CN107526251A - The forming method of solder resist pattern - Google Patents

Abstract

The problem of [problem] present invention is, there is provided a kind of forming method of solder resist pattern, the forming method comprise at least in order：At least there is the step of forming solder mask layer in the circuit substrate of connection pad, with by uncured solder mask layer filming the filming step below the thickness of pad is connected up to the thickness of solder mask layer, in forming method, time needed for the filming of solder mask layer can shorten, and productivity is improved.The forming method of [solution] solder resist pattern, it is characterized in that, the alkaline aqueous solution used in the filming step of uncured solder mask layer filming is being contained into (A) alkali compounds and (B) ammonium ion, (B) ammonium ion is relative to the mol ratio (B/A) of (A) alkali compounds more than 0.00 and less than 1.85.

Description

The forming method of solder resist pattern

Technical field

The present invention relates to the forming method of solder resist pattern.

Background technology

On circuit board inside various electric apparatus, in order to not make solder attachment not need solder in circuit substrate The conducting wiring that (は ん だ) is sticked, solder resist pattern is formed, so as to which the conducting wiring that solder sticks should not needed by solder resist Layer is coated.In addition, solder resist pattern plays following act on：The oxidation of conducting wiring is prevented, be electrically insulated and is protected from external rings Border influences.

It is equipped with circuit substrate in semiconductor packages obtained by the electronic unit of semiconductor chip etc., utilizes flip chip bonding Being mounted in for the electronic unit connect realizes that high speed, densification aspect are effective means.In face-down bonding, conducting wiring A part plays a role as the connection pad of face-down bonding, for example, the solder bump and electricity that are arranged on the connection pad The electrode terminal connection of subassembly.

It is commonly known to have photo-engraving process as the method that solder resist pattern is formed in circuit substrate.In photo-engraving process side In formula, have on insulating barrier 1 and form solder mask layer in the circuit substrate of connection pad 6 and conducting wiring 2.Then, this is hindered Welding flux layer exposure, development, the solder mask layer for removing connection pad 6 periphery, set opening portion.Thus, the welding resistance shown in Fig. 1 is formed Oxidant layer limits (Solder Mask Defined (SMD)) structure or the non-solder mask shown in Fig. 2 limits (Non Solder Mask Defined (NSMD)) structure.

In the SMD structures shown in Fig. 1, the periphery of connection pad 6 is coated to by solder mask layer 3.Therefore, in order to by electricity The electrode terminal and connection pad 6 of subassembly are reliably electrically connected, for the connection formed in the exposed surface of connection pad 6 Portion must assure that necessary amount of solder, the problem of becoming to maximize accordingly, there exist connection pad 6.And then in order that connection pad 6 periphery is reliably coated to by solder mask layer 3, it is contemplated that machining accuracy, it is necessary to more broadly ensures to connect pad 6 in advance The width for the part being coated to by solder mask layer 3, the problem of connection pad 6 further becomes maximization be present.On the other hand, scheming In the case of the connection pad 6 of NSMD structures shown in 2, exposed because connection pad 6 is all by solder mask layer 3, with solder Connection area is big, compared with the situation of SMD structures, can make it that connecting pad 6 minimizes.But in NSMD structures, due to Connection pad 6 is completely exposed from solder mask layer 3, therefore between connection pad 6 adjacent to each other, is existed caused by producing solder The situation of electrical short.

Propose for solving the forming method of the solder resist pattern of this problem.This method be in order comprise at least with The method of lower step：Solder mask layer 3 are formed in the circuit substrate with connection pad 6 the step of, and by uncured welding resistance The filming of oxidant layer 3, until solder mask layer 3 thickness for connection pad 6 thickness below filming step (referring for example to patent Document 1 and 2).In the forming method of the solder resist pattern, as shown in figure 3, having obtained the surface of connection pad 6 from solder mask layer 3 Expose while connect the structure that a part for the side of pad 6 is coated to by solder mask layer 3.In the structure shown in Fig. 3, phase each other Between adjacent connection pad 6, electrical short caused by solder is difficult to occur, for making the electrode terminal and connection pad of electronic unit 6 reliably electrically connect necessary to amount of solder can be ensured, connection pad 6 can minimize, can make electrical connection can By the circuit board of the excellent high-density wiring of property.

In the forming method of the solder resist pattern, alkali-developable solder resist is used as solder resist, by solder resist In the filming step of 3 filming of layer, alkaline aqueous solution is used.

For the acid number of the solder resist of alkali-developable, the polymer with carboxyl is contained by the solder resist, with performance The mode for going out alkali development is adjusted.But the polymer for being used in the solder resist for require insulating reliability, must It must be set by reducing carboxyl-content by acid number relatively low.In the feelings of the solder resist using this polymer low containing acid number Under condition, if forming solder resist pattern by method disclosed in patent document 1 and 2, the time length needed for filming.Therefore, it is Raising productivity, it is desirable to which the time needed for filming shortens.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-192692 publications

Patent document 2：No. 2012/043201 pamphlet of International Publication No..

The content of the invention

The technical problems to be solved by the invention

The present invention problem be to provide a kind of forming method of solder resist pattern, this method comprises at least in order：At least The step of solder mask layer is formed in circuit substrate with connection pad；With by uncured solder mask layer filming until welding resistance The thickness of oxidant layer is the filming step below the thickness of connection pad, in the method, needed for the filming of solder mask layer Time can shorten, and productivity is improved.

For solving the technological means of problem

The present inventor etc. are in depth studied, as a result found, pass through following solder resist patterns to solve above-mentioned problem Forming method, can solve above-mentioned problem.

(1) a kind of forming method of solder resist pattern, it is the solder resist pattern for comprising at least following steps in order Forming method：At least there is the step of forming solder mask layer in the circuit substrate of connection pad, and by uncured solder resist Layer filmization is until the thickness of solder mask layer is the filming step below the thickness of connection pad, it is characterised in that in film Change the alkaline aqueous solution used in step and include (A) alkali compounds and (B) ammonium ion, (B) ammonium ion is relative to (A) alkalization The mol ratio (B/A) of compound is more than 0.00 and less than 1.85.

(2) forming method of the solder resist pattern described in above-mentioned (1), wherein, (A) alkaline chemical combination in alkaline aqueous solution The content of thing is 5~20 mass %.

(3) forming method of the solder resist pattern described in above-mentioned (1) or (2), wherein, (A) alkali compounds is (A1) nothing Machine alkali compounds.

(4) forming method of the solder resist pattern described in above-mentioned (3), wherein, (A1) inorganic alkaline compound is selected from alkali At least one kind of inorganic alkaline chemical combination in metal carbonate, alkali metal phosphate, alkali metal hydroxide and alkali silicate Thing.

(5) forming method of the solder resist pattern described in above-mentioned (4), wherein, (A1) inorganic alkaline compound is alkali metal Silicate, (B) ammonium ion are 0.04~0.71 relative to the mol ratio (B/A) of (A) alkali compounds.

(6) forming method of the solder resist pattern described in above-mentioned (4), wherein, (A1) inorganic alkaline compound is alkali metal Carbonate, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

(7) forming method of the solder resist pattern described in above-mentioned (4), wherein, (A1) inorganic alkaline compound is alkali metal Hydroxide, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

(8) forming method of the solder resist pattern described in above-mentioned (4), wherein, (A1) inorganic alkaline compound is alkali metal Silicate and alkali carbonate, (B) ammonium ion are 0.04~0.45 relative to the mol ratio (B/A) of (A) alkali compounds.

(9) forming method of the solder resist pattern described in above-mentioned (4), wherein, (A1) inorganic alkaline compound is alkali metal Hydroxide and alkali carbonate, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

(10) forming method of the solder resist pattern described in above-mentioned (4), wherein, (A1) inorganic alkaline compound is alkali gold Belong to phosphate, (B) ammonium ion is 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

(11) forming method of the solder resist pattern described in above-mentioned (1) or (2), wherein, (A) alkali compounds is (A2) Organic basic compound.

(12) forming method of the solder resist pattern described in above-mentioned (11), wherein, (A2) organic basic compound be selected from At least one kind of organic basic compound in TMAH and trimethyl -2- hydroxyethylammonium hydroxides.

(13) forming method of the solder resist pattern described in above-mentioned (12), wherein, (A2) organic basic compound is tetramethyl Base ammonium hydroxide, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

(14) forming method of the solder resist pattern described in above-mentioned (12), wherein, (A2) organic basic compound is front three Base -2- hydroxyethylammonium hydroxides, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

(15) forming method of the solder resist pattern described in above-mentioned (1) or (2), wherein, (A) alkali compounds is (A1) Inorganic alkaline compound and (A2) organic basic compound.

(16) forming method of the solder resist pattern described in above-mentioned (15), wherein, (A1) inorganic alkaline compound be selected from At least one kind of inorganic alkaline compound in alkali carbonate and alkali metal hydroxide, (A2) organic basic compound are At least one kind of organic basic compound in TMAH and trimethyl -2- hydroxyethylammonium hydroxides.

(17) forming method of the solder resist pattern described in above-mentioned (16), wherein, (A1) inorganic alkaline compound is alkali gold Belong to carbonate, (A2) organic basic compound is TMAH, and (B) ammonium ion rubs relative to (A) alkali compounds You are 0.04~1.67 than (B/A).

(18) forming method of the solder resist pattern described in above-mentioned (16), wherein, (A1) inorganic alkaline compound is alkali gold Belong to hydroxide, (A2) organic basic compound is trimethyl -2- hydroxyethylammonium hydroxides, and (B) ammonium ion is relative to (A) alkali Property compound mol ratio (B/A) be 0.04~1.67.

Invention effect

According to the present invention it is possible to provide the forming method of solder resist pattern, this method comprises at least following steps in order：Extremely The step of solder mask layer being formed in few circuit substrate with connection pad, and by uncured solder mask layer filming until resistance The thickness of welding flux layer is the filming step below the thickness of connection pad, in the method, needed for the filming of solder mask layer Time can shorten, productivity is improved.

Brief description of the drawings

Fig. 1 represents the explanation figure of the cross section structure (SMD structures) of the solder resist pattern of an example.

Fig. 2 represents the explanation figure of the cross section structure (NSMD structures) of the solder resist pattern of other examples.

Fig. 3 represents the cross section structure of the solder resist pattern formed by the forming method of the solder resist pattern of the present invention The explanation figure of one example.

Fig. 4 represents the explanation figure of an example of the step in the forming method of the solder resist pattern of the present invention.

Fig. 5 represents the explanation figure of other examples of the step in the forming method of the solder resist pattern of the present invention.

Embodiment

The forming method of the solder resist pattern of the present invention comprises at least in order：In the circuit base at least with connection pad The step of solder mask layer is formed on plate, and by uncured solder mask layer filming until the thickness of solder mask layer is connection pad Thickness below filming step.

Using Fig. 4, illustrate the forming method of the solder resist pattern of the present invention.There is the electricity of connection pad 6 on insulating barrier 1 On base board (Fig. 4 a), solder mask layer 3 (Fig. 4 b) is formed in a manner of covering circuit substrate entire surface.Then, will be uncured The filming of solder mask layer 3, until below thickness of the thickness of solder mask layer 3 for connection pad 6, thus, as shown in figure 4d, formed The solder resist pattern that the connection surface of pad 6 is exposed from solder mask layer 3.

Using Fig. 5, illustrate the forming method of other solder resist pattern of the invention.There is conductive fabric on insulating barrier 1 In the circuit substrate (Fig. 5 a) of line 2 and connection pad 6, (the figure of solder mask layer 3 is formed in a manner of covering circuit substrate entire surface 5b).Then, by activate light 5 by except the thickness of thin membranization of solder mask layer 3 to connect pad 6 thickness below region with Outer part (part of non-filming) exposure, thus solidifies solder mask layer 3 (Fig. 5 c).In Fig. 5 c, solder mask layer 3 is via light Mask 4 is exposed, but can also be exposed in a manner of directly describing.Then, by the uncured filming of solder mask layer 3, Until below thickness of the thickness of solder mask layer 3 for connection pad 6, thus as fig 5d, the connection surface of pad 6 is formed from resistance The solder resist pattern that welding flux layer 3 exposes." region below the thickness of thin membranization of solder mask layer 3 to the thickness for connecting pad 6 " can No matter to be the size for connecting pad more than 6, as long as the insulated electro for not influenceing adjacent conducting wiring 2 is resistive, which kind of journey is arrived greatly Degree all has no problem.

, can also be in circuit in the present invention in addition to the forming method of the solder resist pattern shown in Fig. 4 and Fig. 5 On substrate the step of formation solder mask layer 3, by the filming step of the filming of solder mask layer 3, by activating light exposure welding resistance The step of oxidant layer 3 and uncured development step of solder mask layer 3 etc. is removed completely, change the order of each step, each step Condition (for example, thickness the etc. when part of exposure, filming amount, solder mask layer formation) in number, each step etc., carries out group Close, the solder resist pattern with various structures can be formed.

In the present invention, circuit substrate has insulating barrier 1 and the connection pad 6 formed on the surface of insulating barrier 1.Insulating barrier 1 Surface on, formed with conducting wiring 2, connection pad 6 is a part for conducting wiring 2.In the present invention, for circuit board, There is the solder resist pattern comprising solder mask layer 3 on the surface of circuit substrate, a part for connection pad 6 is revealed from solder mask layer 3 Go out.In the case of the circuit board for carrying electronic unit, the connection pad 6 on a surface is that electronic unit connection is used, another The connection pad 6 on surface is that external connection is used.The connection pad 6 of electronic unit connection is connected with electronic unit, external connection Connection pad 6 is connected with the conducting wiring of external electrical substrate.

Each show the present invention solder resist pattern forming method in step an example explanation figure Fig. 4 and Fig. 5, the example of the cross section structure of solder resist pattern that shows to be formed in the forming method of the solder resist pattern of the present invention In the Fig. 3 for illustrating figure, disclose with a layer insulating 1, there is the circuit base of connection pad 6 on a surface of insulating barrier 1 Plate.But as circuit substrate of the present invention, including：The alternately laminated product on the insulated substrate for be equipped with conducting wiring Layer insulating barrier, conducting wiring and make, have on surface insulating barrier 1 and insulating barrier 1 surface formation connection pad 6 Circuit substrate.

As insulated substrate, such as it can enumerate and be included in glass cloth and be impregnated with bismaleimide-triazine resin, epoxy The resin-made substrate of the insulating material of the thermosetting resin of resin etc. etc..As the insulating barrier of lamination, such as can arrange Act is impregnated with the insulating material of thermosetting resin or the heat in epoxy resin etc. in the same manner as insulated substrate in glass cloth Disperse insulating material of inorganic filler of silica etc. etc. in thermosetting resin.

Conducting wiring 2 and connection pad 6 are formed for example, by subraction, semi-additive process, addition process etc..In subraction, For example, forming anti-etching pattern in the layers of copper set on insulating barrier 1, implement exposure, development, etching, resist stripping, formed Conducting wiring 2 and connection pad 6.In semi-additive process, the base of electro-coppering is set on the surface of insulating barrier 1 by non-electrolytic copper facing Bottom metal layer.Then, plating resist is formed on substrate metal layer and applies pattern, plating is formed on the surface of the substrate metal layer exposed Layers of copper.Then, implement the stripping of plating resist application, the sudden strain of a muscle of substrate metal layer erosion (Off ラ ッ シ ュ エ ッ チ Application グ), form conducting wiring 2 With connection pad 6.

As solder resist of the present invention, the solder resist of alkali-developable can be used.In addition, solder resist can be single Liquid type, dual liquid type, the liquid solder resist of any one, dry film shape solder resist.As solder resist, commercially available liquid can also be used to hinder Solder flux, dry film shape solder resist, solder resist ink etc..For the composition of alkali-developable solder resist, such as can containing alkalescence Soluble resin, polymerizable compound, Photoepolymerizationinitiater initiater, filler, thermosetting component etc..

As alkali soluble resin, the polymer (polymer) containing carboxyl in molecule can be used.From can be with polymerizeing Property compound be crosslinked together, curability, for alkaline aqueous solution tolerance in terms of from the point of view of, more preferably further have in molecule The polymer containing carboxyl of ethylenical unsaturated double bonds.Specifically, it can enumerate in following (1)~(9) and enumerate such gather Compound.

(1) there is unsaturated double-bond by the unsaturated carboxylic acid of (methyl) acrylic acid etc. and more than a kind in addition Copolymer compound obtained from, have carboxyl polymer.

(2) unsaturated carboxylic acid for (methyl) acrylic acid etc. and more than a kind in addition has unsaturated double-bond Compound copolymer (copolymer), there is in the molecule of addition one compound, (methyl) third of epoxy radicals and unsaturated double-bond Alkene acyl chlorides etc., ethylenically unsaturated group is set to turn into side chain, the thus obtained polymer containing carboxyl.

(3) compound and the chemical combination with unsaturated double-bond in addition with epoxy radicals and unsaturated double-bond are made The unsaturated carboxylic acid of the copolymer of thing and (methyl) acrylic acid etc. is reacted, and the secondary alcohol groups and multi-anhydride for making generation are reacted, thus The obtained polymer containing carboxyl.

(4) acid anhydrides with unsaturated double-bond of maleic anhydride etc. and the change with unsaturated double-bond in addition are made There is the compound reaction of hydroxyl and unsaturated double-bond in the copolymer of compound and a molecule, thus obtained by it is poly- containing carboxyl Compound.

(5) react the unsaturated monocarboxylic of multi-functional epoxy compound and (methyl) acrylic acid etc., make the reaction of generation Hydroxyl in thing reacts with saturation or unsaturated multi-anhydride, thus obtained by the polymer containing carboxyl.

(6) polymer of the hydroxyl of polyvinyl alcohol derivative etc. is made with after saturation or the reaction of unsaturated multi-anhydride, making There is the compound reaction of epoxy radicals and unsaturated double-bond in the carboxylic acid of generation and a molecule, thus obtained by it is poly- containing carboxyl Compound.

(7) unsaturated monocarboxylic and (c) molecule of (a) multi-functional epoxy compound, (b) (methyl) acrylic acid etc. are made In there is at least one alcohol hydroxyl group and the compound with 1 in addition to the alcohol hydroxyl group reactive group of epoxy reaction (such as dihydromethyl propionic acid etc.) reacts, so as to get reaction product and saturation or unsaturated multi-anhydride react, therefrom The polymer containing carboxyl.

(8) the multifunctional oxetane compound and (methyl) in a molecule with least two oxetanes ring are made The unsaturated monocarboxylic reaction of acrylic acid etc., thus obtains being modified oxetane resin, for obtained modification oxa- ring fourth Primary hydroxyl in alkane resin, it is allowed to and saturation or the reaction of unsaturated multi-anhydride, the thus obtained polymer containing carboxyl.

(9) polyfunctional epoxy resin (such as cresol novolak type epoxy resin etc.) and unsaturated monocarboxylic (example are made Such as (methyl) acrylic acid) after reaction, itself and multi-anhydride (such as tetrabydrophthalic anhydride etc.) are reacted, is thus contained There is the polymer of carboxyl, further make that there is 1 oxirane ring and more than 1 in the polymer for containing carboxyl and a molecule Ethylenically unsaturated group compound (such as (methyl) glycidyl acrylate etc.) reaction, thus obtained from contain carboxyl Polymer.

Polymer containing carboxyl is not limited to the above-mentioned polymer enumerated.In addition, among them, can be used alone, Two or more can also be combined to use.

Among the above-mentioned polymer enumerated, preferably above-mentioned (2), (5), (7), the polymer containing carboxyl of (9), particularly From the aspect of the characteristic of the solder mask layer after curability, solidification, the polymer containing carboxyl of more preferably above-mentioned (9).

It should illustrate, in the present invention, (methyl) acrylic acid refers to be referred to as acrylic acid, methacrylic acid and their mixture Term.(methyl) acrylate refers to the term for being referred to as acrylate, methacrylate and their mixture.As one There is epoxy radicals and the compound of unsaturated double-bond in molecule, (methyl) glycidyl acrylate, (methyl) third can be enumerated Olefin(e) acid 3,4- expoxycyclohexyl methyl esters etc..As the compound in a molecule with hydroxyl and unsaturated double-bond, can enumerate (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters etc..

The above-mentioned polymer containing carboxyl has substantial amounts of free carboxy on the side chain of skeleton polymer (main chain), Therefore can be developed using dilute alkali aqueous solution.

In addition, the acid number of the above-mentioned polymer containing carboxyl is preferably 80~150mgKOH/g scope, more preferably 90 ~120mgKOH/g scope.If the acid number of the polymer containing carboxyl is less than 80mgKOH/g, exists and produced on connection pad 6 The situation of the residue of raw solder resist.On the other hand, if more than 150mgKOH/g, by the thin of uncured solder mask layer filming In membranization step, the solder mask layer 3 of the solidification of exposure portion be present, be easily swelled by the solder mask layer 3 of filming, solder resist The situation that the insulating reliability of pattern reduces.

The matter average molecular weight of polymer containing carboxyl is preferably 5000~150000, and more preferably 10000~100000. In the case that matter average molecular weight is less than 5000, solder mask layer 3 after hardening is deposited for the tolerance reduction of alkaline aqueous solution Tendency, on the other hand, if more than 150000, time needed for filming elongated tendency be present.

The use level of polymer containing carboxyl relative to solder mask layer 3 be preferably 40~65 mass %, more preferably 45~ 55 mass %.In the case that the use level of polymer containing carboxyl is less than 40 mass %, the chemistry of the solder mask layer 3 of solidification be present The tendency that intensity, mechanical strength reduce.It additionally, there are the tendency of envelope variation.If the use level of the polymer containing carboxyl More than 65 mass %, then polymerism reduction be present.

Polymerizable compound is to carry out photopolymerization by actinic light, solidifies solder mask layer 3, hence for alkalescence The insoluble compound of the aqueous solution or contribute to insoluble compound.As this polymerizable compound, second two can be enumerated Two (methyl) esters of acrylic acids of the glycol of alcohol, methoxyl group tetraethylene glycol, polyethylene glycol, propane diols etc.；Hexylene glycol, trihydroxy methyl third The polyalcohol or their ethylene oxide adduct of alkane, pentaerythrite, dipentaerythritol, three-hydroxyethyl chlorinated isocyanurates etc. Or polynary (methyl) esters of acrylic acid of propylene oxide adduct etc.；Phenoxy group (methyl) acrylate, bisphenol-A two (methyl) Acrylate and the ethylene oxide adduct of their phenols or polynary (methyl) acrylate of propylene oxide adduct etc. Class；Glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group are different Polynary (methyl) esters of acrylic acid of the glycidol ether of cyanurate etc.；With melamine (methyl) acrylate etc..

The use level of polymerizable compound is relative to the mass parts of polymer 100 containing carboxyl, preferably 5~100 mass Part, more preferably 10~70 mass parts.In the case that the use level of polymerizable compound is less than 5 mass parts, curability reduces, and deposits Become the situation of difficulty in is formationed using actinic light and the solder resist pattern of filming progress, exist and utilize solder resist Pattern carries out being protected against the situation that the effect of external environment influence can not play.On the other hand, more than the feelings of 100 mass parts Under condition, that the time needed for filming is elongated be present, deposit the situation that solder mask layer 3 after hardening becomes fragile.

As filler, inorganic filler or organic filler can be used.Particularly preferably using barium sulfate, silica, talcum, silicon Resin-oatmeal, nylon powder, fluororesin powder (Off ッ element パ ウ ダ ー) etc., they can be independently matched with, or coordinate two or more.Filler Average grain diameter be preferably in the range of 0.1~20 μm.Above-mentioned average grain diameter be more preferably more than 0.2 μm, more preferably 4 μm with Under, more preferably less than 2 μm.

In addition, for the surface of conducting wiring 2, in order to improve the adaptation with solder mask layer 3, carried out sometimes with etchant Surface roughening.Now, connection pad 6 is a part for conducting wiring 2, therefore connects the surface of pad 6 also by rough surface Change.When thus having carried out being formed solder mask layer 3 on the connection pad 6 of surface roughening treatment, it is thick that filler can enter through surface The bumps on connection pad 6 surface that roughening is formed.In most cases, the thin of the solder mask layer 3 around the filler of bumps is entered Membranization speed is than generally slow.As a result, there is a situation where to connect the residue that solder resist is produced on the surface of pad 6.Therefore, in order to keep away Exempt to produce residue, the average grain diameter of filler is preferably in the range of 0.1~20 μm.

Average grain diameter in the present invention is the D50 (the particle footpath of volume reference 50%) determined by laser diffraction and scattering method.

The use level of filler is more excellent preferably below 300 mass parts relative to the mass parts of polymer 100 containing carboxyl Elect 0.1~300 mass parts, more preferably 0.1~150 mass parts as.Situation of the use level of filler more than 300 mass parts Under, exist for manufacturing the coating fluid of dry film shape solder resist, the viscosity of liquid solder resist uprises, the situation that application property reduces, deposit The situation that solder mask layer 3 after hardening becomes fragile.

As the shape of filler, spherical, needle-like, tabular, flakey, hollow form, amorphous, hexagon, vertical can be used Square shape, flake etc., dispersiveness from solder mask layer 3, for the influence of resolution ratio from the viewpoint of, it is preferably spherical.

As Photoepolymerizationinitiater initiater, can enumerate benzoin, benzoin methyl ether, benzoin ethyl ether etc. benzoin and Its alkyl ether；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 1,1- dichloroacetophenones, 4- (epoxide of the 1- tert-butyl groups two - 1- Methylethyls) acetophenone etc. acetophenones；2-methylanthraquinone, 2- amyl anthraquinones, 2- tert-butyl groups anthraquinone, 1- chloroanthraquinones etc. Anthraquinones；The thioxanthene ketone class of 2,4- diethyl thioxanthones, 2,4- diisopropylthioxanthones, CTX etc.；Acetophenone diformazan The ketal class of base ketal, benzyl dimethyl ketal etc.；Diphenylmethanone, 4- (epoxide -1- Methylethyls of the 1- tert-butyl groups two) hexichol Diphenylmethyl ketone of base ketone, 3,3 ', 4,4 '-four (Epoxide carbonyl of the tert-butyl group two) diphenylmethanones etc. etc..

In addition, as preferable Photoepolymerizationinitiater initiater, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholines can be enumerated For acetone -1,2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butane -1- ketone, 2- (dimethylamino) -2- [(4- Aminomethyl phenyl) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone, N, N- dimethylaminos benzoylformaldoxime (as commercially available product, has イ Le ガ キ ュ ア (Irgacure, registration mark) 907, イ Le ガ キ ュ ア (registration mark) 369, the イ Le ガ of BASF societies キ ュ ア (registration mark) 379 etc.) etc. alpha-aminoacetophenone class；It is 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, double (2,4,6- trimethylbenzoyls)-phenyl phosphine oxide, double (2,6- Dimethoxybenzoyls) -2,4,4- trimethyl-pentyls Phosphine oxide (as commercially available product, there is Le シ リ Application (Lucirin, registration mark) TPO, イ Le ガ キ ュ ア (registrations of BASF societies Trade mark) 819 etc.) etc. acylphosphine oxide class.

The use level of Photoepolymerizationinitiater initiater is 0.01~30 mass parts relative to the mass parts of polymer 100 containing carboxyl, The preferably ratio of 0.5~15 mass parts.If the fit rate of Photoepolymerizationinitiater initiater is relative to the mass of polymer 100 containing carboxyl Part is less than 0.01 mass parts, then that the photo-curable of solder mask layer 3 is insufficient, it is peeling-off solder mask layer 3 to be present be present Situation, the characteristic that the solder mask layer 3 of resistance to chemical reagents etc. be present reduce.On the other hand, if the cooperation of Photoepolymerizationinitiater initiater Amount more than 30 mass parts, then exists due to the light absorbs of Photoepolymerizationinitiater initiater relative to the mass parts of polymer 100 containing carboxyl, The situation that deep curability reduces.

In solder mask layer 3, in order to improve physical strength of solder mask layer 3 etc., thermosetting component can be coordinated as needed. As this thermosetting component, amino resins, the isocyanates of end-blocking of melmac, benzoguano amine resin etc. can be used The heat of compound, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin etc. Thermosetting resin.

The use level of thermosetting component is commonly used ratio, for example, relative to the polymer containing carboxyl and The mass parts of total amount 100 of polymerizable compound, preferably 0.01~20 mass parts.Thermosetting component can be used alone, and also may be used Two or more is combined to use.

And then for the synthesis of the polymer containing carboxyl, the preparation of liquid solder resist, for manufacturing dry film shape solder resist The preparation of coating fluid, the liquid solder resist Huo Tu liquid viscosity regulation etc. purpose, can be used in solder resist organic molten Agent.

As organic solvent, can enumerate ketone, aromatic hydrocarbons, glycol ethers, glycol ethers acetate esters, esters, alcohols, Aliphatic hydrocarbon, oil series solvent etc..

More specifically, the ketone of methyl ethyl ketone, cyclohexanone etc. can be enumerated；Toluene, dimethylbenzene, durol etc. Aromatic hydrocarbons；Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propane diols list first The glycol ethers of base ether, DPGME, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether etc.；Ethyl acetate, second Acid butyl ester, dipropylene glycol methyl ether acetic acid esters, methyl proxitol acetate, propylene glycol ethyl ether acetic acid esters, propane diols butyl The esters of ether acetic acid ester etc.；The alcohols of ethanol, propyl alcohol, ethylene glycol, propane diols etc.；The aliphatic hydrocarbon of octane, decane etc.；Petroleum ether, Oil series solvent of naphtha, hydrotreated naphtha, solvent naphtha etc. etc..Organic solvent can be used alone, can also be with 2 kinds The form of mixture above uses.

The method that solder mask layer 3 is formed in circuit substrate can for any method.Such as the feelings in liquid solder resist Under condition, silk screen print method, rolling method, spray-on process, infusion process, curtain coating method, scraper rubbing method, air knife method, heat can be enumerated Molten method, gravure coating process, bristle rubbing method, lithographic methods etc..In the case of dry film shape solder resist, lamination can be enumerated Method, vacuum lamination method etc..

In exposure in the step of solder mask layer 3 is exposed, for solder mask layer 3, irradiation activation light.Can use with Xenon lamp, high-pressure sodium lamp, low pressure mercury lamp, ultrahigh pressure mercury lamp, UV fluorescent lamps expose for the reflected image of light source, have used photomask One side, it is two-sided it is closely sealed exposure, close to mode, projection pattern, laser scanning exposure etc.., can be with the case of being scanned exposure By by UV laser, He-Ne laser, He-Cd laser, argon laser, krypton ion laser, ruby laser, YAG laser, N_2 laser, The LASER Light Source of dye laser, excimer laser etc. according to emission wavelength carry out SHG wavelength conversions scan exposure or Using liquid crystal grating, the scan exposure of micro mirror array grating, it is exposed.By exposure, solder mask layer 3 is polymerize, consolidate Change.

In the present invention, the filming step of the filming of solder mask layer 3 is included by alkaline aqueous solution (filming processing Liquid) uncured solder mask layer composition is carried out the micellization processing (filming processing) of micellization, and then carry out, pass through Micella removes the micella removing processing that liquid removes micella.The step may further include by washing the resistance that will do not removed completely The surface of welding flux layer 3, the filming treatment fluid of residual attachment and micella remove the drying of washing process, removing washing water that liquid is washed off Processing.

Micellization processing (filming processing) refers to, by alkaline aqueous solution (filming treatment fluid) by solder mask layer composition Micellization, the micella become temporarily insoluble processing for filming treatment fluid.Filming treatment fluid is the alkaline water of high concentration Solution.The forming method of solder resist pattern is provided in the present invention, wherein, alkaline aqueous solution includes (A) alkali compounds and (B) ammonium Ion, (B) ammonium ion more than 0.00 and are less than 1.85 relative to the mol ratio (B/A) of (A) alkali compounds, thus solder mask layer Time needed for 3 filming can shorten, productivity is improved." (B) ammonium ion rubs relative to (A) alkali compounds You are than (B/A) " it is sometimes referred to simply as " mol ratio (B/A) ".

As (A) alkali compounds contained in alkaline aqueous solution, there are (A1) inorganic alkaline compound and (A2) organic base Property compound.

As (A1) inorganic alkaline compound, alkali silicate, alkali metal hydroxide, alkali metal phosphoric acid can be enumerated The inorganic alkaline compound of salt, alkali carbonate etc..As alkali metal, lithium, sodium, potassium etc. can be enumerated.Above-mentioned (A1) is inorganic Alkali compounds can be used alone, and can also use multiple combinations.

As (A2) organic basic compound, MEA, diethanol amine, triethanolamine, methylamine, diformazan can be enumerated Amine, ethamine, diethylamine, triethylamine, cyclohexylamine, TMAH (TMAH), tetraethyl ammonium hydroxide, trimethyl -2- hydroxyls The organic basic compound of base ethyl ammonium hydroxide (choline) etc..Above-mentioned (A2) organic basic compound can be used alone, Multiple combinations can be used.

(A) content of alkali compounds is relative to alkaline aqueous solution, preferably 3~25 mass %, more preferably 5~20 matter Measure %, particularly preferably more preferably 7~17 mass %, 8~13 mass %.(A) content of alkali compounds is less than 3 mass % In the case of, that filming amount becomes uneven be present.If in addition, more than 25 mass %, in (A1) inorganic alkaline compound In the case of, the precipitation of alkali compounds easily occurs, therefore filming treatment fluid elapses asking for existence and stability over time Topic, in the case of (A2) organic basic compound, foul smell is strong, therefore workability variation be present.Alkaline aqueous solution PH be preferably more than 10.Furthermore it is also possible to surfactant, defoamer, solvent etc. are suitably added for alkaline aqueous solution.

In addition, in order that the surface of solder mask layer 3 more uniformly filming, can also add sulfuric acid in alkaline aqueous solution Salt, sulphite.As sulfate or sulphite, the sulfate or sulfurous acid of the alkali metal of lithium, sodium or potassium etc. can be enumerated The sulfate or sulphite of the alkaline-earth metal of salt, magnesium, calcium etc..It is (mole dense as the content of sulfate and/or sulphite Degree), preferably 0.05~1.0 mole/L.In the case of less than 0.05 mole/L, power of saltouing is weak, hydrauture diminishes, therefore exists and carry The situation that the effect of the homogenization of high filming processing is deteriorated.If more than 1.0 moles/L, it is bad to there is easily generation filming Situation.As a result, the precipitation of insoluble composition is found on the surface of solder mask layer 3 after filming, it is tackiness to there is appearance The situation of problem.

It is a feature of the present invention that alkaline aqueous solution includes (B) ammonium ion (NH₄ ⁺).As the supply source of (B) ammonium ion, Ammonium salt can be used.As ammonium salt, can enumerate ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, Ammonium phosphite, ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium acid fluoride, ammonium hydrogen sulfate, ammonium sulfate, Ammonium iodide, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium aurintricarboxylate, ammonium benzoate, aminoquinoxaline, ammonium citrate, two Diethyldithiocar bamic acid ammonium, ammonium formate, ammonium bimalate, ammonium binoxalate, hydrogen phthalate ammonium, ammonium hydrogen tartrate, sulphur Ammonium thiosulfate, ammonium sulfite, ethylenediamine tetra-acetic acid ammonium, ferric ammonium ethylene diamine tetraacetate, ammonium lactate, malic acid ammonium, maleic acid ammonium, grass Sour ammonium, ammonium phthalate, ammonium picrate, APDC, ammonium salicylate, ammonium succinate, p-aminophenyl Ichthyodin, ammonium tartrate, ammonium mercaptoacetate, 2,4,6- ammonium trinitrophenolates etc., wherein, preferred ammonium carbonate.It should illustrate, can be with And with multiple supply sources.

In the present invention, mol ratio (B/A) is more than 0.00 and less than 1.85.Mol ratio (B/A) is more preferably more than 0.03, enters One step is preferably more than 0.04, and particularly preferably more than 0.10.In addition, mol ratio (B/A) is more preferably less than 1.67, more preferably For less than 1.00, more preferably less than 0.71, particularly preferably less than 0.50, most preferably less than 0.45.Mol ratio (B/ A) more than 0.00, if but mol ratio (B/A) be less than 0.03, due to (B) ammonium ion content deficiency, shorten filming needed for when Between effect diminish, with without (B) ammonium ion, mol ratio (B/A) be 0.00 situation compared with, the time needed for filming be present Situation about having almost no change, therefore mol ratio (B/A) is more preferably more than 0.03.If in addition, mol ratio (B/A) be 1.85 with On, then to be excessive compared with without (B) ammonium ion, the situation that mol ratio (B/A) is 0.00, there is film in (B) ammonium ion content Time needed for changing is identical, or situation elongated on the contrary.

(A) in the case that alkali compounds is (A1) inorganic alkaline compound, (A1) inorganic alkaline compound is preferably to select From at least one kind of inorganic alkaline in alkali carbonate, alkali metal phosphate, alkali metal hydroxide and alkali silicate Compound.For the nearly all of (A1) inorganic alkaline compound, as long as in the range of above-mentioned mol ratio (B/A), it is possible to Obtain the effect of the present invention.But in the case that (A1) inorganic alkaline compound is alkali silicate, if mol ratio (B/A) More than 0.71, then that " gelation " occurs for alkaline aqueous solution be present.In addition, (A1) inorganic alkaline compound is alkali metal silicon In the case of hydrochlorate and alkali carbonate, that is, it is used as (A1) inorganic alkaline compound, and with alkali silicate and alkali metal In the case of carbonate, if more than 0.45, the state that alkaline aqueous solution can not keep " aqueous solution " be present in mol ratio (B/A), The situation of " gelation " occurs.In the case that gelation occurs for alkaline aqueous solution, that filming amount becomes uneven be present, There is a situation where to connect the residue that solder mask layer 3 is produced on pad 6, thus it is not preferred.

(A) in the case that alkali compounds is (A2) organic basic compound, (A2) organic basic compound is preferably to select At least one kind of organic basic compound from TMAH and trimethyl -2- hydroxyethylammonium hydroxides.

(A) in the case that alkali compounds is (A1) inorganic alkaline compound and (A2) organic basic compound, i.e. conduct (A) alkali compounds, and with (A1) inorganic alkaline compound and (A2) organic basic compound in the case of, it is preferred that (A1) inorganic alkaline compound is at least one kind of inorganic alkaline chemical combination in alkali carbonate and alkali metal hydroxide Thing, (A2) organic basic compound are at least 1 in TMAH and trimethyl -2- hydroxyethylammonium hydroxides The organic basic compound of kind.

In addition, alkaline aqueous solution includes more than a kind of (A1) inorganic alkaline compound and more than a kind (A2) organic basic In the case of compound, the mass ratio of (A1) inorganic alkaline compound and (A2) organic basic compound is preferably 1：1~1：10, More preferably 1：1~1：6, more preferably 1：1~1：3.

As filming processing, impregnation, paddle-tumble processing (processing of パ De Le) can be used, spraying treatment, brushes, scrape The method of wiping etc., impregnation is preferable.For the processing method beyond impregnation, easily produced in filming treatment fluid Bubble, the caused bubble are attached to the surface of solder mask layer 3 in filming processing, the feelings that filming amount becomes uneven be present Condition.The temperature of alkaline aqueous solution is preferably 15~35 DEG C, more preferably 20~30 DEG C.If temperature is too low, alkalescence be present Compound is in the case of the wetting-out rate of solder mask layer 3 is slack-off, for filming to required thickness, it is necessary to for a long time.Separately On the one hand, if temperature is too high, while alkali compounds is impregnated with for solder mask layer 3, dissolving diffusion occurs, production thus be present The filming amount of raw solder mask layer 3 becomes the situation of uneven part.

In the micella removing processing for removing the micella of the solder mask layer composition insoluble for filming treatment fluid, pass through Micella of spraying removes liquid, and micella at one stroke dissolving is removed.

Liquid is removed as micella, running water, industrial water, pure water etc. can be used.In addition, micella, which removes liquid, includes alkalescence Compound, pH are 5~10, thus the easy redisperse of solder mask layer composition insoluble in filming treatment fluid.Removed as micella The alkali compounds gone included in liquid, it can enumerate as (A) alkali included in alkaline aqueous solution (filming treatment fluid) Alkali compounds exemplified by property compound.It is further preferred, that alkaline aqueous solution and micella remove the alkalescence included in liquid Compound is one species.In the case that the pH of micella removing liquid is less than 5, solder mask layer composition condenses, and is formed insoluble Sludge, the sludge may be attached to the surface of solder mask layer 3 of filming.On the other hand, micella removes the pH of liquid more than 10 In the case of, excessive dissolution diffusion occurs for solder mask layer 3, that filming amount becomes uneven be present.In addition, micella removes liquid PH can be adjusted using sulfuric acid, phosphoric acid, hydrochloric acid etc..

Spray condition in being handled for micella removing illustrates.The condition (temperature, time, atomisation pressure) of spraying is matched somebody with somebody Suitably adjusted together in the dissolution velocity of solder mask layer 3.Specifically, treatment temperature is preferably 10~50 DEG C, more preferably 15 ~35 DEG C.In addition, atomisation pressure is preferably 0.01~0.5MPa, more preferably 0.1~0.3MPa.Micella removes the supply stream of liquid Amount is relative to 1cm²Solder mask layer 3, preferably 0.030~1.0L/min, more preferably 0.050~1.0L/min, further Preferably 0.10~1.0L/min.If solder mask layer 3 surface of the supply flow rate after the scope, filming will not remain insoluble The sludge of property, substantially (generally) can equably remove micella in face.Relative to 1cm²Supply flow rate be less than 0.030L/ In the case of min, that solubilizing poorly occurs for thawless solder mask layer composition be present.On the other hand, if supply flow rate surpasses 1.0L/min is crossed, then the part that pump etc. necessary to being used to supply be present becomes huge, it is necessary to huge device.Enter And in the case of the supply flow rate more than 1.0L/min, the effect that the dissolving for solder mask layer composition is spread will not change Become.

Micella removing processing after, can be washed away by washing process do not remove completely solder mask layer 3, in solder mask layer 3 The filming treatment fluid and micella of remained on surface attachment remove liquid.As the method for washing process, supplied from diffusion velocity and liquid From the viewpoint of the uniformity given, preferred spray pattern.As washing water, running water, industrial water, pure water etc. can be used. Wherein, preferably using pure water.Pure water can use the pure water generally used in industrial use.

In drying process, the dry arbitrary form of heated-air drying, room temperature blowing can be used, but is preferably, high pressure is empty Gas is supplied gas from air gun or supplied gas from air blower by substantial amounts of air, and the water of the remained on surface of solder mask layer 3 is dispelled with air knife Drying means.

In the forming method of the solder resist pattern of the present invention, to form the thickness after solder mask layer 3 and uncured welding resistance Oxidant layer 3 is by the amount of filming, it is determined that connecting the thickness of the solder mask layer 3 around pad 6.In addition, the solder resist pattern of the present invention Forming method in, can freely adjust filming amount in 0.01~500 μm of scope.From the solder mask layer 3 after filming Height to the top surface of connection pad 6 is suitably adjusted according to required amount of solder.Specifically, the top surface of pad 6 is connected Distance with the top surface of the solder mask layer 3 after filming is preferably more than 1 μm and less than 50 μm.

In the present invention, after the filming step of the filming of solder mask layer 3, it is preferable to carry out consolidating solder mask layer 3 The step of changing processing (post cure step).Other steps can be included between filming step and post cure step.By rear Curing schedule, solder resist pattern well can effectively play and prevent the oxidation of conducting wiring, be electrically insulated and be protected from outside The effect that environment influences.As curing process, such as heating, the entire surface irradiation work for solder mask layer 3 can be enumerated Change the exposure-processed of light and with heating and exposure-processed etc..In the case of being heated, it is preferred that in nitrogen gas In atmosphere, the temperature from room temperature to 450 DEG C is selected, carries out staged heating, or selects a certain temperature range, continuous warming, together When implement 5 points~5 hours.The maximum temperature of heating is preferably 120~450 DEG C, more preferably 130~450 DEG C.For example, At 130 DEG C, 200 DEG C, 400 DEG C, each carry out heating for 30 minutes.Alternatively, it is also possible to 2 hours from room temperature to 400 DEG C Ramped thermal is carried out, is heated.Furthermore it is also possible to select a certain temperature, certain time heating is carried out.

Embodiment

Hereinafter, embodiment, in further detail the explanation present invention, but the present invention is not limited by the embodiment are passed through.

<The synthesis of polymer containing carboxyl>

Feed intake first in the detachable flask for possessing mixer, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe Phenol-novolac type epoxy resin (Japanese chemical drug society system, trade name：EOCN-104S) 660.0 mass parts, carbitol acetate 432 mass parts and the mass parts of solvent naphtha 188.0, are heated to 90 DEG C, are stirred simultaneously, dissolved.Then, it is temporarily cold But to 60 DEG C, the mass parts of acrylic acid 216, the mass parts of triphenylphosphine 4.0, the mass parts of methyl hydroquinone 1.3 are added, at 100 DEG C Lower reaction 12 hours.Then, tetrabydrophthalic anhydride 290.0g mass parts are added, are heated to 90 DEG C, are reacted 6 hours.Thus, Obtain the solution of the mass % of nonvolatile component 65 polymer containing carboxyl.Hereinafter, by the solution of the polymer for containing carboxyl Referred to as " polymer A-1 ".It should illustrate, polymer A-1 acid number is low, and solid constituent acid number is 85mgKOH/g.Acid number foundation JIS K2501：2003 are measured.

Coordinate each material according to the ratio (mass parts) shown in table 1, after being pre-mixed with mixer, with 3 roller mills It is kneaded, prepares solder resist.

[table 1]

(embodiment and comparative example)

By copper-clad laminated board (area 170mm × 200mm, 18 μm of copper thickness, base material thickness 0.4mm), by using against corrosion The subraction of agent, being produced on insulating barrier 1 has 80 μm of conducting wiring width, the conducting wiring 2 of 80 μm of conductive fabric wire spacing Circuit substrate.Then, above-mentioned solder resist is respectively coated using applicator on foregoing circuit plate, implemented 30 minutes at 70 DEG C Dry.Thus, the welding resistance that the dry film thickness from the surface of insulating barrier 1 to the surface of solder mask layer 3 is 35 μm is formed in circuit substrate Oxidant layer 3.

Then, connection pad 6 will partly be regarded corresponding to the beginning and end of conducting wiring 2 as, for away from beginning and end The area illumination activation light 5 of 80 μm of the end of corresponding part more laterally, using the photomask 4 with this pattern, is used Closely sealed exposure machine, with 200mJ/cm²Energy, for solder mask layer 3 implement expose.

Then, using the alkaline aqueous solution (filming treatment fluid) shown in 2~table of table 11, impregnation is carried out.As (B) The supply source of ammonium ion uses ammonium carbonate.It should illustrate, the time needed for impregnation in alkaline aqueous solution is recorded in table 2 " processing time " of~table 11.Then, using running water, implement micella and remove processing and washing, then, processing is dried, By the uncured filming of solder mask layer 3, until the average thickness of the solder mask layer 3 of unexposed portion is 12 μm.Then, exist 150 DEG C, 60 points of condition implementation solidify afterwards, form solder resist pattern.

Alkaline aqueous solution contains (A) alkali compounds and (B) ammonium ion, mol ratio (B/A) more than 0.00 and less than 1.85 Embodiment in the case of, with alkaline aqueous solution (filming treatment fluid) only comprising (A) alkali compounds, do not contain (B) ammonium from Son, the comparative example that mol ratio (B/A) is 0.00 are compared, and can confirm that the effect of the time shortening needed for the filming of solder mask layer Fruit.

Hereinafter, for the variety classes of (A) alkali compounds, illustrate in more detail.2~table of table 7 is (A) alkalization Compound is the example of (A1) inorganic alkaline compound, and table 8 and table 9 are that (A) alkali compounds is (A2) organic basic compound Example, table 10 and table 11 are example of (A) alkali compounds for (A1) inorganic alkaline compound and (A2) organic basic compound.

[table 2]

Table 2 is the example that (A1) inorganic alkaline compound is sodium metasilicate (alkali silicate).(A1) inorganic alkaline In the case that the content of compound is equal, alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) be more than 0.00 and 0.71 with Under embodiment processing time with alkaline aqueous solution without (B) ammonium ion, mol ratio (B/A) be 0.00 comparative example compared with, Shorten (embodiment 1-1~1-7 and comparative example 1-1, embodiment 1-8~1-14 and comparative example 1-3, embodiment 1-15~1-21 and Comparative example 1-5, embodiment 1-22~1-28 and comparative example 1-7).

In addition, in the case that the content of (A1) inorganic alkaline compound is equal, mol ratio (B/A) is 0.04~0.71 reality Apply in example, confirm the effect that processing time shortens it is high (embodiment 1-2~1-7, embodiment 1-9~1-14, embodiment 1-16~ 1-21, embodiment 1-23~1-28).

And then in the comparative example of mol ratio (B/A) more than 0.71, filming treatment fluid can not keep the shape of " aqueous solution " State, occur " gelation " (comparative example 1-2,1-4,1-6,1-8).

[table 3]

Table 3 is the example that (A1) inorganic alkaline compound is potassium carbonate (alkali carbonate).(A1) inorganic alkaline chemical combination In the case that the content of thing is equal, alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and less than 1.85 Processing time of embodiment with alkaline aqueous solution without (B) ammonium ion, the comparative example that mol ratio (B/A) is 0.00, contain (B) ammonium Ion, the comparative example that mol ratio (B/A) is more than 1.85 are compared, and shorten (embodiment 2-1~2-8 and comparative example 2-1~2-2, reality Apply a 2-9~2-16 and comparative example 2-3~2-4, embodiment 2-17~2-24 and comparative example 2-5~2-6, embodiment 2-25~2- 32 and comparative example 2-7~2-8).

In addition, in the case that the content of (A1) inorganic alkaline compound is equal, mol ratio (B/A) is 0.04~1.67 reality Apply in example, confirm effect height (embodiment 2-2~2-7, embodiment 2-10~2-15, embodiment 2-18 that processing time shortens ~2-23, embodiment 2-26~2-31).

[table 4]

Table 4 is the example that (A1) inorganic alkaline compound is sodium hydroxide (alkali metal hydroxide).(A1) inorganic alkaline In the case that the content of compound is equal, alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and is less than The processing time of 1.85 embodiment and alkaline aqueous solution without (B) ammonium ion, the comparative example that mol ratio (B/A) is 0.00, contain There is (B) ammonium ion, the comparative example that mol ratio (B/A) is more than 1.85 is compared, shortening (embodiment 3-1~3-8 and comparative example 3-1 ~3-2, embodiment 3-9~3-16 and comparative example 3-3~3-4, embodiment 3-17~3-24 and comparative example 3-5~3-6, embodiment 3-25~3-32 and comparative example 3-7~3-8).

In addition, in the case that the content of (A1) inorganic alkaline compound is equal, (B) ammonium ion is relative to (A1) inorganic alkaline The mol ratio (B/A) of compound is in 0.04~1.67 embodiment, confirms effect height (the embodiment 3- that processing time shortens 2~3-7, embodiment 3-10~3-15, embodiment 3-18~3-23, embodiment 3-26~3-31).

[table 5]

Table 5 is that (A1) inorganic alkaline compound is sodium metasilicate (alkali silicate) and potassium carbonate (alkali metal carbonic acid Salt), the mass ratio of sodium metasilicate and potassium carbonate be 5：1 example.(A1) in the case that the content of inorganic alkaline compound is equal, Alkaline aqueous solution contains (B) ammonium ion, the processing time and alkalescence of the embodiment of mol ratio (B/A) more than 0.00 and less than 0.45 The aqueous solution is compared without (B) ammonium ion, the comparative example that mol ratio (B/A) is 0.00, shortens (embodiment 4-1~4-7 and comparative example 4-1, embodiment 4-8~4-14 and comparative example 4-3, embodiment 4-15~4-21 and comparative example 4-5, embodiment 4-22~4-28 and Comparative example 4-7).

In addition, in the case that the content of (A1) inorganic alkaline compound is equal, mol ratio (B/A) is 0.04~0.45 reality Apply in example, confirm the effect that processing time shortens it is high (embodiment 4-2~4-7, embodiment 4-9~4-14, embodiment 4-16~ 4-21, embodiment 4-23~4-28).

And then in the comparative example of mol ratio (B/A) more than 0.45, filming treatment fluid can not keep the shape of " aqueous solution " State, occur " gelation " (comparative example 4-2,4-4,4-6,4-8).

[table 6]

Table 6 is that (A1) inorganic alkaline compound is sodium hydroxide (alkali metal hydroxide) and potassium carbonate (alkali metal carbonic acid Salt), the mass ratio of sodium hydroxide and potassium carbonate be 1：1 example.(A1) in the case that the content of inorganic alkaline compound is equal, The processing time for the embodiment that alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and less than 1.85 and alkalescence The aqueous solution is 1.85 without (B) ammonium ion, the comparative example that mol ratio (B/A) is 0.00, containing (B) ammonium ion, mol ratio (B/A) Comparative example above is compared, and shortens (embodiment 5-1~5-8 and comparative example 5-1~5-2, embodiment 5-9~5-16 and comparative example 5-3~5-4, embodiment 5-17~5-24 and comparative example 5-5~5-6, embodiment 5-25~5-32 and comparative example 5-7~5-8).

In addition, in the case that the content of (A1) inorganic alkaline compound is equal, mol ratio (B/A) is 0.04~1.67 reality Apply in example, confirm effect height (embodiment 5-2~5-7, embodiment 5-10~5-15, embodiment 5-18 that processing time shortens ~5-23, embodiment 5-26~5-31).

[table 7]

Table 7 is the example that (A1) inorganic alkaline compound is tertiary sodium phosphate (alkali metal phosphate).(A1) inorganic alkaline In the case that the content of compound is equal, alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and less than 1.85 Embodiment processing time and alkaline aqueous solution without (B) ammonium ion, the comparative example that mol ratio (A/B) is 0.00, contain (B) Ammonium ion, the comparative example that mol ratio (B/A) is more than 1.85 are compared, shorten (embodiment 6-1~6-8 and comparative example 6-1~6-2, Embodiment 6-9~6-16 and comparative example 6-3~6-4, embodiment 6-17~6-24 and comparative example 6-5~6-6, embodiment 6-25~ 6-32 and comparative example 6-7~6-8).

In addition, in the case that the content of (A1) inorganic alkaline compound is equal, mol ratio (B/A) is 0.04~1.67 reality Apply in example, confirm effect height (embodiment 6-2~6-7, embodiment 6-10~6-15, embodiment 6-18 that processing time shortens ~6-23, embodiment 6-26~6-31).

[table 8]

Table 8 is the example that (A2) organic basic compound is TMAH (TMAH).(A2) organic basic chemical combination In the case that the content of thing is equal, alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and less than 1.85 Processing time of embodiment with alkaline aqueous solution without (B) ammonium ion, the comparative example that mol ratio (A/B) is 0.00, contain (B) ammonium Ion, the comparative example that mol ratio (B/A) is more than 1.85 are compared, and shorten (embodiment 7-1~7-8 and comparative example 7-1~7-2, reality Apply a 7-9~7-16 and comparative example 7-3~7-4, embodiment 7-17~7-24 and comparative example 7-5~7-6, embodiment 7-25~7- 32 and comparative example 7-7~7-8).

In addition, in the case that the content of (A2) organic basic compound is equal, mol ratio (B/A) is 0.04~1.67 reality Apply in example, confirm effect height (embodiment 7-2~7-7, embodiment 7-10~7-15, embodiment 7-18 that processing time shortens ~7-23, embodiment 7-26~7-31).

[table 9]

Table 9 is the example that (A2) organic basic compound is trimethyl -2- hydroxyethylammonium hydroxides (choline).(A2) have In the case that the content of machine alkali compounds is equal, alkaline aqueous solution contain (B) ammonium ion, mol ratio (B/A) more than 0.00 and The processing time of embodiment less than 1.85 is with alkaline aqueous solution without (B) ammonium ion, the comparison that mol ratio (A/B) is 0.00 Example, compare containing (B) ammonium ion, the comparative example that mol ratio (B/A) is more than 1.85, shorten and (embodiment 8-1~8-8 and compare Example 8-1~8-2, embodiment 8-9~8-16 and comparative example 8-3~8-4, embodiment 8-17~8-24 and comparative example 8-5~8-6, Embodiment 8-25~8-32 and comparative example 8-7~8-8).

In addition, in the case that the content of (A2) organic basic compound is equal, mol ratio (B/A) is 0.04~1.67 reality Apply in example, confirm effect height (embodiment 8-2~8-7, embodiment 8-10~8-15, embodiment 8-18 that processing time shortens ~8-23, embodiment 8-26~8-31).

[table 10]

Table 10 is that (A2) organic basic compound is TMAH, and (A1) inorganic alkaline compound is potassium carbonate (carbonic acid K, alkali gold Belong to carbonate), TMAH：Carbonic acid K mass ratio is 2：1 example.(A) in the case that the content of alkali compounds is equal, alkalescence The processing time for the embodiment that the aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and less than 1.85 and alkalescence are water-soluble Liquid is more than 1.85 without (B) ammonium ion, the comparative example that mol ratio (A/B) is 0.00, containing (B) ammonium ion, mol ratio (B/A) Comparative example compare, shorten (embodiment 9-1~9-8 and comparative example 9-1~9-2, embodiment 9-9~9-16 and comparative example 9-3~ 9-4, embodiment 9-17~9-24 and comparative example 9-5~9-6, embodiment 9-25~9-32 and comparative example 9-7~9-8).

In addition, in the case that the content of (A) alkali compounds is equal, mol ratio (B/A) is 0.04~1.67 embodiment In, confirm effect height (embodiment 9-2~9-7, embodiment 9-10~9-15, embodiment 9-18~9- that processing time shortens 23rd, embodiment 9-26~9-31).

[table 11]

Table 11 is that (A2) organic basic compound is choline, (A1) inorganic alkaline compound be sodium hydroxide (hydroxide Na, Alkali metal hydroxide salt), choline：Hydroxide Na mass ratio is 2：1 example.(A) content of alkali compounds is equal In the case of, when alkaline aqueous solution contains (B) ammonium ion, mol ratio (B/A) more than 0.00 and is less than the processing of 1.85 embodiment Between with alkaline aqueous solution without (B) ammonium ion, mol ratio (A/B) be 0.00 comparative example, contain (B) ammonium ion, mol ratio (B/ A) compared for more than 1.85 comparative example, shorten (embodiment 10-1~10-8 and comparative example 10-1~10-2, embodiment 10-9~ 10-16 and comparative example 10-3~10-4, embodiment 10-17~10-24 and comparative example 10-5~10-6, embodiment 10-25~10- 32 and comparative example 10-7~10-8).

In addition, in the case that the content of (A) alkali compounds is equal, mol ratio (B/A) is 0.04~1.67 embodiment In, confirm effect height (embodiment 10-2~10-7, embodiment 10-10~10-15, embodiment 10-18 that processing time shortens ~10-23, embodiment 10-26~10-31).

Industrial applicability

The forming method of the solder resist pattern of the present invention is applied to for example possess face-down bonding for the part in wiring Connect the purposes of the formation of the circuit substrate progress solder resist pattern of pad.

Symbol description

1 insulating barrier

2 conducting wirings

3 solder mask layers

4 photomasks

5 activation light

6 connection pads

Claims (18)

1. a kind of forming method of solder resist pattern, it is the formation side of the solder resist pattern including at least following steps in order Method：At least there is the step of forming solder mask layer in the circuit substrate of connection pad, and by uncured solder mask layer film Change until the thickness of solder mask layer is the filming step below the thickness of connection pad, it is characterised in that in filming step The middle alkaline aqueous solution used includes (A) alkali compounds and (B) ammonium ion, and (B) ammonium ion is relative to (A) alkali compounds Mol ratio (B/A) is more than 0.00 and less than 1.85.

2. the forming method of the solder resist pattern described in claim 1, wherein, (A) alkali compounds in alkaline aqueous solution Content is 5~20 mass %.

3. the forming method of the solder resist pattern described in claim 1 or 2, wherein, (A) alkali compounds is (A1) inorganic alkaline Compound.

4. the forming method of the solder resist pattern described in claim 3, wherein, (A1) inorganic alkaline compound is to be selected from alkali metal At least one kind of inorganic alkaline compound in carbonate, alkali metal phosphate, alkali metal hydroxide and alkali silicate.

5. the forming method of the solder resist pattern described in claim 4, wherein, (A1) inorganic alkaline compound is alkali metal silicate Salt, (B) ammonium ion are 0.04~0.71 relative to the mol ratio (B/A) of (A) alkali compounds.

6. the forming method of the solder resist pattern described in claim 4, wherein, (A1) inorganic alkaline compound is alkali metal carbonic acid Salt, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

7. the forming method of the solder resist pattern described in claim 4, wherein, (A1) inorganic alkaline compound is alkali metal hydrogen-oxygen Compound, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

8. the forming method of the solder resist pattern described in claim 4, wherein, (A1) inorganic alkaline compound is alkali metal silicate Salt and alkali carbonate, (B) ammonium ion are 0.04~0.45 relative to the mol ratio (B/A) of (A) alkali compounds.

9. the forming method of the solder resist pattern described in claim 4, wherein, (A1) inorganic alkaline compound is alkali metal hydrogen-oxygen Compound and alkali carbonate, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

10. the forming method of the solder resist pattern described in claim 4, wherein, (A1) inorganic alkaline compound is alkali metal phosphorus Hydrochlorate, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

11. the forming method of the solder resist pattern described in claim 1 or 2, wherein, (A) alkali compounds is (A2) organic base Property compound.

12. the forming method of the solder resist pattern described in claim 11, wherein, (A2) organic basic compound is to be selected from tetramethyl At least one kind of organic basic compound in base ammonium hydroxide and trimethyl -2- hydroxyethylammonium hydroxides.

13. the forming method of the solder resist pattern described in claim 12, wherein, (A2) organic basic compound is tetramethyl hydrogen Amine-oxides, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

14. the forming method of the solder resist pattern described in claim 12, wherein, (A2) organic basic compound be trimethyl- 2- hydroxyethylammonium hydroxides, (B) ammonium ion are 0.04~1.67 relative to the mol ratio (B/A) of (A) alkali compounds.

15. the forming method of the solder resist pattern described in claim 1 or 2, wherein, (A) alkali compounds is (A1) inorganic base Property compound and (A2) organic basic compound.

16. the forming method of the solder resist pattern described in claim 15, wherein, (A1) inorganic alkaline compound is selected from alkali gold Belong at least one kind of inorganic alkaline compound in carbonate and alkali metal hydroxide, (A2) organic basic compound be selected from At least one kind of organic basic compound in TMAH and trimethyl -2- hydroxyethylammonium hydroxides.

17. the forming method of the solder resist pattern described in claim 16, wherein, (A1) inorganic alkaline compound is alkali metal carbon Hydrochlorate, (A2) organic basic compound are TMAH, (B) ammonium ion relative to (A) alkali compounds mol ratio (B/A) it is 0.04~1.67.

18. the forming method of the solder resist pattern described in claim 16, wherein, (A1) inorganic alkaline compound is alkali metal hydrogen Oxide, (A2) organic basic compound are trimethyl -2- hydroxyethylammonium hydroxides, and (B) ammonium ion is relative to (A) alkalization The mol ratio (B/A) of compound is 0.04~1.67.