TWI700559B - Thinning device for barrier layer - Google Patents

Abstract

OP-M

OP-B。 The barrier layer thinning device, the micelle removal processing unit has a pH sensor and an acid solution addition pump. The pH sensor is installed at a position capable of monitoring the pH of the micelle removal solution, and the acid solution addition pump is installed at a When the pH of the micellar removal solution rises, the acidic solution is added to the position in the micellar removal solution. The acidic solution addition pump adds the acidic solution to the position when the actual pH-M of the micellar removal solution is above pH-A. In the micellar removal solution, the actual output of the acidic solution addition pump OP-M at pH-M is controlled by the output of the acidic solution addition pump OP-A at pH-A and the pH of the micelle removal solution. The acidic solution addition pump output OP-B at the time of B is determined by the ratio control, OP-M relative to the acid solution addition pump maximum output OP-X is 10% to 50%, pH-A<pH -B, OP-A

OP-M

OP-B.

Description

Thinning device for barrier layer

The invention relates to a device for thinning a barrier layer.

With the miniaturization, weight reduction, and multi-functionalization of electrical and electronic components, photosensitive resins (photosensitive materials) starting from dry film barrier layers and solder resist layers for circuit formation are designed to cope with the high density of printed circuit boards. It requires high resolution. Image formation by these photosensitive resins is performed by exposing the photosensitive resin and developing it.

In order to cope with the miniaturization and higher functionality of printed circuit boards, there is a tendency for the photosensitive resin to be thinned. With regard to photosensitive resins, there are liquid barrier layers of the type used for applying liquid and dry film barrier layers of dry film type. Recently, a dry film barrier layer with a thickness of 15 μm or less has been developed and commercialization is also developing. However, such a thin dry film barrier layer has insufficient adhesion and conformability to irregularities compared with a barrier layer of conventional thickness, and there are problems such as peeling and voids.

In order to solve these problems, a method capable of achieving high resolution while using a thick photosensitive resin has been proposed. For example, in the method of making a conductive pattern by the subtraction method, the following conductive pattern is disclosed The formation method (for example, refer to Reference 1) is characterized in that a metal layer is provided on one or both sides of the insulating layer to form a laminated substrate, and a dry film resist for resist is bonded to the laminated substrate to form a barrier After that, the filming process of the barrier layer is performed, followed by the exposure process, development process, and etching process of the circuit pattern. In addition, among the methods for forming the solder resist pattern, the following method for forming the solder resist pattern is disclosed (for example, refer to Patent Document 2 and Patent Document 3), which is characterized in that a circuit board having a conductive pattern A barrier layer formed by the solder resist layer is formed on the top, and then the barrier layer is thinned, followed by a pattern exposure process, and the barrier layer is thinned again.

In addition, Patent Document 4 discloses a barrier layer thinning device including at least the following four processing units: a thin filming processing unit that immerses (dip) the substrate on which the barrier layer is formed in a high concentration of alkali In the aqueous solution (thinning treatment solution), the micelles of the barrier layer are temporarily insoluble, making it difficult to dissolve and diffuse in the treatment solution; the micelle removal treatment unit, spraying the micelle removal solution The micelles are dissolved and removed in one fell swoop; the water washing treatment unit is used to wash the surface with water; the drying treatment unit is used to remove the water for washing.

A part of the thin film forming apparatus disclosed in Patent Document 4 will be described using the schematic cross-sectional view shown in FIG. 13. In the thinning processing unit 11, the substrate 3 on which the barrier layer is formed is introduced from the input port 7. The substrate 3 is transported from the entrance roller pair (sometimes abbreviated as "entry roller pair") 4 of the immersion tank to the immersion tank 2, and is transported into the immersion tank 2 while being immersed in the thin film treatment liquid 1. Thin film treatment of barrier layer. Afterwards, The substrate 3 is transported to the micelle removal processing unit 12. In the micelle removal processing unit 12, to the substrate 3 transported by the transport roller 29 of the micelle removal processing unit, the micelle removal liquid spray 22 is supplied from the micelle removal liquid nozzle 21 through the micelle removal liquid supply pipe 20. The barrier layer of the substrate 3 is in the immersion tank 2 inside the thin film treatment unit 11, and the thin film treatment liquid 1 which is a high-concentration alkaline aqueous solution is passed through, so that the micelles of the barrier layer components are temporarily insoluble in the thin film treatment liquid 1化. Thereafter, the micelles are removed by spraying 22 of the micelle removing liquid, whereby the barrier layer is thinned.

The pH of the micelle removal liquid is lower than the pH of the thin film treatment liquid. In addition, by maintaining the pH of the micelle removal liquid in the range of 5.0 to 10.0, the solubility and diffusion of the barrier layer into the micelle removal liquid can be kept constant, and stable continuous thin film formation is possible (for example, refer to Patent Document 3). However, the thinning treatment liquid is a high-concentration alkaline aqueous solution. Therefore, compared to the substrate in the state where the surface of the barrier layer is covered by the liquid film of the thinning treatment liquid, if the micelle removal liquid is supplied and sprayed, the thinning treatment liquid and micelles Since the removal liquid is mixed, the pH of the micellar removal liquid rises.

In order to decrease the pH of the rising micelle removal liquid, an acidic solution is added to the micelle removal liquid. The mixing amount of the thinning treatment liquid into the micellar removal liquid per unit time depends on the coverage of the thinning treatment liquid on the surface of the barrier layer, the adhesion amount of the thinning treatment liquid on the substrate surface, and the frequency of the thinning treatment (number of inputs, interval of inputs) Etc.). It is difficult to maintain the pH of the micelle removal liquid within a desired range only by adding an acidic solution by a simple method. In particular, when the micelle removal solution has a buffering effect, it is impossible to control the removal of micelles when only an acid solution is added corresponding to the pH of the micelle removal solution. The pH of the liquid. Generally, the acidic solution is added in response to the increase in the pH of the micellar removal solution, and the addition of the acid solution is stopped in response to the decrease in the pH. However, the pH of the micelle removal solution is maintained at When such a buffering effect is certain, the acidic solution is continuously added even if the pH does not rise. Furthermore, in a state where the buffering effect is active, even when the thinning treatment is completed without mixing of the thinning treatment liquid, the pH of the micelle removal liquid does not drop immediately, and the pH change is delayed during the time delay period. , Add an acid solution in excess. The degree of the buffering effect of the micellar removal solution differs depending on the components of the mixed thinning treatment solution. Generally, the micelle removal solution is an aqueous solution containing a basic compound mixed with a weak acid and a conjugated base, and a significant buffering effect can be obtained. If the acidic solution is added more than the required amount in this way, the pH may be excessively lowered, the micelle removal performance may vary, and the amount of the barrier layer may become uneven. In addition, if there is a part thinner than the barrier layer after thinning, it will cause circuit disconnection in the formation of the conductive pattern by the subtractive method, and it will cause the deterioration of the weather resistance in the pattern formation of the solder resist. All of them have the problem of causing a decrease in the yield in production. In addition, if the pH of the micelle removal liquid drops excessively, there is a problem that the components of the barrier layer aggregate to become insoluble sludge and adhere to the surface of the barrier layer after thinning.

Patent Document 1: Japanese Patent No. 5339626.

Patent Document 2: Japanese Patent No. 5444050.

Patent Document 3: International Patent Publication No. 2012/043201 Handbook.

Patent Document 4: Japanese Patent Publication No. 2012-27299.

The subject of the present invention is to provide a barrier layer thinning device, which is used in a barrier layer thinning treatment method performed as follows: the components in the barrier layer are made to pass through a thinning treatment solution that is a high-concentration alkaline aqueous solution The micelles are temporarily insolubilized at the same time, and the micelles are removed by spraying the micelle removal solution. Among them, even when the mixing amount of the thinning treatment solution to the micelle removal solution per unit time changes, the The micellar removal solution has a buffering effect and there is a time delay in the pH fluctuation of the micellar removal solution at the end of the thinning treatment, the pH of the micelle removal solution can also be maintained within a desired range, which can solve the barrier layer The problem that the amount of processing for thinning of the film becomes uneven, and that the components of the barrier layer aggregate to become insoluble sludge and adhere to the surface of the barrier layer after thinning.

The inventors found that these problems can be solved by the following invention.

OP-M

OP-B)。 A device for thinning a barrier layer includes a thinning treatment unit that micelles components in a barrier layer formed on a substrate through a thinning treatment liquid, and a micelle removal processing unit that removes micelles through the micelle removal liquid, The feature is that the micelle removal processing unit has a pH sensor and an acid solution addition pump, the pH sensor is installed at a position that can monitor the pH of the micelle removal solution, and the acid solution addition pump is installed in the micelle When the pH of the removal solution rises, the position where the acid solution can be added to the micellar removal solution. The acid solution addition pump adds the acid solution to the gel when the actual pH-M of the micelle removal solution is above pH-A. In the beam removal solution, the actual output of the acid solution addition pump OP-M at pH-M is controlled by the output of the acid solution addition pump OP-A at pH-A and the pH control target value of the micelle removal solution pH- The ratio of the output OP-B of the acidic solution addition pump at B is determined by controlling the ratio, and the OP-M relative to the maximum output of the acidic solution addition pump OP-X is 10% to 50% (wherein, pH -A<pH-B, OP-A

OP-M

OP-B).

According to the barrier layer thinning device of the present invention, it is possible to provide the barrier layer thinning device as follows: even when the mixing amount of the thinning treatment liquid to the micelle removal liquid per unit time changes, the micelle The removal solution has a buffering effect and there is a time delay in the pH fluctuation of the micelle removal solution at the end of the thinning treatment, the pH of the micelle removal solution can also be maintained within a desired range, and the barrier film can be solved. The problem that the amount of chemical treatment becomes uneven, and that the components of the barrier layer aggregate to become insoluble sludge and adhere to the surface of the barrier layer after thinning.

1‧‧‧Thin film treatment liquid

2‧‧‧Soaking tank

3‧‧‧Substrate

4‧‧‧Entrance roller pair of soaking tank

5‧‧‧Outlet roller pair of soaking tank

6‧‧‧Transfer roller pair at the boundary

7‧‧‧Inlet

8‧‧‧Transfer roller of soaking tank

9‧‧‧The conveying roller of the micelle removal processing unit

10‧‧‧Micelle removal solution

11‧‧‧Thin film processing unit

12‧‧‧Micelle removal processing unit

13‧‧‧Thin film treatment liquid storage tank

14‧‧‧Filming treatment liquid suction port

15‧‧‧Filmization treatment liquid supply pipe

16‧‧‧Filmization treatment liquid recovery pipe

17‧‧‧Film treatment liquid drain pipe

18‧‧‧Micellar removal liquid storage tank

19‧‧‧Micellar removal liquid suction port (for spraying pump)

20‧‧‧Micellar removal liquid supply pipe (for spraying)

21‧‧‧Nozzle for micelle removal liquid

22‧‧‧Micellar removal liquid spray

23‧‧‧Micellar removal liquid drain pipe

26‧‧‧Micellar removal liquid suction port (for circulation pump)

28‧‧‧pH sensor (for control and monitoring)

29‧‧‧Acid solution supply pump

30‧‧‧acid solution

31‧‧‧Acid solution supply pipe

FIG. 1 is a graph showing the relationship between the pH-M of a prior art micelle removal solution and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M.

Fig. 2 is a graph showing the relationship between the pH-M of the prior art micelle removal liquid and the actual output OP-M of the acidic solution addition pump at the time of pH-M.

Fig. 3 is a graph showing the relationship between the pH-M of a prior art micelle removal liquid and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M.

Fig. 4 is a graph showing the relationship between the pH-M of the prior art micelle removal liquid and the actual output OP-M of the pump for adding acidic solution at the time of pH-M.

Fig. 5 is a graph showing the relationship between the pH-M of the prior art micelle removal liquid and the actual output OP-M of the pump for adding acidic solution at the time of pH-M.

Fig. 6 is a graph showing the relationship between the pH-M of the prior art micelle removal liquid and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M.

Fig. 7 is a graph showing the relationship between the pH-M of the prior art micelle removal liquid and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M.

Fig. 8 is a graph showing the pH-M and pH-M of the micelle removal liquid in the present invention Graph of the relationship between the actual output OP-M of the pump for acidic solution addition.

Fig. 9 is a graph showing the relationship between the pH-M of the micelle removal liquid in the present invention and the actual output OP-M of the pump for adding acidic solution at the time of pH-M.

Fig. 10 is a graph showing the relationship between the pH-M of the micelle removal liquid in the present invention and the actual output OP-M of the acidic solution addition pump at the time of pH-M.

Fig. 11 is a graph showing the relationship between the pH-M of the micelle removal liquid in the present invention and the actual output OP-M of the acidic solution addition pump at the time of pH-M.

Fig. 12 is a graph showing the relationship between the pH-M of the micelle removal liquid in the present invention and the actual output OP-M of the acid solution addition pump at the time of pH-M.

Fig. 13 is a schematic cross-sectional view showing a part of a barrier layer thinning device.

Fig. 14 is a schematic cross-sectional view showing a part of the barrier layer thinning device of the present invention.

<Thin Film Process>

The thin-filming process for thinning the barrier layer includes a thin-filming process and a micelle removal process. Thin film treatment is the following treatment: through The thinning treatment liquid makes the components in the barrier layer micelles, makes the micelles temporarily insoluble in the thinning treatment liquid, and is difficult to dissolve and diffuse in the thinning treatment liquid. The micelle removal treatment refers to the treatment of removing micelles through the micelle removal liquid. After the micelle removal treatment, water washing treatment and drying treatment may also be performed. The water washing treatment refers to the treatment of washing the substrate surface with water, and is the treatment of washing away the micelles on the surface of the barrier layer that have not been completely removed by the micelle removal treatment, the remaining thinning treatment liquid, and the micelle removal liquid. In addition, the drying process is a process of drying the substrate and removing water for washing.

In the present invention, the thickness of the barrier layer after being thinned is determined by the thickness of the barrier layer formed on the substrate and the thickness of the barrier layer being thinned (amount of thinning). The thickness of the barrier layer can be adjusted freely within the range of 0.01 to 500 μm.

<Thin Film Treatment>

The thinning treatment is a treatment performed by immersing (soaking, dip) the substrate on which the barrier layer is formed in a thinning treatment liquid. Treatment methods other than immersion treatment (for example, kneading treatment, spray treatment, scrubbing, scraping, etc.) may easily generate bubbles in the thinning treatment liquid, and the generated bubbles adhere to the surface of the barrier layer and the film thickness becomes uneven. Therefore, immersion treatment is preferable. When the barrier layer is formed on the upper surface of the substrate, the thinning treatment liquid can also be supplied by roll coating.

<Micelle removal treatment>

Micelle removal treatment is to block the formation of micelles through thin film treatment The components in the layer are dissolved and removed in one fell swoop through the micellar removal liquid. In order to dissolve and remove in one fell swoop, spray treatment is preferably used.

<Barrier layer>

As the barrier layer, an alkali development type barrier layer can be used. The barrier layer may be a liquid barrier layer or a dry film barrier layer. In addition, the liquid barrier layer may be a single liquid or a dual liquid. As a barrier layer, as long as it can be thinned through the thinning process using a high-concentration alkaline aqueous solution (thinning treatment solution), and can be developed by a developer that is a lower concentration of alkaline aqueous solution than the thinning treatment solution The barrier layer, any barrier layer can be used. The alkali development type barrier layer contains a photocrosslinkable resin component, for example, an alkali-soluble resin, a photopolymerizable compound (monofunctional monomer, polyfunctional monomer), a photopolymerization initiator, and the like. In addition, epoxy resin, thermosetting agent, inorganic filler, etc. may also be contained.

As alkali-soluble resins, for example, acrylic resins, meth acrylic resins, styrene resins, epoxy resins, and polyamide resins can be cited. Resins, polyamide epoxy resins, alkyd resins, and phenol resins. As an alkali-soluble resin, what is obtained by polymerizing (radical polymerization etc.) the monomer (polymerizable monomer) which has an ethylenically unsaturated double bond is preferable. These polymers soluble in an alkaline aqueous solution may be used alone or in combination of two or more kinds.

Examples of monomers having ethylenically unsaturated double bonds Such as styrene derivatives, acrylamide, acrylonitrile, vinyl alcohol (vinyl alcohol) esters, (meth)acrylic acid, (meth)acrylate (( meth)acrylic ester, (meth)acrylate and other (meth)acrylic monomers, maleic acid monomers, fumaric acid, cinnamic acid, α-cyanide Cinnamic acid (α-cyanocinnamic acid), itaconic acid (itaconic acid), crotonic acid (crotonic acid), propiolic acid (propiolic acid), etc.

As the photopolymerizable compound, for example, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol; a bisphenol A (bisphenol A)-based (meth)acrylate compound; α, β-unsaturated carboxylic acid and glycidyl (glycidyl)-containing compound obtained by reacting; (meth)acrylate compound with urethane bond in the molecule, etc. urethane formic acid Ester monomer; γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate (γ-chloro-β-hydroxypropyl-β'-(meth) )acryloyloxyethyl-o-phthalate), β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl-o-phthalate (β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl-o -phthalate) and other phthalate compounds; (meth) acrylate (alkyl (meth) acrylate), nonylphenoxy polyethyleneoxy (meth) acrylate (nonylphenoxy polyethyleneoxy (meth) acrylate) ) And other EO, PO modified nonylphenyl methyl (meth)acrylate, etc. Here, EO and PO mean ethylene oxide and propylene oxide. The compound modified by EO is a substance having a block structure of ethylene oxide group, and the compound modified by PO is A substance with a block structure of propylene oxide group. These photopolymerizable compounds may be used alone or in combination of two or more kinds.

As photopolymerization initiators, aromatic ketones, quinones, benzoin compounds, 2,4,5-triaryl imidazole dimer (2,4,5-triaryl imidazole dimer), acridine can be cited (acridine) derivatives, N-phenylglycine (N-phenylglycine) derivatives, coumarin-based compounds, etc. The substituents of the aromatic groups of the two 2,4,5-triarylimidazoles in the above 2,4,5-triarylimidazole dimer can provide the same and symmetrical compound, or provide different and Asymmetric compound. In addition, a thioxantone-based compound and a tertiary amine compound may be combined like a combination of diethylthioxantone and dimethylaminobenzoic acid. These can be used individually or in combination of 2 or more types.

)反應而令其交聯，實現耐熱性和抗化學藥劑性的提高，但羧酸和環氧即使在常溫下也會進行反應，因此保存穩定性差，鹼顯影型阻焊層一般地多採取在使用前混合的雙液體的方式。另外，也存在使用無機填料的情況，能列舉出例如滑石、硫酸鋇、二氧化矽等。 Epoxy resin is sometimes used as a hardener. By making alkali-soluble resin carboxylic acid and epoxy (

) It is cross-linked by the reaction to improve heat resistance and chemical resistance. However, carboxylic acid and epoxy will react even at room temperature, so the storage stability is poor. Alkaline-developed solder resists are generally used in The two-liquid method of mixing before use. In addition, there are cases where inorganic fillers are used, and examples thereof include talc, barium sulfate, and silica.

The method of forming a barrier layer on the surface of the substrate may be any method, for example, a screen printing method, a roll coating method, a spray coating method, a dip method, a screen Curtain coating method, bar coating method, air knife coating Air knife coating method, hot-melt coating method, gravure coating method, brush coating method, offset printing method. In the case of a dry film barrier layer, a laminating method is preferably used.

<Substrate>

Examples of the substrate include a printed circuit board substrate, a lead frame substrate, and a circuit substrate obtained by processing a printed circuit board substrate and a lead frame substrate.

Examples of the printed circuit board substrate include flexible substrates and rigid substrates.

The thickness of the insulating layer of the flexible substrate is 5 to 125 μm, and a metal layer of 1 to 35 μm is provided on both sides or one side of the flexible substrate to form a laminated substrate with high flexibility. The material of the insulating layer usually uses polyimide, polyamide, polyphenylene sulfide, polyethylene terephthalate, liquid crystal polymer, etc. The material having a metal layer on the insulating layer can be manufactured by any of the following methods: bonding method of bonding with an adhesive, casting method of coating a metal foil with a resin liquid, sputtering, The deposition method is a thin conductive layer (seed layer) with a thickness of several nanometers formed on a resin film. The sputtering/plating method is used to form a metal layer by electroplating, and it is joined by hot pressing. Laminating method, etc. As the metal of the metal layer, any metal such as copper, aluminum, silver, nickel, chromium, or alloys thereof can be used, and copper is generally used.

Examples of rigid substrates include the following laminated substrates provided with a metal layer. An insulating substrate impregnated with epoxy resin or phenol resin is superimposed on a paper substrate or a glass substrate as an insulating layer. The metal foil is placed on it, and it is laminated by heating and pressing to provide a metal layer. In addition, after the inner layer wiring pattern is processed, a multi-layer shielding plate prepared by laminating a prepreg, metal foil, etc., and a multilayer board having through holes and non-through holes can be cited. The thickness is 60μm~3.2mm, and the material and thickness are selected according to the final use form of the printed circuit board. As the material of the metal layer, copper, aluminum, silver, gold, etc. can be cited, and copper is the most common. Examples of these printed circuit board substrates are described in "Printed Circuit Technology Handbook-Second Edition -" (edited by the Society of Printed Circuits, 1987, published by Nikkan Kogyo Shimbun), "Multilayer Printed Circuit Manual" (JAScarlett Edited, 1992 issue, (published by Modern Chemical Society).

Examples of substrates for lead frames include substrates such as iron-nickel alloys and copper-based alloys.

The circuit board is a board in which connection pads for connecting electronic components such as semiconductor chips are formed on an insulating substrate. The connection pad is formed of metal such as copper. In addition, conductor wiring may be formed on the circuit board. The method of manufacturing a circuit board can include, for example, a subtractive method, a semi-additive method, and an additive method. In the subtractive method, for example, a resist pattern is formed on the above-mentioned printed circuit board substrate, and an etching process and a barrier layer peeling process are performed to produce a circuit board. The semi-additive method is to provide a base metal layer for electrolytic copper plating on the surface of the insulating layer through electroless copper plating. Then form the electroplating barrier layer pattern, and implement the electrolytic copper electroplating process Sequence, barrier layer stripping process, flush etching process to make the circuit substrate.

<Thin Film Treatment Liquid>

Examples of the basic compound used in the alkaline aqueous solution used as the thin film treatment liquid include alkali metal silicate (Alkali Metal Silicate), alkali metal hydroxide (Alkali Metal Hydroxide), and alkali metal phosphoric acid. Salt (Alkali Metal Phosphate), Alkali Metal Carbonate (Alkali Metal Carbonate), ammonium phosphate, ammonium carbonate and other inorganic basic compounds; monoethanolamine (monoethanolamin), diethanolamine (diethanolamin), triethanolamin (triethanolamin), methylamine (methylamine), dimethylamine (ethylamine), diethylamine (diethylamine), triethylamine (triethylamine), cyclohexylamine, Tetramethylammonium Hydroxide (TMAH) , Tetraethylammonium hydroxide (tetraethylammonium hydroxide), 2-hydroxyethyltrimethylammonium hydroxide (2-hydroxyethyltrimethylammonium hydroxide, choline, Choline) and other organic alkaline compounds. Examples of alkali metals include lithium (Li), sodium (Na), potassium (K), and the like. The above-mentioned inorganic basic compounds and organic basic compounds may be used alone or in combination of a plurality of them. It is also possible to use a combination of an inorganic basic compound and an organic basic compound. Tap water, industrial water, pure water, etc. can be used as water as the medium of the thin film treatment liquid, but pure water is particularly preferably used.

In addition, in order to thin the surface of the barrier layer more uniformly, Sulfate and sulfite can also be added to the thin film treatment liquid. Examples of sulfates or sulfites include alkali metal sulfates or sulfites such as lithium, sodium, or potassium, and alkaline earth metal sulfates or sulfites such as magnesium (Mg) and calcium (Ca).

The basic compound as the thin film treatment solution can be particularly preferably used among these: inorganic basic compounds selected from alkali metal carbonates, alkali metal phosphates, alkali metal hydroxides, and alkali metal silicates; from TMAH , Organic alkaline compounds selected from choline. These basic compounds can be used alone or as a mixture. In addition, an alkaline aqueous solution having a content of the alkaline compound of 5 to 25% by mass can make the surface thinner more uniformly, so it can be preferably used. When the content of the basic compound is less than 5% by mass, unevenness may easily occur in the thinning process. In addition, if it exceeds 25% by mass, precipitation of a basic compound may easily occur, and the stability of the liquid with time and workability may be poor. More preferably, the content of the basic compound is 7 to 17% by mass, and still more preferably 8 to 13% by mass. The pH of the alkaline aqueous solution used as the thin film treatment liquid is preferably 10 or more. In addition, surfactants, defoamers, solvents, etc. can also be added as appropriate.

The temperature of the thin film treatment liquid is preferably 15 to 35°C, more preferably 20 to 30°C. If the temperature is too low, the permeation rate of the thin film treatment liquid into the barrier layer may be slow, and it may take a long time for the thickness to be thinned. On the other hand, if the temperature is too high, the barrier layer dissolves and diffuses into the thin film treatment liquid while the thin film treatment liquid penetrates into the barrier layer, and this may easily cause film thickness unevenness.

As the micelle removal liquid, water can also be used, but it is preferable to use an aqueous solution containing a basic compound and having a pH of 5 to 10, which is thinner than the thin film treatment liquid. The micelles of the barrier layer components that have been insolubilized under the thinning treatment liquid are redispersed and dissolved and removed by the micelle removal liquid. As the water used for the micelle removal liquid, tap water, industrial water, pure water, etc. can be used, but pure water is particularly preferably used. When the pH of the micelle removal solution is less than 5, the components of the barrier layer may aggregate to form insoluble sludge and adhere to the surface of the barrier layer after thinning. On the other hand, when the pH of the micelle removal solution exceeds 10, the barrier layer may be excessively dissolved and diffused, and the thickness of the barrier layer formed into a thin film may become uneven, resulting in uneven processing. In addition, the pH of the micelle removal liquid is adjusted using sulfuric acid, phosphoric acid, hydrochloric acid, or the like.

Generally, the procedures of thinning treatment and micelle removal treatment are carried out continuously, if it is considered that when the substrate is transferred from the thinning treatment unit to the micelle removal treatment unit, the alkaline compound contained in the thinning treatment liquid is mixed into the micelle removal liquid In the case of, the basic compound contained in the micellar removal solution is generally the same as the basic compound contained in the thin film treatment solution. When the micelle removal solution is an aqueous solution containing a basic compound formed by mixing a weak acid and a conjugated base, it has a buffering effect in a specific pH range to prevent a sharp rise in pH or a drop in pH, and it is unlikely to cause film thickness variations. It is helpful to maintain excellent in-plane uniformity.

<Thin Film Device>

Fig. 14 is a schematic cross-sectional view showing an example of the barrier layer thinning device of the present invention. The thin film device is equipped with a thin film processing unit 11 and glue The device of the beam removal processing unit 12, the thinning processing unit 11 passes through the thinning treatment liquid 1 to micelle components in the barrier layer formed on the substrate, and the micelle removal processing unit 12 removes the micelles through the micelle removing liquid . Although not shown, after the micelle removal processing unit 12, a water washing processing unit for washing the surface of the substrate with water and a drying processing unit for removing water for washing can be provided.

The thin film treatment unit 11 has a immersion tank 2 for supplying the thin film treatment liquid 1 to the barrier layer of the substrate 3. In the thin film treatment unit 11, the substrate 3 with the barrier layer formed from the input port 7 is transferred to the immersion tank 2 containing the thin film treatment liquid 1 through the inlet roller pair 4 of the immersion tank, and passes through the immersion tank 2 Exit roller pair 5. In the meantime, the barrier layer component on the substrate 3 passes through the thinning treatment liquid 1 and is transformed into micelles, and the micelles are insoluble in the thinning treatment liquid 1. With respect to the barrier layer on the upper surface of the substrate 3, the thinning treatment liquid 1 may be applied by roll coating, or a coating roller for this purpose may be provided in the thinning treatment unit 11.

In the micelle removal processing unit 12, the substrate 3 in which the barrier layer is insoluble in the thinning processing liquid in the thinning processing unit 11 is transported by the transport roller 9. With respect to the substrate 3 being conveyed, the micelle removing liquid 10 is supplied through the micelle removing liquid spray 22, and the micelles of the barrier layer component are dissolved and removed at one stroke.

The conditions (temperature, spray pressure, supply flow rate) of the micelle removal liquid spraying 22 are appropriately adjusted in accordance with the dissolution rate of the barrier layer to be thinned. Specifically, the treatment temperature is preferably 10 to 50°C, more preferably 15 to 35°C. In addition, the spray pressure is preferably 0.01 to 0.5 MPa, and more preferably 0.1 to 0.3 MPa. The supply flow rate of the micelle removal liquid 10 is preferably 0.030 to 1.0 L/min per 1 cm ^{2 of the} barrier layer, more preferably 0.050 to 1.0 L/min, and even more preferably 0.10 to 1.0 L/min. If the supply amount is within this range, the micelle component will not remain on the surface of the barrier layer after thinning, and the micelle will be easily dissolved and removed substantially uniformly. When the supply flow rate of the barrier layer per 1 cm ^{2 is} less than 0.030 L/min, poor dissolution of micelles may occur. On the other hand, if the supply amount exceeds 1.0 L/min, components such as pumps necessary for supply may become huge, and large-scale equipment may be required. Furthermore, when the supply amount exceeds 1.0 L/min, the effect on the dissolution and removal of micelles may not change. In order to make an efficient liquid flow on the surface of the barrier layer, the spray direction of spraying is preferably sprayed from a direction inclined with respect to the direction perpendicular to the surface of the barrier layer.

When the substrate 3 is transported from the thinning treatment unit 11 to the micelle removal treatment unit 12, the surface of the barrier layer is covered by the liquid film of the thinning treatment liquid 1 which is a high-concentration alkaline aqueous solution, so the micelle removal treatment unit 12 In this case, when the micelle removal liquid spray 22 is supplied, the thinning treatment liquid 1 and the micelle removal liquid 10 are mixed, and therefore the pH of the micelle removal liquid 10 rises.

In order to lower the pH of the micelle-removed liquid 10 that has risen, the acidic solution 30 is added to the micelle-removed liquid 10. In the present invention, the micelle removal processing unit 12 includes a pH sensor 28 and a pump 29 for adding an acid solution.

The pH sensor 28 is installed at a position capable of monitoring the pH of the micelle removal liquid 10. The pH sensor 28 can be installed in, for example, micellar removal liquid The inside of the storage tank 18, in the middle of the circulation path of the micelle removal liquid 10 through the micelle removal liquid supply pipe (not shown) through the micelle removal liquid circulation pump (not shown) from the micelle removal liquid suction port 26 . The pH sensor 28 in FIG. 14 is provided inside the micelle removal liquid storage tank 18.

The acid solution addition pump 29 is installed at a position where the acid solution 30 can be added to the micelle removal from the acid solution supply tank (not shown) through the acid solution supply pipe 31 when the pH of the micelle removal solution 10 rises. Position in liquid 10. For example, the acidic solution addition pump 29 can be installed at a position where it can be directly added to the inside of the micellar removal liquid storage tank 18 through the acid solution supply pipe 31, and can be supplied to the micelle removal liquid suction port 26 via the micelle The removal liquid supply pipe (not shown) passes through the position where the acid solution supply pipe 31 is added in the middle of the circulation path of the micelle removal liquid 10 of the micelle removal liquid circulation pump (not shown). The acidic solution addition pump 29 in FIG. 14 is installed at a position where it can be directly added to the micellar removal liquid 10 in the micelle removal liquid storage tank 18 through the acidic solution supply pipe 31.

When the thinning treatment liquid 1 is mixed with the micelle removal liquid 10, the actual pH value of the micelle removal liquid, pH-M, starts to rise. When the pH-M is pH-A or higher, the acidic solution addition pump 29 adds the acidic solution 30 to the micelle removal liquid 10 for the purpose of lowering the pH-M.

OP-M

OP-B。通過這樣地控制OP-M，能夠防止酸性溶液30被過剩添加到膠束除去液10中。此外，為了更高精度地防止酸性溶液30的過剩添加，在膠束除去液的pH為pH5~10時，優選為7.0

pH-A<pH-B

9.0。 In the present invention, the actual output OP-M of the acidic solution addition pump at pH-M is controlled by the output OP-A of the acidic solution addition pump at pH-A and the pH control target value of the micelle removal liquid. The ratio between the output OP-B of the acidic solution addition pump at B is controlled and determined, and the maximum output OP-X of the OP-M relative to the acidic solution addition pump is 10% or more and 50% or less. Among them, pH-A<pH-B, and OP-A

OP-M

OP-B. By controlling OP-M in this way, it is possible to prevent the acid solution 30 from being added to the micelle removal liquid 10 excessively. In addition, in order to prevent excessive addition of the acidic solution 30 with higher accuracy, when the pH of the micelle removal solution is pH 5 to 10, it is preferably 7.0.

pH-A<pH-B

9.0.

1 to 12 are graphs showing the relationship between the pH-M of the micelle removal liquid and the actual output OP-M of the acid solution addition pump at the time of pH-M.

pH-M

pH-B的區域中，根據(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。在pH-B<pH-M的區域中，OP-M是100%。在圖1的情況下，即使在不足pH7的酸性區域也將酸性溶液30添加到膠束除去液10中，因此添加需要量以上的酸性溶液30，pH-M過度下降。另外，在pH-B<pH-M的區域中，OP-M被維持在100%，因此即使在每單位時間的薄膜化處理液的混入量不同的情況下，只要pH-M不變成pH-B以下，則過剩的酸性溶液就被持續添加，在薄膜化處理結束時，pH-M過度下降。 Fig. 1 is a graph showing the relationship between the pH-M of a prior art micelle removal solution and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M. In Figure 1, pH-A is 6.5 and pH-B is 8.5. And, OP-A is 0%, and OP-B is 100%. Start adding acidic solution 30 from the acidic area less than pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined according to the ratio control between (pH-A, OP-A) and (pH-B, OP-B). In the region of pH-B<pH-M, OP-M is 100%. In the case of FIG. 1, the acidic solution 30 is added to the micellar removal solution 10 even in an acidic region less than pH 7, and therefore the acidic solution 30 is added in an amount greater than necessary, and the pH-M is excessively lowered. In addition, in the region of pH-B<pH-M, OP-M is maintained at 100%. Therefore, even when the mixing amount of the thin film treatment liquid per unit time is different, as long as the pH-M does not become pH- Below B, the excess acid solution is continuously added, and the pH-M drops excessively at the end of the thin film treatment.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。在pH-B<pH-M的區域中，OP-M為100%。與圖1的情況不同，在圖2以及圖3的情況下，在不足pH7的酸性區域中沒有添加酸性溶液。但是，在pH-B<pH-M的區域中，與圖1同樣，OP-M被維持為100%，因此即使在每單位時間的薄膜化處理液的混入量不同的情況下，只要pH-M不變成不足pH-B，過剩的酸性溶液就被持續添加，在薄膜化處理結束時，pH-M過度下降。 2 and 3 are also graphs showing the relationship between the pH-M of the prior art micellar removal solution and the actual output OP-M of the acidic solution addition pump at the time of pH-M. In Figure 2, pH-A is 7.5 and pH-B is 9.5. And, OP-A is 0%, and OP-B is 100%. In Figure 3, pH-A is 7.5 and pH-B is 8.5. And, OP-A is 0%, and OP-B is 100%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). In the region of pH-B<pH-M, OP-M is 100%. Unlike the case of Fig. 1, in the cases of Figs. 2 and 3, no acidic solution is added to the acidic region of less than pH7. However, in the region of pH-B<pH-M, OP-M is maintained at 100% as shown in Fig. 1. Therefore, even when the mixing amount of the thin film treatment liquid per unit time is different, the pH- M does not become less than pH-B, and excess acidic solution is continuously added. At the end of the thin film treatment, pH-M drops excessively.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並且，因為沒有設定OP-M的上限值，所以即使在pH-B<pH-M的區域中，OP-M也透過(pH-A，OP-A)與(pH-B，OP-B)之間的 比例控制確定，OP-M比OP-B持續變大，酸性溶液的添加量持續增加。因此，與圖1~圖3的情況同樣，即使在每單位時間的薄膜化處理液的混入量不同的情況下，過剩的酸性溶液也被持續添加，在薄膜化處理結束時，pH-M過度下降。 4 to 6 are also graphs showing the relationship between the pH-M of the prior art micellar removal solution and the actual output OP-M of the pump for acidic solution addition at the time of pH-M. In Figure 4, pH-A is 7.5 and pH-B is 8.5. Also, OP-A is 0% and OP-B is 75%. In Figure 5, pH-A is 7.5 and pH-B is 8.5. Also, OP-A is 0% and OP-B is 50%. In Figure 6, pH-A is 7.5 and pH-B is 8.5. Also, OP-A is 0% and OP-B is 25%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). Moreover, because the upper limit of OP-M is not set, even in the region of pH-B<pH-M, OP-M also penetrates (pH-A, OP-A) and (pH-B, OP-B) The ratio between) is determined, OP-M is continuously larger than OP-B, and the amount of acidic solution added continues to increase. Therefore, as in the case of FIGS. 1 to 3, even when the mixing amount of the thin film treatment liquid per unit time is different, the excess acidic solution is continuously added, and at the end of the thin film treatment, the pH-M becomes excessive. decline.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並且，因為OP-M的上限值被設定成75%，所以在pH-B<pH-M的區域中，OP-M維持該上限值。通過設定上限值，在每單位時間的薄膜化處理液的混入量不同的情況下，能抑制過剩的酸性溶液的添加，在薄膜化處理結束時，能夠防止pH-M過度下降，但在該上限值相對於酸性溶液添加用泵的最大輸出OP-X為75%時，很難完全防止pH-M過度下降。 FIG. 7 is also a graph showing the relationship between the pH-M of the prior art micellar removal solution and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M. In Figure 7, pH-A is 7.5 and pH-B is 8.5. Also, OP-A is 0% and OP-B is 75%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). Furthermore, since the upper limit of OP-M is set to 75%, in the region of pH-B<pH-M, OP-M maintains the upper limit. By setting the upper limit, when the mixing amount of the thin film treatment liquid per unit time is different, the addition of excess acidic solution can be suppressed, and at the end of the thin film treatment, the pH-M can be prevented from dropping excessively. When the upper limit is 75% relative to the maximum output OP-X of the pump for adding acidic solution, it is difficult to completely prevent an excessive drop in pH-M.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並 且，因為OP-M的上限值被設定成50%，所以在pH-B<pH-M的區域中，OP-M維持該上限值。通過設定上限值，在每單位時間的薄膜化處理液的混入量不同的情況下，能抑制過剩的酸性溶液的添加，在薄膜化處理結束時，能夠防止pH-M過度下降。在該上限值相對於酸性溶液添加用泵的最大輸出OP-X為50%的圖8的情況下，能夠防止pH-M過度下降。 Fig. 8 is a graph showing the relationship between the pH-M of the micelle removal solution of the present invention and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M. In Figure 8, pH-A is 7.5 and pH-B is 8.5. Also, OP-A is 0% and OP-B is 50%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). In addition, since the upper limit of OP-M is set to 50%, in the region of pH-B<pH-M, OP-M maintains the upper limit. By setting the upper limit, when the mixing amount of the thin film treatment liquid per unit time is different, the addition of an excessive acidic solution can be suppressed, and an excessive drop in pH-M can be prevented at the end of the thin film treatment. In the case of FIG. 8 where the upper limit value is 50% with respect to the maximum output OP-X of the pump for adding acidic solution, it is possible to prevent the pH-M from falling excessively.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並且，因為OP-M的上限值被設定成25%，所以在pH-B<pH-M的區域中，OP-M維持該上限值。通過設定上限值，在每單位時間的薄膜化處理液的混入量不同的情況下，能抑制過剩的酸性溶液的添加，在薄膜化處理結束時，能夠防止pH-M過度下降。在該上限值相對於酸性溶液添加用泵的最大輸出OP-X為25%的圖9的情況下，能夠防止pH-M過度下降。 Fig. 9 is a graph showing the relationship between the pH-M of the micelle removal solution of the present invention and the actual output OP-M of the pump for adding an acidic solution at the time of pH-M. In Figure 9, pH-A is 7.5 and pH-B is 8.5. Also, OP-A is 0% and OP-B is 25%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). In addition, since the upper limit of OP-M is set to 25%, in the region of pH-B<pH-M, OP-M maintains the upper limit. By setting the upper limit, when the mixing amount of the thin film treatment liquid per unit time is different, the addition of an excessive acidic solution can be suppressed, and an excessive drop in pH-M can be prevented at the end of the thin film treatment. In the case of FIG. 9 where the upper limit value is 25% with respect to the maximum output OP-X of the pump for adding acidic solution, it is possible to prevent the pH-M from being excessively lowered.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並且，因為OP-M的上限值被設定成50%，所以在pH-B<pH-M的區域中，OP-M維持該上限值。通過設定上限值，在每單位時間的薄膜化處理液的混入量不同的情況下，能抑制過剩的酸性溶液的添加，在薄膜化處理結束時，能夠防止pH-M過度下降。在該上限值相對於酸性溶液添加用泵的最大輸出OP-X為50%的圖10的情況下，能夠防止pH-M過度下降。 Fig. 10 is a graph showing the relationship between the pH-M of the micelle removal solution of the present invention and the actual output OP-M of the pump for adding an acid solution at the time of pH-M. In Figure 10, pH-A is 7.0 and pH-B is 7.5. Also, OP-A is 0% and OP-B is 50%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). In addition, since the upper limit of OP-M is set to 50%, in the region of pH-B<pH-M, OP-M maintains the upper limit. By setting the upper limit, when the mixing amount of the thin film treatment liquid per unit time is different, the addition of an excessive acidic solution can be suppressed, and an excessive drop in pH-M can be prevented at the end of the thin film treatment. In the case of FIG. 10 in which the upper limit value is 50% with respect to the maximum output OP-X of the pump for adding acidic solution, it is possible to prevent the pH-M from being excessively lowered.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並且，因為OP-M的上限值被設定成25%，所以在pH-B<pH-M的區域中，OP-M維持該上限值。通過設定上限值，在每單位時間的薄膜化處理液的混入量不同的情況下，能夠抑制過剩的酸性溶液的添加，在薄膜化處理結束時，能夠防止pH-M過度下降。在該上限值相對於酸性溶液添加用泵的最大輸出OP-X物25%的圖11的情況下，能夠防止pH-M過度下降。 Fig. 11 is a graph showing the relationship between the pH-M of the micelle removal solution of the present invention and the actual output OP-M of the pump for adding acidic solution at the time of pH-M. In Figure 11, pH-A is 8.5 and pH-B is 9.0. Also, OP-A is 0% and OP-B is 25%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). In addition, since the upper limit of OP-M is set to 25%, in the region of pH-B<pH-M, OP-M maintains the upper limit. By setting the upper limit, when the mixing amount of the thin film treatment liquid per unit time is different, the addition of an excessive acidic solution can be suppressed, and an excessive drop in pH-M can be prevented at the end of the thin film treatment. In the case of FIG. 11 where the upper limit value is 25% of the maximum output OP-X product of the acid solution addition pump, it is possible to prevent an excessive drop in pH-M.

pH-M

pH-B的區域中，透過(pH-A，OP-A)與(pH-B，OP-B)之間的比例控制，確定OP-M。並且，因為OP-M的上限值被設定成25%，所以即使在(pH-A，OP-A)與(pH-B，OP-B)之間，OP-M也不會變得比上限值25%更大。另外，在pH-B<pH-M的區域中，OP-M維持該上限值。通過設定上限值，在每單位時間的薄膜化處理液的混入量不同的情況下，能夠抑制過剩的酸性溶液的添加，在薄膜化處理結束時，能夠防止pH-M過度下降。在該上限值相對於酸性溶液添加用泵的最大輸出OP-X為25%的圖12的情況下，能夠防止pH-M過度下降。 Fig. 12 is a graph showing the relationship between the pH-M of the micelle removal solution of the present invention and the actual output OP-M of the pump for adding acidic solution at the time of pH-M. In Fig. 12, pH-A is 8.5 and pH-B is 9.0. And, OP-A is 0%, and OP-B is 100%. Start adding acidic solution 30 from the area over pH7, at pH-A

pH-M

In the pH-B area, OP-M is determined by controlling the ratio between (pH-A, OP-A) and (pH-B, OP-B). Also, because the upper limit of OP-M is set to 25%, even if it is between (pH-A, OP-A) and (pH-B, OP-B), OP-M will not become more The upper limit is 25% greater. In addition, in the region of pH-B<pH-M, OP-M maintains the upper limit. By setting the upper limit, when the mixing amount of the thin film treatment liquid per unit time is different, the addition of an excessive acidic solution can be suppressed, and an excessive drop in pH-M can be prevented at the end of the thin film treatment. In the case of FIG. 12 in which the upper limit value is 25% with respect to the maximum output OP-X of the pump for adding acidic solution, it is possible to prevent an excessive decrease in pH-M.

As the pH sensor 29 for monitoring the pH of the micelle removal liquid, a pH glass electrode can be used. It is possible to investigate the pH of an aqueous solution at a predetermined temperature by measuring the pH sensor as described below. The pH sensor has a temperature compensation function that corresponds to the temperature characteristics of the pH glass electrode. The function of correcting the property change caused by temperature) and the temperature conversion function corresponding to the temperature characteristics of the aqueous solution (the function of converting the pH at a certain temperature).

It is preferable to use an aqueous solution containing sulfuric acid, phosphoric acid, hydrochloric acid, etc. and having a concentration of 0.01 to 1.0% by mass as the acidic solution added to adjust the pH of the micelle removal liquid. An acidic solution with a low concentration can prevent a rapid pH drop, but when a large amount of alkaline compound is mixed to cause a rapid pH rise, the pH change may not be able to follow. On the other hand, the concentration in acidic solutions When it is high, the pH may drop excessively and the barrier layer component dissolved and dispersed in the micelle removal solution may precipitate.

[Example]

Hereinafter, the present invention will be explained in more detail based on an embodiment, but the present invention is not limited to this embodiment.

(Example 1)

The copper clad laminate (area 340×400 mm, copper foil thickness 18 μm, base thickness 0.8 mm) was used to produce a circuit board having connection pads with a wiring width of 50 μm and a wiring width interval of 50 μm. Next, using vacuum lamination, a solder resist film with a thickness of 30μm (manufactured by Taiyo Ink Manufacturing Co., Ltd., trade name: PFR-800 AUS-410) was vacuum thermocompression bonded (lamination temperature 75°C, suction time 30 seconds, Pressing time 10 seconds) on the above circuit board. In this way, a barrier layer-formed substrate 3 having a film thickness of 38 μm from the surface of the insulating substrate to the surface of the barrier layer was obtained.

Next, after peeling off the carrier film of the solder resist layer, the barrier layer is thinned through the thinning device (FIG. 14) equipped with the thinning processing unit 11 and the micelle removal processing unit 12 for the barrier layer. The aforementioned thinning processing unit 11 is equipped with a immersion tank 2, and the micelle removal processing unit 12 removes micelles from the micelle removal liquid 10.

As the thin film treatment liquid 1, a 10% by mass sodium metasilicate aqueous solution (liquid temperature 25° C.) was used to continuously process 20 substrates 3 at a conveying speed of 3.0 m/min and an interval between the substrates 3 of 50 mm. Substrate 3 From the exit roller pair 5 of the immersion tank of the thin film processing unit 11, passing through the conveying roller pair 6 at the boundary portion, in the micelle removal processing unit 12, the insoluble micelles are removed, and after washing and drying, the obtained The barrier layer is thinned.

As the micelle removal liquid 10, an aqueous solution (liquid temperature 25°C) containing 0.01% by mass of sodium metasilicate and pH 7.0 was used. In addition, as an acidic solution added to adjust the pH of the micelle removal liquid, a 0.5% by mass sulfuric acid solution was used. The pH of the micellar removal solution 10 is monitored through the pH sensor 28 provided in the micelle removal solution storage tank 18 of the micelle removal processing unit 12, and the actual pH value of the micelle removal solution pH-M becomes pH- In the case of A or more, the acid solution 30 is directly added to the micelle removal solution 10 in the micelle removal solution storage tank 18 through the acid solution supply pipe 31 through the acid solution addition pump 29. In Example 1, the acid solution addition pump 32 was operated according to the relationship between pH-M and OP-M shown in FIG. 8 to add the acid solution 30.

Regarding the micelle removal liquid, Table 1 shows the initial pH value before the start of thinning, the end pH value after the continuous treatment of 20 sheets, and the minimum pH value in the continuous treatment of 20 sheets.

Observation of the surface of the barrier layer after thinning of the 20th substrate 3 under an optical microscope confirmed that there was no unevenness in the treatment and it was a smooth surface.

(Examples 2~4)

Except that the acidic solution addition pump 32 is operated to add the acidic solution 30 according to the relationship between pH-M and OP-M shown in FIGS. 9 to 11, the barrier layer is thinned in the same manner as in Example 1.

Regarding the micelle removal liquid, Table 1 shows the initial pH value before the start of thinning, the end pH value after the continuous treatment of 20 sheets, and the minimum pH value in the continuous treatment of 20 sheets.

Observation of the surface of the barrier layer after thinning of the 20th substrate 3 under an optical microscope confirmed that there was no unevenness in the treatment and it was a smooth surface.

(Comparative Examples 1~7)

Except that the acidic solution addition pump 32 is operated to add the acidic solution 30 according to the relationship between pH-M and OP-M shown in FIGS. 1 to 7, the barrier layer is thinned in the same manner as in Example 1.

Regarding the micelle removal liquid, Table 1 shows the initial pH value before the start of thinning, the end pH value after the continuous treatment of 20 sheets, and the minimum pH value in the continuous treatment of 20 sheets. In addition, when the minimum pH value becomes less than 5.0 during the continuous treatment, the continuous treatment is terminated (there is no result of ending the pH value).

In any of Comparative Examples 1 to 7, the minimum pH became less than 5.0 during the continuous treatment. Observed under an optical microscope the surface of the barrier layer after the final treatment of the substrate 3 was thinned, and it was confirmed that the cause was considered to be the sludge (agglomerate) of the barrier layer component of the micelles removed by the micelle removal solution 10 of low pH. )’S attachment.

[Industrial availability]

The barrier layer thinning device of the present invention can be applied to the application of forming barrier layer patterns in the production of printed circuit boards and circuit boards of lead frames, and the production of integrated circuit substrates equipped with connection pads for flip chip connection.

1‧‧‧Thin film treatment liquid

2‧‧‧Soaking tank

3‧‧‧Substrate

4‧‧‧Entrance roller pair of soaking tank

5‧‧‧Outlet roller pair of soaking tank

6‧‧‧Transfer roller pair at the boundary

7‧‧‧Inlet

8‧‧‧Transfer roller of soaking tank

9‧‧‧The conveying roller of the micelle removal processing unit

10‧‧‧Micelle removal solution

11‧‧‧Thin film processing unit

12‧‧‧Micelle removal processing unit

13‧‧‧Thin film treatment liquid storage tank

14‧‧‧Filming treatment liquid suction port

15‧‧‧Filmization treatment liquid supply pipe

16‧‧‧Filmization treatment liquid recovery pipe

17‧‧‧Film treatment liquid drain pipe

18‧‧‧Micellar removal liquid storage tank

19‧‧‧Micellar removal liquid suction port (for spraying pump)

20‧‧‧Micellar removal liquid supply pipe (for spraying)

21‧‧‧Nozzle for micelle removal liquid

22‧‧‧Micellar removal liquid spray

23‧‧‧Micellar removal liquid drain pipe

26‧‧‧Micellar removal liquid suction port (for circulation pump)

28‧‧‧pH sensor (for control and monitoring)

29‧‧‧Acid solution supply pump

30‧‧‧acid solution

31‧‧‧Acid solution supply pipe

Claims (1)

A device for thinning a barrier layer includes a thinning treatment unit that micelles components in a barrier layer formed on a substrate through a thinning treatment liquid, and a micelle removal processing unit that removes micelles through the micelle removal liquid, The feature is that the micelle removal processing unit has a pH sensor and an acid solution addition pump, the pH sensor is installed at a position that can monitor the pH of the micelle removal solution, and the acid solution addition pump is installed in the micelle When the pH of the removal solution rises, the acid solution can be added to the position of the micelle removal solution. The acid solution addition pump adds the acid solution to the micelles when the actual pH value of the micelle removal solution pH-M is above pH-A. In the removal solution, the actual output of the acid solution addition pump at pH-M OP-M is the output of the acid solution addition pump at pH-A OP-A and the pH control target value of the micelle removal solution pH-B It is determined by controlling the ratio between the output OP-B of the pump for acid solution addition at the time, and the maximum output OP-X of OP-M relative to the pump for acid solution addition is 10% to 50%, where pH- A<pH-B, OP-A

OP-M

OP-B.

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