, more preferably 1.5 mass% or more, and particularly 2 mass% or more.
  • the content of the third component depends on the components constituting the third component, but is, for example, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less. It may be.
  • Alcohol compounds examples include monoalcohol compounds [eg, alkanols (eg, ethanol, propanol, butanol, pentanol, hexanol, etc.), alicyclic monools (eg, Cyclohexanol) and other non-aromatic monool compounds (aliphatic monools) and the like, and polyol compounds and the like.
  • alkanols eg, ethanol, propanol, butanol, pentanol, hexanol, etc.
  • alicyclic monools eg, Cyclohexanol
  • other non-aromatic monool compounds aliphatic monools
  • polyol compounds and the like examples include polyol compounds and the like.
  • the alcohol compounds may be used alone or in combination of two or more.
  • the alcohol compound may preferably include a polyol compound.
  • the alcohol compound may be an aromatic alcohol compound [an aromatic alcohol compound described later (for example, benzyl alcohol, phenoxyethanol, etc.)], or a non-aromatic alcohol compound (non-aromatic monool compound, non-aromatic compound). Polyol compound), or both of them may be contained.
  • the non-aromatic alcohol compound may be either a saturated or unsaturated compound.
  • the alcohol compound often contains at least a non-aromatic alcohol compound (particularly, a non-aromatic polyol compound).
  • the aromatic alcohol compound may be suitably combined with the third component (further, the first component and the second component).
  • the content of the alcohol compound depends on the total content of the third component and the like, but is, for example, 0.1% by mass or more, 0.5% by mass or more, preferably 1% by mass or more.
  • the content may be at least mass%, more preferably at least 2 mass%, and particularly at least 3 mass%. Further, the content of the alcohol compound may be, for example, 60% by mass or less, 50% by mass or less, 40% by mass or less, and the like.
  • the third component is composed of an alcohol compound
  • the content of the alcohol compound (for example, a polyol compound) used in the etching solution of the present invention is small (for example, less than 3% by mass)
  • the performance of collectively dispersing Is insufficient and too large for example, more than 60% by mass
  • the particles may be excessively collected and the removability may be insufficient. Therefore, the content of the alcohol compound (for example, the polyol compound) depends on the total content of the third component and the like, but it is preferable to select it in a range where the removability can be efficiently realized, and more preferably 10 to 40 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. Moreover, as the polyol compound, a compound having three or more hydroxyl groups is preferable.
  • preferable polyol compounds include compounds in which hydroxyl groups are present in relatively close proximity.
  • the molecular weight per hydroxy group may be, for example, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, 35 or less.
  • the polyol compound may be either an aliphatic polyol compound or an aromatic polyol compound, but it is particularly preferable to use at least an aliphatic polyol compound (alkane polyol or the like).
  • the polyol compound may be sugar or sugar alcohol.
  • polyols having three or more hydroxyl groups include polyols having three or more hydroxyl groups [eg, alkanetriol (eg, C 3-10 alkanetriol such as glycerin and trimethylolpropane), alkanetetraol (eg, erythritol, pentaerythritol, etc. C 4-12 alkanetetraol), an alkane polyol having 5 or more hydroxyl groups (eg, sorbitol, xylitol, boremitol, etc.), and a multimer of a polyol having 3 or more hydroxyl groups (eg, diglycerin, dipenta).
  • alkanetriol eg, C 3-10 alkanetriol such as glycerin and trimethylolpropane
  • alkanetetraol eg, erythritol, pentaerythritol, etc. C 4-12 alkanetetraol
  • diol eg poly(alkanediol) [eg poly C 2-6 alkanediol such as diethylene glycol, dipropylene glycol]], alkane diol (eg C 2 such as ethylene glycol, propylene glycol, butanediol) -10 alkanediol) and the like].
  • alkane diol eg C 2 such as ethylene glycol, propylene glycol, butanediol) -10 alkanediol
  • glycerin is particularly preferable.
  • the polyol compound one kind may be used alone, or two or more kinds may be used in combination.
  • Carboxylic acid compound examples of the carboxylic acid compound (may be simply referred to as “carboxylic acid”) include carboxylic acid, carboxylic acid derivative (for example, carboxylic acid salt) and the like.
  • the carboxylic acid compound (carboxylic acid, carboxylic acid salt, etc.) may be a hydrate or the like.
  • carboxylic acid examples include monocarboxylic acid (monovalent carboxylic acid), polyvalent carboxylic acid (such as polyvalent carboxylic acid described below), and hydroxy acid (such as hydroxy acid described below).
  • Examples of the monocarboxylic acid include fatty acids [eg, alkanoic acids such as formic acid, acetic acid, and propionic acid (eg, C 1-10 alkanoic acid)] and the like.
  • alkanoic acids such as formic acid, acetic acid, and propionic acid (eg, C 1-10 alkanoic acid)
  • propionic acid eg, C 1-10 alkanoic acid
  • carboxylic acid may be an amino acid (aminocarboxylic acid).
  • the salt is not particularly limited, and examples thereof include metal salts [eg, alkali metal salts (eg, lithium salt, sodium salt, potassium salt, etc.), alkaline earth metal salts (eg, magnesium salt, calcium salt, etc.), zinc. Salt, etc.], amine salt, ammonium salt and the like.
  • metal salts eg, alkali metal salts (eg, lithium salt, sodium salt, potassium salt, etc.), alkaline earth metal salts (eg, magnesium salt, calcium salt, etc.), zinc. Salt, etc.], amine salt, ammonium salt and the like.
  • Carboxylic acid compounds may be used alone or in combination of two or more.
  • Preferred carboxylic acid compounds include polycarboxylic acid compounds and hydroxy acid compounds. Therefore, the carboxylic acid compound may include at least one selected from a polycarboxylic acid compound and a hydroxy acid compound.
  • the content of the carboxylic acid compound depends on the total content of the third component and the like, but is, for example, 0.1% by mass or more, 0.5% by mass or more, preferably May be 1% by mass or more, more preferably 1.5% by mass or more, and particularly 2% by mass or more. Further, the content of the carboxylic acid compound may be, for example, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less.
  • the third component is composed of a polyvalent carboxylic acid compound
  • the content of the polyvalent carboxylic acid compound used in the etching liquid of the present invention is low (for example, less than 2% by mass)
  • the performance of collectively dispersing Becomes insufficient
  • the amount is large for example, more than 20% by mass
  • the amount is too large and the removability may be insufficient. Therefore, the content of the polyvalent carboxylic acid compound depends on the total content of the third component and the like, but it is preferable to select it in a range where the removability can be efficiently realized, and more preferably 3 to 15% by mass. ..
  • the polyvalent carboxylic acid (polyvalent carboxylic acid compound) used in the etching solution of the present invention also includes a derivative of the polyvalent carboxylic acid (for example, a salt or the like) or a hydrate.
  • the polyvalent carboxylic acid may be either an aliphatic polyvalent carboxylic acid or an aromatic polyvalent carboxylic acid, and typically an aliphatic polyvalent carboxylic acid may be preferably used.
  • Such aliphatic polycarboxylic acid may be either saturated or unsaturated fatty acid.
  • the number of carboxyl groups may be 2 or more, and may be, for example, 2 to 10 (eg, 2 to 6).
  • polycarboxylic acids include compounds in which carboxyl groups are present in a relatively close cluster.
  • the molecular weight per one carboxyl group may be, for example, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, 35 or less.
  • alkane polycarboxylic acids eg, C 2-12 alkanes such as oxalic acid, malonic acid, succinic acid, and glutaric acid.
  • alkene polycarboxylic acid eg, C 4-12 alkene dicarboxylic acid such as maleic acid, fumaric acid
  • carboxyalkylamine eg, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), L-asparagine Acid-N,N-2 acetic acid (ADSA), diethylenetriamine pentaacetic acid (DTPA)] and derivatives (salts and the like) thereof.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • ADSA L-asparagine Acid-N,N-2 acetic acid
  • DTPA diethylenetriamine pentaacetic acid
  • polyvalent carboxylic acids polyvalent carboxylic acid compounds
  • malonic acid maleic acid
  • ethylenediamine tetraacetic acid (EDTA) diethylenetriamine pentaacetic acid (DTPA)
  • salts thereof are alkali-insoluble resins, organic fillers and inorganic fillers.
  • malonic acid and ethylenediaminetetraacetic acid (EDTA) and these Salts are more preferable
  • ethylenediaminetetraacetic acid (EDTA) and its salts are particularly preferable.
  • the polycarboxylic acid polycarboxylic acid compound
  • one kind may be used alone, or two or more kinds may be used in combination.
  • the third component is composed of a hydroxy acid compound
  • the content of the hydroxy acid compound used in the etching solution of the present invention is small (for example, less than 2% by mass)
  • the performance of collectively dispersing becomes insufficient.
  • the amount is too large (for example, more than 20% by mass)
  • the amount is too large and the removability may be insufficient. Therefore, although the content of the hydroxy acid compound depends on the total content of the third component and the like, it is preferable to select it in a range that can achieve the removability efficiently, and more preferably 3 to 15 mass %.
  • the hydroxy acid (hydroxy acid compound) used in the etching solution of the present invention also includes a hydroxy acid derivative (for example, a salt or the like) as described above.
  • a hydroxy acid derivative for example, a salt or the like
  • the hydroxy acid or the salt thereof may be a hydrate.
  • the hydroxy acid may be either an aliphatic hydroxy acid or an aromatic hydroxy acid, and the aliphatic hydroxy acid may be either a saturated or unsaturated fatty acid.
  • the number of hydroxyl groups may be 1 or more, and may be, for example, 1 to 10 (eg, 1 to 5).
  • the number of carboxyl groups may be 1 or more, and may be, for example, 1 to 10 (eg, 1 to 5).
  • Preferred hydroxy acids include compounds in which hydroxy groups and carboxy groups are present in relatively close proximity.
  • the molecular weight per total amount of hydroxyl groups and carboxyl groups may be, for example, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, 35 or less.
  • hydroxy acid (hydroxy acid compound) used in the etching solution of the present invention examples include aliphatic hydroxy acids [eg, hydroxyalkanecarboxylic acids (eg, glycolic acid, lactic acid, tartronic acid, glyceric acid, leucic acid, malic acid, Tartaric acid, gluconic acid, citric acid, isocitric acid, mevalonic acid, pantoic acid, hydroxypentanoic acid, hydroxyhexanoic acid, etc.), hydroxyalkyl-carboxyalkylamines (eg, hydroxyethyliminodiacetic acid, hydroxyiminodisuccinic acid, etc.), Alicyclic hydroxy acid (eg, quinic acid) and the like], aromatic hydroxy acid [eg, salicylic acid, 4-hydroxyphthalic acid, 4-hydroxyisophthalic acid, creosote acid (homosalicylic acid, hydroxy(methyl)benzoic acid), Vanillic acid, sylic acid
  • hydroxy acids hydroxy acid compounds
  • malic acid, tartaric acid, gallic acid, 4-hydroxyisophthalic acid and salts thereof are used in the process of removing a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler. More preferably, the resin composition layer containing the resin composition can be stably removed without 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.
  • the etching liquid may contain an aromatic alcohol compound.
  • the aromatic alcohol compound corresponds to the alcohol compound (that is, the third component), but particularly, the other third component [for example, a non-aromatic alcohol compound (polyol compound, etc.), a carboxylic acid compound (polyhydric compound). Carboxylic acid compound, hydroxy acid compound, etc.)] and the like] (used as the fourth component).
  • the etching liquid of the present invention preferably contains an aromatic alcohol compound (for example, 0.1 to 3% by mass of aromatic alcohol compound) as the fourth component.
  • an aromatic alcohol compound for example, 0.1 to 3% by mass of aromatic alcohol compound
  • the effect of simultaneously dispersing and removing the alkali-insoluble resin, the organic filler and the dissolved inorganic filler becomes high. Therefore, in the ⁇ etching method> described below, the resin composition layer can be removed without a residue without performing the ultrasonic wave irradiation step.
  • an etching solution containing an aromatic alcohol as the fourth component may be used to carry out the etching method of the present invention having an ultrasonic wave irradiation step.
  • the etching liquid contains another third component (for example, a polyol compound, a polycarboxylic acid compound and/or a hydroxy acid compound, etc.), it has a function of collecting the components whose film shape cannot be maintained, and removes them at the same time. It is thought that the performance is improved. It is considered that the etching liquid further contains an aromatic alcohol compound to improve the performance of removing the undissolved alkali-insoluble resin and organic filler. It is considered that the effect increases the margin of the processing time in which no residue remains, and the resin composition containing the alkali-insoluble resin, the organic filler and the inorganic filler can be stably removed.
  • another third component for example, a polyol compound, a polycarboxylic acid compound and/or a hydroxy acid compound, etc.
  • the content of the aromatic alcohol compound depends on the total content of the third component and the like, but is, for example, 0.1% by mass or more and 0.5% by mass or more. It may be 20% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less.
  • the content of the aromatic alcohol compound used in the etching liquid of the present invention is, for example, about 0.1% by mass or more, the performance of removing the alkali-insoluble resin and the organic filler is excellent, and about 3% by mass or less.
  • the content of the aromatic alcohol compound is more preferably 0.5 to 2.5% by mass.
  • aromatic alcohol compound used in the etching solution of the present invention examples include aralkyl alcohol (eg, benzyl alcohol, 4-methylbenzyl alcohol, 3-methylbenzyl alcohol, 2-methylbenzyl alcohol, 2-phenylethanol, 3 -Phenylpropanol, 1-phenyl-1-propanol, 1-phenyl-2-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 1-phenyl-2-butanol, 2-phenyl-2- Butanol), (poly)alkanediol monoaryl ether (eg, 2-phenoxyethanol, phenyldiglycol, phenylpropylene glycol, phenyldipropylene glycol, etc.), (poly)alkanediol monoaralkyl ether (eg, benzyl glycol, benzyldiene) Glycol and the like) are exemplified.
  • aralkyl alcohol
  • the resin composition layer containing the resin composition in the process of removing the resin composition containing the alkali-insoluble resin, the organic filler and the inorganic filler, the resin composition layer containing the resin composition can be stably contained without residue.
  • benzyl alcohol and 2-phenoxyethanol are more preferable, and 2-phenoxyethanol is particularly preferable.
  • the aromatic alcohol may be used alone or in combination of two or more.
  • a coupling agent, a leveling agent, a coloring agent, a surfactant, a defoaming 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, it is preferable to use pure water. In the present invention, pure water generally used for industry can be used.
  • the pretreatment liquid according to the present invention is, for example, an acidic aqueous solution containing 2.5 to 7.5% by mass of an anionic surfactant.
  • lauryl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, alkylbenzene sulfonate, dodecylbenzene sulfonate, alkyl examples thereof include naphthalene sulfonate, dialkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkane sulfonate and alkenyl succinate.
  • anionic surfactants polyoxyethylene alkyl ether sulfates and alkylnaphthalene sulfonates have a small-diameter opening treatment such that the opening diameter of the opening in the resin composition layer is ⁇ 100 ⁇ m or less, and unetched parts Is preferable, and 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 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 in which the opening diameter of the opening in the resin composition layer is ⁇ 100 ⁇ m or less. It is preferable to have.
  • the pH is preferably 1 or more from the viewpoint that the obtained effect does not increase, it is uneconomical, and 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 for 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 resin composition according to the present invention is a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler.
  • the content of the organic filler in the resin composition is, for example, 20 to 40% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.
  • the content of the organic filler is less than 20% by mass, the influence of the difference in expansion coefficient generated by the etching solution containing an alkali metal hydroxide on the entire resin composition is small, and the etching does not proceed. If the content of the organic filler exceeds 40% by mass, the fluidity of the resin composition is lowered, so that the flexibility tends to be lowered, which may be inferior in practicality.
  • the content of the inorganic filler is, for example, 30 to 50% by mass based on 100% by mass of the nonvolatile content in the resin composition.
  • the content of the inorganic filler is less than 30% by mass, the amount of the inorganic filler as a site dissolved by the etching solution containing an alkali metal hydroxide is too small with respect to the entire resin composition, so that the etching proceeds. There are cases where it does not.
  • the content of the inorganic filler exceeds 50% by mass, the fluidity of the resin composition is lowered, so that the flexibility tends to be lowered, which may be inferior in practicality.
  • examples of the organic filler include polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy polymer (PFA), chlorotrifluoroethylene (CTFE) and tetra At least one fluororesin selected from the group consisting of fluoroethylene-chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polychlorotrifluoroethylene (PCTFE) are listed. These resins may be used alone or in combination of two or more. From the viewpoint of lowering the dielectric constant of the resin composition layer, PTFE is preferable.
  • 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, and barium titanate.
  • 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 of these may be used alone, or two or more of them 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 it in an alkaline aqueous solution, and has an acid value (JIS K2501) as an index of the content of free carboxyl groups 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 resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; phenol novolac type epoxy resin, cresol novolac type epoxy resin and other novolac type epoxy resins. Can be mentioned.
  • Examples of the epoxy resin further 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.
  • the heat curing agent is not particularly limited as long as it has a function of curing an epoxy resin, but preferable examples include a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, Cyanate ester resin etc. are mentioned.
  • a thermosetting agent one of these may be used alone, or two or more of them may be used in combination.
  • a curing accelerator can be 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, an organic filler and an inorganic filler can be formed by thermosetting to form an insulating resin composition layer, but etching using the etching solution of the present invention is usually The process proceeds in the A stage (before the start of the curing reaction) or the B stage (the intermediate stage of the curing reaction). Even in the A stage or the B stage, the alkali-insoluble resin does not dissolve in the etching solution of the present invention, but the inorganic filler partially or completely dissolves in the etching solution of the present invention and the alkali-insoluble resin against the etching solution. Due to the difference in the expansion coefficient of the organic filler, the dispersion removal of the resin composition proceeds. When 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 penetrate into the resin composition layer, which makes uniform etching difficult. There is.
  • 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 When heated at a high temperature of more than 160° C., thermosetting further progresses, which may make it difficult to perform an etching treatment using the etching solution of the present invention.
  • 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.
  • step (I) a conductor pattern is formed by patterning a copper foil 3'on the surface of a copper clad laminate 1'composed of an insulating layer 2 and a copper foil 3', and a circuit board having solder connection pads 3 is formed. 1 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 to form a metal mask 5 as an etching resist 5.
  • the copper foil 3'and the copper foil 6 can be patterned by, for example, a copper etching process using a ferric chloride solution, a cupric chloride solution or the like.
  • the resin composition layer is exposed through the etching resist 5 until a part or all of the solder connection pad 3 is exposed by the etching solution for the resin composition layer. 4 is etched.
  • the affinity between the etching liquid and the resin composition layer 4 is improved by the pretreatment step of bringing the pretreatment liquid into contact with the resin composition layer 4 and the etching resist 5.
  • the resin composition layer 4 can be etched through the etching resist 5 with an etching solution for the resin composition layer until a part or all of the solder connection pad 3 is exposed.
  • step (IV)-2 the resin residue 8 is removed in the water washing step following the etching treatment.
  • step (IV)-2 the resin residue 8 can be removed by irradiating ultrasonic waves in a water washing step following the etching step.
  • 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 pretreatment time is not particularly limited, but even in a small-diameter opening treatment in which 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 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 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 more
  • the temperature is preferably 60 to 85°C, more preferably 70 to 85°C.
  • part or all of the inorganic filler filled with a high content is gradually dissolved from the surface layer of the resin composition layer, and the alkali-insoluble resin and the organic filler are dispersed, Removal of the resin composition layer proceeds.
  • a method such as dipping treatment, paddle treatment, spraying treatment, brushing, scraping or the like can be used for the pretreatment step and the etching step.
  • the immersion treatment is preferable from the viewpoint of the uniformity of the etching treatment.
  • the etching liquid remaining on the surface of the resin composition is washed, and the resin adhered to the surface of the connection pad 3 and the wall surface of the resin composition layer 4 is removed.
  • a water washing step is an ultrasonic wave irradiation step of applying ultrasonic waves.
  • the ultrasonic irradiation is preferably performed by a dipping method.
  • the resin residue 8 attached to the surface of the connection pad 3 and the wall surface of the resin composition layer 4 is brought into contact with water, which is preferably subjected to ultrasonic vibration of 20 to 150 kHz, for 10 to 300 seconds.
  • the frequency of ultrasonic vibration is preferably 20 to 150 kHz.
  • the contact time is preferably 10 to 300 seconds.
  • the washing step by spraying with the washing step after the washing step by ultrasonic irradiation in the immersion method.
  • the spray pressure is preferably 0.02 to 0.3 MPa.
  • the temperature of the washing water is preferably equal to or lower than the temperature of the etching solution, and the temperature difference between the etching solution and the washing water is preferably 40 to 50°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.
  • Examples of the method for exposing a dry film resist according to the present invention include a xenon lamp, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh 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 photocrosslinkable resin layer to be 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 release solution suitable for the photo-crosslinkable resin layer 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.
  • the alkali-insoluble resin, the inorganic filler and the organic filler can be dispersed and removed at the same time.
  • the mechanism of this effect is beyond speculation, but it is considered that the dispersion state of the alkali-insoluble resin, the inorganic filler, and the organic filler remaining in the etched portion immediately after the etching step is related.
  • the alkali-insoluble resin, the inorganic filler, and the organic filler remaining in the etching-treated portion are in a dispersed state in which they are mixed with each other immediately after the etching step, and the resin composition can be quickly washed with water in this dispersed state.
  • the layer can be removed without residue.
  • the time from the end of the etching step to the start of the water washing step exceeds 30 seconds, the separation of the alkali-insoluble resin, the inorganic filler, and the organic filler progresses, so that components that are easily removed by water washing and components that are difficult to be removed by water washing Therefore, it is considered that a residue of the resin composition layer is generated after washing with water.
  • PTFE 25 mass % As an organic filler, PTFE 25 mass %, as an inorganic filler, spherical fused silica 40 mass %, as an epoxy resin, biphenyl aralkyl type epoxy resin 16 mass %, as a thermosetting agent, phenol novolac type cyanate resin 16 mass %, curing acceleration
  • triphenylphosphine (2% by mass) As the agent, triphenylphosphine (2% by mass), 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 onto 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 formed of a resin composition containing an alkali-insoluble resin, an inorganic filler and an organic 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.
  • An 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 temperature is set to 100° C. and the pressure is set to 1 on the epoxy resin glass cloth base material on which the conductor pattern is formed, using a vacuum heat press type laminator. After vacuum thermocompression bonding at 0.0 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, an opening was formed in a predetermined region of the copper foil, and the resin composition layer 4 with an etching resist (metal mask) was prepared.
  • the resin composition layer 4 was subjected to an etching process by immersion treatment at 80° C. with the etching liquids shown in Tables 1 and 2 through the etching resist 5.
  • the etching liquid remaining on the surface of the resin composition layer 4 is washed, and the resin residue 8 attached on the surface of the connection pad 3 and the wall surface of the resin composition layer 4 is removed by irradiating ultrasonic waves.
  • an immersion type ultrasonic wave irradiation step with pure water was performed as a water washing step.
  • the ultrasonic wave irradiation step was performed by bringing the resin residue 8 adhering to the surface of the connection pad 3 and the wall surface of the resin composition layer 4 into contact with pure water subjected to ultrasonic vibration of 45 kHz for 60 seconds.
  • a+2b in the opening length a of the etching resist 5, 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.
  • the processing time when it became c was defined as "standard processing time". Specifically, since the opening length a of the etching resist 5 is 60 ⁇ 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 100 ⁇ m ⁇ 5 ⁇ m.
  • the treatment time was defined as "standard treatment time” and shown in Tables 1 and 2.
  • Evaluation Criteria Resin residue does not remain inside the opening after ultrasonic water washing, or even if it remains, it is a level that can be removed by an additional water washing step by spraying.
  • ⁇ Stisfaction
  • X Unsatisfaction
  • Example 1-13 Etching treatment was carried out in the same manner as in Example 1-3, except that the content of PTFE was 23 mass %, the content of spherical fused silica was 33 mass %, and the content of biphenylaralkyl-type epoxy resin was 25 mass %. I went. The results are shown in Table 2.
  • Example 1-15 Etching treatment was performed in the same manner as in Example 1-3, except that the content of PTFE was 15% by mass, the content of spherical fused silica was 40% by mass, and the content of biphenylaralkyl-type epoxy resin was 26% by mass. I went. Although the etching time was extended to 30 minutes (1800 seconds), there was a large amount of resin residue 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.
  • Example 1-16 Etching treatment was carried out in the same manner as in Example 1-3, except that the content of PTFE was 25% by mass, the content of spherical fused silica was 25% by mass, and the content of biphenylaralkyl-type epoxy resin was 31% by mass. I went. Although the etching time was extended to 30 minutes, there was a large amount of resin residue on the conductor pattern surface and the epoxy resin glass cloth substrate, and the resin composition layer could not be etched. The results are shown in Table 2.
  • Example 1-23 The resin composition layer 4 with an etching resist obtained by the same method as in Example 1-1 was subjected to a wet blast treatment, and then the etching resist 5 was removed. As a result of observing this with an optical microscope, there was variation in the etching amount of the resin composition layer 4, and there was a portion where the resin composition remained on the epoxy resin glass cloth substrate. In addition, a large number of scratches formed by the wet blast treatment were confirmed on the conductor pattern with a part or all of the surface exposed.
  • Examples 2-1 to 2-14 In the water washing step after the etching treatment, the resin residue obtained by the etching process by the same etching method as in Examples 1-1 to 1-14, except that the water washing step by spraying is performed instead of the ultrasonic wave irradiation step.
  • the evaluation results of are shown in Tables 3 and 4.
  • the resin composition containing the alkali-insoluble resin, the organic filler and the inorganic filler can be efficiently removed (in particular, stable removal without resin residue). it can.
  • Examples 3-1 to 3-10, 3-12, 3-15 to 3-21 Etching treatment was carried out in the same manner as in Example 1-1, except that the etching solutions shown in Table 5 or Table 6 were used. The results are shown in Tables 5 and 6.
  • Example 3-11 Etching treatment was carried out by the same method as in Example 3-3, except that the content of PTFE was 23 mass %, the content of spherical fused silica was 33 mass %, and the content of biphenylaralkyl-type epoxy resin was 25 mass %. I went. The results are shown in Table 6.
  • Example 3-13 Etching treatment was carried out in the same manner as in Example 3-3, except that the content of PTFE was 15% by mass, the content of spherical fused silica was 40% by mass, and the content of biphenylaralkyl-type epoxy resin was 26% by mass. I went. Although the etching time was extended to 30 minutes (1800 seconds), there was a large amount of resin residue 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 6.
  • Example 3-14 Etching treatment was carried out by the same method as in Example 3-3, except that the content of PTFE was 25 mass %, the content of spherical fused silica was 25 mass %, and the content of biphenylaralkyl-type epoxy resin was 31 mass %. I went. Although the etching time was extended to 30 minutes, there was a large amount of resin residue on the conductor pattern surface and the epoxy resin glass cloth substrate, and the resin composition layer could not be etched. The results are shown in Table 6.
  • Examples 4-1 to 4-12 In the water washing step after the etching treatment, the resin residue when the etching process is performed by the same etching method as in Examples 3-1 to 3-12 except that the water washing step by spraying is performed instead of the ultrasonic wave irradiation step.
  • the evaluation results of are shown in Tables 7 and 8.
  • a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler can be efficiently removed (in particular, stable removal without resin residue). it can.
  • Examples 5-1 to 5-10, 5-12, 5-15 to 5-22 Etching treatment was carried out by the same method as in Example 1-1, except that the etching solutions shown in Table 9 or Table 10 were used. The results are shown in Table 9 and Table 10.
  • Example 5-11 Etching treatment was carried out in the same manner as in Example 5-3, except that the content of PTFE was 23 mass %, the content of spherical fused silica was 33 mass %, and the content of biphenylaralkyl-type epoxy resin was 25 mass %. I went. The results are shown in Table 10.
  • Example 5-13 Etching treatment was carried out in the same manner as in Example 5-3, except that the content of PTFE was 15% by mass, the content of spherical fused silica was 40% by mass, and the content of biphenylaralkyl-type epoxy resin was 26% by mass. I went. Although the etching time was extended to 30 minutes (1800 seconds), there was a large amount of resin residue 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 10.
  • Example 5-14 Etching treatment was carried out in the same manner as in Example 5-3, except that the content of PTFE was 25% by mass, the content of spherical fused silica was 25% by mass, and the content of biphenylaralkyl-type epoxy resin was 31% by mass. I went. Although the etching time was extended to 30 minutes, there was a large amount of resin residue on the conductor pattern surface and the epoxy resin glass cloth substrate, and the resin composition layer could not be etched. The results are shown in Table 10.
  • Example 6-1 to 6-12 In the water washing step after the etching treatment, the resin residue when the etching process is performed by the same etching method as in Examples 5-1 to 5-12 except that the water washing step by spraying is performed instead of the ultrasonic wave irradiation step.
  • the evaluation results of are shown in Tables 11 and 12.
  • Example 7 As an organic filler, PTFE 25 mass %, as an inorganic filler, spherical fused silica 40 mass %, as an epoxy resin, biphenyl aralkyl type epoxy resin 16 mass %, as a thermosetting agent, phenol novolac type cyanate resin 16 mass %, curing acceleration As the agent, triphenylphosphine (2% by mass), 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 onto 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 formed of a resin composition containing an alkali-insoluble resin, an organic filler 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.
  • An 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 temperature is set to 100° C. and the pressure is set to 1 on the epoxy resin glass cloth base material on which the conductor pattern is formed, using a vacuum heat press type laminator. After vacuum thermocompression bonding at 0.0 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, an opening was formed 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+2b in the opening length a of the metal mask 5, 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.
  • the processing time when it became c was defined as "standard processing time". Specifically, since the opening length a of the metal mask 5 is 50 ⁇ 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 90 ⁇ m ⁇ 5 ⁇ m. Tables 13 and 14 show the different processing times as the "standard processing time".
  • the pH of each pretreatment liquid was adjusted using sulfuric acid or potassium hydroxide.
  • Evaluation Criteria (Good): Out of 100 small-diameter openings in the standard processing time, there are 95 or more resin openings.
  • ⁇ (Satisfaction): The number of resin openings is 85 or more and less than 95 out of 100 openings with a small diameter in the standard processing time.
  • X (Unsatisfaction): The number of resin openings is less than 85 out of 100 openings having a small diameter in the standard processing time.
  • the unetched portion is formed even in the small-diameter opening treatment such that the opening diameter of the opening in the resin composition layer containing the alkali-insoluble resin, the organic filler and the inorganic filler is ⁇ 100 ⁇ m or less. Can be suppressed and the etching process can be performed.
  • Example 8-1 to 8-9 As an organic filler, PTFE 25 mass %, as an inorganic filler, spherical fused silica 40 mass %, as an epoxy resin, biphenyl aralkyl type epoxy resin 16 mass %, as a thermosetting agent, phenol novolac type cyanate resin 16 mass %, curing acceleration As the agent, triphenylphosphine (2% by mass), 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 onto 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 formed of a resin composition containing an alkali-insoluble resin, an organic filler 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 400 mm x 500 mm, copper foil thickness 12 ⁇ m, base material thickness 0.1 mm) is used to pattern the copper foil 3'on one surface, and the conductor pattern A is a surface.
  • 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, an opening was formed in a predetermined area of the copper foil 6, and a resin composition layer 4 with an etching resist (metal mask) 5 was prepared.
  • an etching process was carried out by immersion treatment at 80° C. on the resin composition layer 4 with the etching solution shown in Table 16 through the etching resist 5.
  • the alkali-insoluble resin, the organic filler, and the inorganic filler remaining in the etching-treated portion by ultrasonic irradiation of a pure water immersion method are removed.
  • a water washing step of removing with water was carried out. Then, it was further washed by spraying with pure water.
  • the etching solution of the present invention is used in the etching method for etching a resin composition containing an alkali-insoluble resin, 20 to 40% by mass of an organic filler and 30 to 50% by mass of an inorganic filler. It can be seen that the in-plane uniformity is high by including the etching process by and the water washing process in this order. It can also be seen that the occurrence of undercut is small. Further, it is understood that the residue of the resin composition is small and can be stably removed when the time from the end of the etching step to the start of the water washing step is within 30 seconds.
  • Example 9-1 to 9-8 As an organic filler, PTFE 25 mass %, as an inorganic filler, spherical fused silica 40 mass %, as an epoxy resin, biphenyl aralkyl type epoxy resin 16 mass %, as a thermosetting agent, phenol novolac type cyanate resin 16 mass %, curing acceleration As the agent, triphenylphosphine (2% by mass), 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 onto 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 formed of a resin composition containing an alkali-insoluble resin, an inorganic filler and an organic 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.
  • An 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 temperature is set to 100° C. and the pressure is set to 1 on the epoxy resin glass cloth base material on which the conductor pattern is formed, using a vacuum heat press type laminator. After vacuum thermocompression bonding at 0.0 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, an opening was formed in a predetermined region of the copper foil, and the resin composition layer 4 with an etching resist (metal mask) was prepared.
  • the resin composition layer 4 was subjected to an etching treatment by immersion treatment at 80° C. with the etching liquids shown in Table 17 through the etching resist 5. After the etching treatment, a cleaning step was performed to remove the etching liquid remaining on the surface of the resin composition layer 4. In the cleaning process, a spray method using pure water was used.
  • a+2b in the opening length a of the etching resist 5, 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.
  • the processing time when it became c was defined as "standard processing time". Specifically, since 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 c of the opening of the resin composition layer 4 is 90 ⁇ m ⁇ 5 ⁇ m.
  • Table 17 shows the standard processing time as the standard processing time. Whether the resin composition layer 4 was reliably removed inside the opening of the metal mask 5 was evaluated by the above-mentioned “resin residue”. The results are shown in Table 17.
  • a resin composition containing an alkali-insoluble resin, an organic filler and an inorganic filler can be efficiently removed (particularly, stable removal without resin residue).
  • the resin composition could be efficiently removed without using ultrasonic water washing.
  • the etching solution and the etching method of the present invention are for processing an insulating resin composition layer which is filled with a high content of an organic filler and an inorganic filler and has excellent heat resistance, dielectric properties, mechanical strength, chemical resistance, etc.
  • it can be applied to fine processing of insulating resin in a multilayer build-up wiring board, a component built-in module board, a flip chip package board, a package board mounting mother board, and the like.
  • Circuit Board 1'Copper Clad Laminate 2 Insulation Layer 3 Solder Connection Pad, Connection Pad 3'Copper Foil 4 Resin Composition Layer 5 Etching Resist (Metal Mask, Dry Film Resist Pattern) 6 Copper foil, dry film resist 8 Resin residue a Opening length of etching resist b Film thickness of resin composition layer 4 Bottom length of resin composition layer 4

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