CN101278235A - Photosensitive resin composition, photosensitive element, and method for manufacturing printed wiring board - Google Patents

Abstract

Disclosed is a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having a polymerizable ethylenically unsaturated group, and (C) a photopolymerization initiator. The component (B) of this photosensitive resin composition contains a specific bisphenol A (meth)acrylate compound, a specific alkoxylated trimethylolpropane tri(meth)acrylate compound, and a specific nonylphenyl polyalkyleneglycol (meth)acrylate compound. Also disclosed are a photosensitive element using such a photosensitive resin composition and a method for manufacturing a printed wiring board.

Description

The manufacture method of photosensitive polymer combination, photosensitive element and printed circuit board (PCB)

Technical field

The present invention relates to the manufacture method of photosensitive polymer combination, photosensitive element and printed circuit board (PCB).

Background technology

In the past, in the manufacturing field of printed circuit board (PCB), be purpose with the attenuating of circuit protection and contact resistance etc., in the enterprising row metal plating of circuit processing.In addition, along with popularizing of portable e-machine, the form of employed installing component increases rapidly to comparatively favourable chip size packages of miniaturization (CSP) or BGA Package (BGA).This installing component, in comprehensive formation surface resin layer (soldering-resistance layer) except printed board circuit conductor that pad (bond pads) etc. is installed, wait the processing of enforcement metal-plated in pad (pad) part, by being carried out the pad and the solder ball (solder ball) of plating processing, be connected with distributing board.In metal-plated processing,, use gold-plated in most situations for guaranteeing the good metal combination.

And the gold-plated method in above-mentioned field is from the electroplating method electroless plating method that swerves.This is based on the progress of the small-sized high densityization of printed circuit board (PCB), does not need electrode just can obtain the coating film thickness of homogeneous and smooth surface etc. with lead-in wire, and carrying e-machine to the transfer of electroless plating has in substrate particularly remarkable.

But, portable phone of enlarging rapidly of market etc. carries the employed substrate of e-machine in recent years, cause bending according to drop impact or by the pressure of enter key, cause installing components such as CSP or BGA take place from problems such as substrate surface come off easily, one of them reason, be considered to the printed circuit board (PCB) that is obtained by electroless plating method and compare with the printed circuit board (PCB) that is obtained by electroplating method, the tin ball connects fiduciary level to be reduced.Be head it off, proposed not implement electroless plating, and the part beyond it implemented the method (patent documentation 1) of electroless plating in the part (copper circuit) of carrying installing component.

In addition, not only have excellent sharpness in order to provide, connecting airtight property, photo sensitivity and plating patience, and can fully lower the photosensitive polymer combination of the pollution of plating solution, following photosensitive polymer combination is disclosed: contain the optical polymerism compound, Photoepolymerizationinitiater initiater, the colorant that have at least 1 polymerisable ethene unsaturated link in binder polymer, the molecule, and the total light transmittance under its uncured state is (for example with reference to a patent documentation 2) more than 60%.

Patent documentation 1: the international pamphlet that discloses No. 98/04407

Patent documentation 2: TOHKEMY 2004-12812 communique

Summary of the invention

The problem that invention will solve

Can under higher fiduciary level, carry out the printed circuit board (PCB) of the mounted on surface of electronic units such as CSP or BGA, think and upward form on the multilayer board of surface resin layer (soldering-resistance layer) with predetermined pattern by formed substrate (being formed with the substrate of circuit pattern) at circuit, the layer (corrosion-resisting pattern) of the solidfied material of photosensitive polymer combination is formed the mode that circuit pattern exposes to the open air, after carrying out electroless plating on the circuit pattern, remove this solidfied material layer (corrosion-resisting pattern), just can make.

But solidfied material layer (corrosion-resisting pattern) was also insufficient from the fissility of surface resin layer behind electroless plating in the past, and the part of solidfied material layer is not peeled off and remained on the surface resin layer, causes the residual problem of resist.

Therefore, the purpose of this invention is to provide a kind of in order to have formed and to form solidfied material layer (corrosion-resisting pattern) on the surface resin layer on the substrate and when using, can obtain the photosensitive polymer combination of sufficient fissility being formed at circuit.In addition, the purpose of this invention is to provide a kind of manufacture method of using the photosensitive element of this photosensitive polymer combination and using their printed circuit board (PCB).

The technical scheme of dealing with problems

The invention provides a kind of photosensitive polymer combination, it contains (A) binder polymer, (B) and has the optical polymerism compound of polymerisable ethene unsaturated group and (C) Photoepolymerizationinitiater initiater, wherein, (B) composition contains the poly-alkane glycol acrylate compounds of nonyl phenyl shown in triacrylic ester of alkoxylating trimethylolpropane compound shown in the system of bisphenol-A shown in the following general formula (1) (methyl) acrylate compounds, the following general formula (2) and the following general formula (3).

In the formula (1), X ¹And X ²The alkylidene of representing carbon number 2～6 independently of one another, R ¹And R ²Represent hydrogen atom or methyl independently of one another, p and q represent the positive integer of p+q=4～40; In the formula (2), X ³, X ⁴And X ⁵The alkylidene of representing carbon number 2～6 independently of one another, R ³, R ⁴And R ⁵Represent hydrogen atom or methyl independently of one another, k, m and n represent the positive integer of k+m+n=3～30; In the formula (3), X ⁶The alkylidene of expression carbon number 2～6, R ⁶Expression hydrogen atom or methyl, r represents 1～20 integer.

Photosensitive element of the present invention possesses support and the photographic layer of being located on this support that is formed by the invention described above photosensitive polymer combination.

Photosensitive polymer combination of the present invention and photosensitive element, as the optical polymerism compound and used above-mentioned specific compound, thereby formed on the surface resin layer on the substrate when using being formed at circuit, can obtain sufficient shape compliance and fissility in order to form solidfied material layer (corrosion-resisting pattern).

In photosensitive polymer combination of the present invention and photosensitive element, (C) composition is to contain 2,4, and 5-triarylimidazoles dipolymer is good.In addition, make (A) composition and (B) when the total amount of composition is 100 mass parts, (A) amount of composition is 40～80 mass parts, (B) amount of composition is 20～60 mass parts, and (C) amount of composition is good with 0.1～20 mass parts.

The photographic layer of the photosensitive element of the invention described above, better for the ultraviolet transmitance of wavelength 365nm with 5～75%.

The present invention relates to possess the manufacture method of the printed circuit board (PCB) of the following step, have circuit and form with substrate and be formed at circuit formation and formed substrate with the circuit of the circuit pattern on the substrate and formed at circuit on the face of the surface resin layer side that forms the 1st multilayer board that makes the surface resin layer that circuit pattern exposes to the open air on the substrate possessing, the 1st step of the stacked photographic layer that is shaped in advance by above-mentioned arbitrary photosensitive polymer combination; The solidfied material layer that development and formation are patterned behind the established part irradiation active ray of photographic layer, acquisition has formed the 2nd step of the 2nd multilayer board that possesses surface resin layer and solidfied material layer on the substrate in turn at circuit; Carry out electroless plating and on circuit pattern, form the 3rd step of plating layer for the 2nd multilayer board.

In this manufacture method, preferred consolidation thing layer is patterned into the part of circuit pattern is exposed to the open air, and at comprehensive formation plating layer of the exposed portion of circuit pattern.

The invention effect

Photosensitive polymer combination of the present invention and photosensitive element have formed on the surface resin layer on the substrate when using in order to form solidfied material layer (corrosion-resisting pattern) being formed at circuit, can obtain sufficient fissility.In addition, photosensitive polymer combination of the present invention and photosensitive element are being excellence aspect sharpness, connecting airtight property, plating patience and the shape compliance.

In addition, the manufacture method of printed circuit board (PCB) of the present invention, the imbedibility of photographic layer (photosensitive polymer combination layer) and the fissility of solidfied material layer (corrosion-resisting pattern) are good, and then can fully reduce the pollution of plating solution.

Description of drawings

Fig. 1 is the sectional view of an embodiment of expression photosensitive element of the present invention.

Fig. 2 is the block diagram of an embodiment of expression board, printed circuit board manufacturing method of the present invention.

Fig. 3 is the block diagram of other embodiment (to the 2nd step) of expression board, printed circuit board manufacturing method of the present invention.

Fig. 4 is the block diagram of other embodiment (the 3rd step) of expression board, printed circuit board manufacturing method of the present invention.

Fig. 5 is the vertical view of expression clathrate exposure tool (phototool) (mask pattern).

Symbol description:

1: photosensitive element, 10: support, 20: photographic layer; 22: exposure portion, 24: solidfied material layer (corrosion-resisting pattern), 30: diaphragm; 40: circuit forms uses substrate; 50,51: circuit pattern, 50a, 51a: expose portion to the open air, 55: plating layer; 55a: nickel coating; 55b: Gold plated Layer, 60: surface resin layer, 70: peristome; 80: circuit has formed substrate; 90: mask pattern, 90a: shielding portion, 90b: hyalomere; 92: active ray; 100: the 1 multilayer boards, 200: the 2 multilayer boards, 300: printed circuit board (PCB).

Embodiment

Below, described in detail with regard to appropriate embodiment of the present invention.In addition; (methyl) acrylic acid is meant acrylic acid and the methacrylic acid corresponding with it in this instructions; (methyl) acrylate is meant acrylate and the methacrylate corresponding with it, and (methyl) acryloyl group is meant acryloyl group and the methacryl corresponding with it.

As the binder polymer of (A) composition, then can unconfinedly use among the present invention if play the polymkeric substance of the bonding agent effect of photosensitive polymer combination.Particularly, for example can exemplify acrylic resin, phenylethylene resin series, epoxy base system resin, acid amides is that resin, acid amides epoxy base system resin, alkyd are that resin, phenol are resin.From the viewpoint of alkali-developable, be good with acrylic resin.These can be used alone or in combination of two or more kinds.

Binder polymer for example gives polymerizable monomer the incompatible manufacturing of radical polymerization.As above-mentioned polymerizable monomer, can give an example as styrene, vinyltoluene, α-Jia Jibenyixi etc. are at alpha-position or the nuclear substituted polymerisable styrene derivative of fragrance, acrylamides such as diacetone acrylamide, vinyl cyanide, the ester class of vinyl alcohols such as vinyl n-butyl ether, (methyl) alkyl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3-tetrafluoro propyl group (methyl) acrylate, (methyl) acrylic acid, α-bromine (methyl) acrylic acid, α-chlorine (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid monoesters such as maleic acid list isopropyl ester, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid.

Above-mentioned (methyl) alkyl acrylate is shown in for example following general formula (4).In the formula (4), R ⁷Expression hydrogen atom or methyl, R ⁸Expression can have the alkyl of substituent carbon number 1～12.As having R ⁸Substituting group, hydroxyl, epoxy radicals, halogen etc. are arranged.

As R ⁸In alkyl, for example can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and these constitutional isomer.

The concrete example aspect of (methyl) alkyl acrylate shown in the formula (4) can exemplify (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate.These can be used alone or in combination of two or more kinds.

Binder polymer from the viewpoint of alkali-developable, is good to have carboxyl.Binder polymer with carboxyl can be for example, and polymerizable monomer and other polymerizable monomer with carboxyl carry out the incompatible manufacturing of radical polymerization.

In addition, binder polymer preferably contains styrene or styrene derivative as monomeric unit from the viewpoint of resistance to chemical reagents.It is good to want as polymeric composition comprising body connecting airtight property and fissility to be styrene or styrene derivative, and binder polymer is good to contain these 2～40 quality %, and is better to contain 3～28 quality %, good to contain 5～27 quality % spies.This content does not connect airtight sexual orientation in reduction when reaching 2 quality %, and stripping film becomes big when surpassing 40 quality %, and splitting time tends to elongated.

The weight-average molecular weight of binder polymer is good with 20000～300000, and is better with 40000～150000.This weight-average molecular weight does not reach 20000 o'clock anti-developer solution sexual orientations in reduction, surpasses 300000 o'clock development times and tends to elongated.

The acid number of binder polymer is good with 30～250mgKOH/g, and is better with 50～200mgKOH/g.When this acid number does not reach 30mgKOH/g development time tend to elongated, when surpassing 250mgKOH/g through the anti-developer solution sexual orientation of the corrosion-resisting pattern of photocuring in reduction.

These binder polymers can be used alone or in combination of two or more kinds.Binder polymer combined aspects in combination situation of use more than 2 kinds, can exemplify the binder polymer more than 2 kinds that for example forms by the different copolymer composition, the binder polymer more than 2 kinds of different weight-average molecular weight, the binder polymer more than 2 kinds of different dispersion degree.

Be the optical polymerism compound with polymerisable ethene unsaturated group of (B) composition, contain triacrylic ester of alkoxylating trimethylolpropane compound shown in the system of bisphenol-A shown in the above-mentioned general formula (1) (methyl) acrylate compounds, the above-mentioned general formula (2), reach the poly-alkane glycol acrylate compounds of nonyl phenyl shown in the above-mentioned general formula (3).

In the formula (1), X ¹And X ²The alkylidene of representing carbon number 2～6 independently of one another, R ¹And R ²Represent hydrogen atom or methyl independently of one another, p and q represent the positive integer of p+q=4～40.X ¹Or X ²Carbon number not in 2～6 scope, or the p+q situation in 4～40 scopes not, the connecting airtight property of photographic layer is difficult to abundant acquisition, the splitting time of solidfied material layer (corrosion-resisting pattern) tends to elongated.With regard to the viewpoint of connecting airtight property and fissility, X ¹And X ²With vinyl is good, and p+q is good with 10～30.

There is bisphenol A polyethenoxy dimethylacrylate (2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-) the appropriate concrete example aspect of formula (1) compound.2, two (4-((methyl) acryloxy polyethoxy) phenyl) the propane aspects of 2-, for example have 2, two (4-((methyl) acryloxy diethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy triethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy tetraethoxy) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy five ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy six ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy seven ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy eight ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy nine ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy ten ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy 11 ethoxys) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy ten diethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy ten triethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy ten tetraethoxies) phenyl) propane of 2-, 2, two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane of 2-.2, two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-, can be by buying BPE-500 (Xin Zhong village chemical industry Co., Ltd. system on the market, trade name), 2, two (4-(the methacryloxy 15 ethoxys) phenyl) propane of 2-can be by buying BPE-1300 (Xin Zhong village chemical industry Co., Ltd. system, trade name) on the market.These can be used alone or in combination of two or more kinds.

In the formula (2), X ³, X ⁴And X ⁵The alkylidene of representing carbon number 2～6 independently of one another, R ³, R ⁴And R ⁵Represent hydrogen atom or methyl independently of one another, k, m and n represent to become the positive integer of k+m+n=3～30.X ³, X ⁴Or X ⁵Carbon number be not in 2～6 scope, or be not the situation in the scope of k+m+n=3～30, the obdurability of solidfied material layer (corrosion-resisting pattern) or fissility tend to reduce.With regard to the viewpoint that the obdurability and the fissility of solidfied material layer (corrosion-resisting pattern) all can improve, X ³, X ⁴And X ⁵The aspect is good with vinyl.In addition, being good in the scope of k+m+n=6～27, with at 9～27 scope Nei Gengjia.There is ethoxylated trimethylolpropane triacrylate the appropriate concrete example aspect of formula (2) compound.

In the formula (3), X ⁶The alkylidene of expression carbon number 2～6, R ⁶Expression hydrogen atom or methyl, r represents 1～20 integer.X ⁶Carbon number be not in 2～6 scope, or r is not the situation in 1～20 scope, it is residual that peeling off of solidfied material layer (corrosion-resisting pattern) produced, or splitting time tends to elongated.With regard to the residual viewpoint that all can improve with fissility of peeling off of solidfied material layer (corrosion-resisting pattern), X ⁶The aspect is good with vinyl.In addition, r to be being good in 2～16 scope, with at 4～12 scope Nei Gengjia.There is nonyl phenyl polyethylene glycol acrylate the appropriate concrete example aspect of formula (3) compound.

(B) composition can and then contain above-mentioned optical polymerism compound in addition.Other optical polymerism compound aspect, can enumerate polyol reaction α, beta-unsaturated carboxylic acid and compound, to containing the glycidyl compound reaction alpha, beta-unsaturated carboxylic acid and compound, γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester, beta-hydroxy ethyl-β '-(methyl) acryloxy ethyl-phthalic ester, (methyl) alkyl acrylate etc.

(C) the Photoepolymerizationinitiater initiater aspect of composition, can exemplify for example benzophenone, N, N '-tetramethyl-4,4 '-diaminobenzophenone (michler's ketone), N, N '-tetraethyl-4,4 '-diaminobenzophenone, 4-methoxyl-4 '-dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-aromatic ketone such as 2-morpholino-acetone-1 grade, the 2-EAQ, phenanthrenequione, 2-tert-butyl group anthraquinone, the prestox anthraquinone, 1,2-benzo anthraquinone, 2,3-benzo anthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, the 1-chloroanthraquinone, 2-methylanthraquinone, 1, the 4-naphthoquinones, 9, the 10-phenanthrenequione, the 2-methyl isophthalic acid, the 4-naphthoquinones, 2, quinones such as 3-dimethyl anthraquinone, the benzoin methyl ether, the benzoin ethylether, benzoin ether compounds such as benzoin phenyl ether, benzoin, the methylbenzene accidental cause, benzoin compounds such as ethylbenzene accidental cause, benzil derivants such as dibenzoyl dimethyl acetal, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4,5-two (methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc. 2,4,5-triarylimidazoles dipolymer, the 9-phenylacridine, 1, acridine derivatives such as two (9, the 9 '-acridine) heptane of 7-, N-phenylglycine, the N-phenylglycine derivant, coumarin series compounds.And for example the combination of diethyl thioxanthone and dimethylaminobenzoic acid is such, and the combination of thioxanthones based compound and tertiary amine compound also can.These can be used alone or in combination of two or more kinds.

(C) with 2,4,5-triarylimidazoles dipolymer spy is good in these for composition.2,4,5-triarylimidazoles dipolymer is, two 2,4, the identical symmetrical compound of the substituting group of the aryl of 5-triarylimidazoles also can, the different asymmetric compound of substituting group also can.

The amount of binder polymer, (A) composition and (B) total of composition measure in 100 mass parts, be good with 40～80 mass parts, better with 45～70 mass parts.This use level is easy to become fragile at 40 mass parts time of less than solidfied material, films sexual orientation in reduction in the situation of using as photosensitive element, and photo sensitivity tends to reduce when surpassing 80 mass parts.

(B) amount of the optical polymerism compound of composition, (A) composition and (B) total of composition measure in 100 mass parts, be good with 20～60 mass parts, better with 30～55 mass parts.Photo sensitivity tends to reduce during these quantity not sufficient 20 mass parts, surpasses 60 mass parts time solidfied materials and tends to become fragile.

(B) in the total amount of composition, bisphenol-A shown in the general formula (1) is the ratio that contains of (methyl) acrylate compounds, is good with 10 quality %～50 quality %, and is better with 15 quality %～40 quality %.When not reaching 10 quality %, have the tendency that the residual inhibition effect of peeling off of solidfied material layer (corrosion-resisting pattern) diminishes, then have photographic layer to connect airtight when surpassing 50 quality % and the tendency that plating slips into (め つ I も ぐ り) takes place due to the deficiency.

(B) in the total amount of composition, the acrylate compounds of oxyalkylated trihydroxy methyl-propane three (methyl) shown in the general formula (2) contain ratio, be good with 20 quality %～80 quality %, better with 25 quality %～75 quality %, good with 30 quality %～65 quality % spies.Have photographic layer and connect airtight the tendency that plating slips into takes place due to the deficiency when not reaching 20 quality %, it is residual to produce peeling off of solidfied material layer (corrosion-resisting pattern) when surpassing 80 quality %, or solidfied material layer (corrosion-resisting pattern) tends to become fragile.

(B) in the total amount of composition, nonyl phenyl shown in the general formula (3) gathers the ratio that contains of alkane glycol (methyl) acrylate compounds, is good with 10 quality %～40 quality %, and is better with 15 quality %～30 quality %.Do not reach the tendency that 10 quality % have the fissility deterioration of solidfied material layer (corrosion-resisting pattern), when surpassing 40 quality %, having the not enough tendency of connecting airtight of photographic layer.

(C) amount of the Photoepolymerizationinitiater initiater of composition, with respect to (A) composition and (B) total of composition measure 100 mass parts, be good with 0.1～20 mass parts, better with 0.2～10 mass parts, good with 2～5 mass parts spies.This amount photo sensitivity when not reaching 0.1 mass parts tends to reduce, and can the absorption on the photographic layer surface increase when exposure when surpassing 20 mass parts, has interior lights to solidify the inadequate tendency that becomes easily.

Photosensitive polymer combination, except as above-mentioned composition, can contain dyestuff, tribromo phenylsulfone, leuco crystal violet plastifier, pigment, filling agent, defoamer, fire retardant, stabilizing agents such as light colour coupler, solar heat protection colour coupler, para toluene sulfonamide such as (leuco crystal violet) such as peacock green, give the agent of connecting airtight property, levelling agent, peel off promoter, antioxidant, spices, preparation, thermal cross-linking agent etc. as required.The amount of these compositions, with respect to (A) composition and (B) total of composition measure 100 mass parts with separately about 0.01～20 mass parts for good.These can be used alone or in combination of two or more kinds.

Photosensitive polymer combination of the present invention, can be as required, be dissolved in methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, in dinethylformamide, propylene glycol monomethyl ether equal solvent or these the mixed solvent, with solid suitable use of solution state that forms about part 30～60 quality %.

The solution of this photosensitive polymer combination for example is coated on the metal covering, and is dry to form photographic layer, is covered diaphragm as required and is used in the formation of solidfied material layer (corrosion-resisting pattern).This moment is as metal, there is no particular restriction, can exemplify iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, and just with the viewpoint of the connecting airtight property of solidfied material layer (corrosion-resisting pattern) and electron conduction and Yan Yitong, copper series alloy, iron-based alloy are good.

Perhaps, photosensitive polymer combination of the present invention, state that can photosensitive element is suitable to be used.Fig. 1 is the diagrammatic cross-section of an appropriate embodiment of expression photosensitive element of the present invention.Photosensitive element 1 shown in Figure 1 comprises support 10, is arranged at photographic layer 20 on the support 10, is arranged at the diaphragm 30 on the photographic layer 20.

Photographic layer 20 is that the photosensitive polymer combination by the invention described above forms.The thickness of photographic layer 20 is different because of purposes, but is good with 1～100 μ m, and is better with 1～50 μ m.This thickness in the industrial coating processing difficulties of tending to, can not make effect of the present invention reduce when surpassing 100 μ m when reaching 1 μ m, and bonding force, sharpness are tended to reduce.

Photographic layer 20 is good for the ultraviolet transmitance of wavelength 365nm with 5～75%, and is with 7～60% better, special good with 10～40%.This transmitance does not reach at 5% o'clock and connects airtight sexual orientation in reduction, surpasses 75% o'clock sharpness and tends to reduce.This transmitance can be measured with the UV spectrometer.Aspect the UV spectrometer, can exemplify the system 228A of Hitachi Ltd. type W beam spectrophotometer etc.

Photographic layer 20 preferred solution by the above-mentioned photosensitive polymer combination of modulation, this solution of coating forms on support 10.Coating can be undertaken by for example known method such as roll-coater, funny point type coating machine, intaglio printing coating machine, Kohler coater, extrusion coater (die coater), excellent coating machine.In addition, drying can be carried out about 5～30 minutes at 70～150 ℃.

Support 10 is good with thickness 5～25 μ m, and is better with 8～20 μ m, good with 10～16 μ m spies.Easily tend to break when peeling off support when this thickness does not reach 5 μ m before development, sharpness is tended to reduce when surpassing 25 μ m.

The mist degree of support 10 is good with 0.001～5.0, and is with 0.001～2.0 better, special good with 0.01～1.8.This mist degree surpasses at 2.0 o'clock, and sharpness is tended to reduce.Mist degree is that accurate mensuration according to JIS K 7105 obtains, and can use NDH-1001DP commercially available mensuration such as nephelometer such as (Japanese electric look Industrial Co., Ltd system, trade names).

Aspect support 10 and diaphragm 30, suitable use polymer films such as polyethylene terephthalate, polypropylene, tygon, polyester because aspect thermotolerance and solvent resistance excellence.

Diaphragm 30 is good with thickness 5～30 μ m, and is better with 10～28 μ m, good with 15～25 μ m spies.When this thickness does not reach 5 μ m when lamination diaphragm 30 tend to easily break, it is poor to tend to cheapness when surpassing 30 μ m.

The pulling strengrth of diaphragm 30 length directions is to be good more than the 13MPa, and is better with 13～100MPa, better with 14～100MPa, and then better with 15～100MPa, and then with 16～100MPa the best.When this pulling strengrth did not reach 13MPa, diaphragm 30 tended to easily break when lamination.

The pulling strengrth of the Width of diaphragm 30 is to be good more than the 9MPa, and is better with 9～100MPa, better with 10～100MPa, and then better with 11～100MPa, and then with 12～100MPa the best.When this pulling strengrth does not reach 9MPa when lamination diaphragm 30 tend to easily break.

Above-mentioned pulling strengrth can accurately be measured according to JIS C 2318-1997 (5.3.3), can the grand commercially available mensuration such as instron such as (TENSILON) of Japan Powerleader temperature (Baldwin) Co., Ltd. system trade name sky happiness.

Support 10 and diaphragm 30 must be removed from photographic layer 20 in subsequent handling, so can not implement the surface treatment that can not remove, can handle as required but there is no particular restriction.Support 10 and diaphragm 30 can be implemented electrostatic prevention as required and handle.

Photosensitive element of the present invention is not limited to above-mentioned embodiment, except photographic layer, support and diaphragm, also can have middle layer or protective seams such as cushion, adhesive linkage, light absorbing zone, gas barrier layer.

Photosensitive element 1 for example can directly or be wound into volume core cylindraceous at the further stacked guard film 30 of other face of photographic layer 20 and preserve.

An embodiment of the manufacture method of the printed circuit board (PCB) that uses photosensitive polymer combination of the present invention then, is described.In the manufacture method of the printed circuit board (PCB) of present embodiment, circuit has formed substrate and has been meant the person that is contained in the printed circuit board (PCB), has circuit and forms with substrate and circuit pattern (circuit lead).Circuit has formed substrate, also can have through hole etc., in addition, also can have multi-ply construction.

Use resist in the present embodiment.Resist is to form in order selectively to carry out etching, solder or film, and covers or protect the lining material of the specific region of printed circuit board (PCB), plays the effect of plating diaphragm.Typically use photoresist, utilize its photonasty, the zone of fine and correct pattern in regulation formed with the high precision lining, protect protected object.In the manufacture method of printed circuit board (PCB) of the present invention, resist can be divided into 2 kinds according to purpose.

Wherein a kind of is soldering-resistance layer (surface resin layer), for example is coated with the zone that only makes by solder formation bonding part to expose to the open air, exposes, and forms lining (protection) pattern with expectation.Also be that soldering-resistance layer (surface resin layer) forms, make the circuit of removing circuit pattern form comprehensive lining of substrate.

Another then is the resistance plated film.The resistance plated film is to use the stacked photographic layer of photosensitive element, exposes, and forms to have the solidfied material layer (corrosion-resisting pattern) that only makes lining (protection) pattern that the zone of carrying out electroless plating exposes to the open air.Also promptly, this solidfied material layer (corrosion-resisting pattern) is formed, and welding disk is installed is graded and do not expect to adhere to the mode that comprehensively is covered that the circuit of metal due to the plating has formed substrate.

Below use accompanying drawing to be described in more detail present embodiment.Fig. 2 is the block diagram of an embodiment of expression board, printed circuit board manufacturing method of the present invention.In embodiment shown in Figure 2, at first preparing the 1st multilayer board 100, the 1 multilayer boards 100 has the circuit that has formed circuit pattern 50 on circuit forms with substrate 40 and has formed substrate 80, and has been formed at circuit and formed surface resin layer (soldering-resistance layer) 60 (Fig. 2 (a)) on the substrate 80.Be formed with the peristome 70 that the 50a of the portion that exposes to the open air of circuit pattern 50 exposes on the surface resin layer 60.Then, on the face of surface resin layer 60 sides of the 1st multilayer board 100, photosensitive element 1 is laminated into the mode ((Fig. 2 (b)) that photographic layer 20 and surface resin layer 60 are connected airtight.

Then, for having formed photographic layer stacked on the substrate 80 20, make active ray 92 shine into image shape (Fig. 2 (c)) by mask pattern 90 at circuit.Mask pattern 90 has shielding portion 90a that covers active ray 92 and the hyalomere 90b that sees through active ray 92.Thus, make a part (the exposure portion 22) exposure of photographic layer 20, form the solidfied material of photosensitive polymer combination.After the exposure, support 10 and unexposed portion removed developed, form the solidfied material layer (corrosion-resisting pattern) 24 (Fig. 2 (d)) that is patterned.So, obtain to have formed the 2nd multilayer board 200 that possesses surface resin layer 60 and solidfied material layer (corrosion-resisting pattern) 24 on the substrate 80 in turn at circuit.Solidfied material layer (corrosion-resisting pattern) 24 is the mode that exposes to the open air with the 50a of the portion that exposes to the open air of circuit pattern 50, forms with the purpose of resistance plated film.This solidfied material layer (corrosion-resisting pattern) 24 can at random carry out the back thereafter and solidify.

Surface resin layer 60 and solidfied material layer (corrosion-resisting pattern) 24 as mask, are carried out the Ni electroless plating for the 2nd multilayer board 200, on circuit pattern 50, form plating layer 55 (Fig. 2 (e)).Then, hang oneself the 2nd multilayer board 200 of electroless plating is removed solidfied material layer 24 and is obtained printed circuit board (PCB) 300 (Fig. 2 (f)).

Fig. 3 and Fig. 4 are the block diagram of other embodiment of manufacture method of expression printed circuit board (PCB) of the present invention, and Fig. 3 is the block diagram of expression to its 2nd step, and Fig. 4 is the block diagram of its 3rd step of expression.In the 1st step shown in Figure 3, at first prepare, have the circuit that on circuit forms with substrate 40, has formed circuit pattern 50 and 51 and formed substrate 80, and be formed at the 1st multilayer board 100 (Fig. 3 (a)) that circuit has formed the surface resin layer 60 on the substrate 80.In surface resin layer 60, be formed with the 50a of the portion that exposes to the open air of circuit pattern 50 and 51 and the peristome 70 that 51a exposes to the open air.Then, on the face of surface resin layer 60 sides of the 1st multilayer board 100, make photosensitive element 1 be laminated into the mode ((Fig. 3 (b)) that photographic layer 20 and surface resin layer 60 are connected airtight.

In the 2nd step, formed photographic layer 20 on the substrate 80 for being layered in circuit, make active ray 92 shine into image shape (Fig. 3 (c)) by mask pattern 90.Mask pattern 90 have the shielding portion 90a that covers active ray 92, with the hyalomere 90b that sees through active ray 92.Thus, make a part (the exposure portion 22) exposure of photographic layer 20, form the solidfied material of photosensitive polymer combination.After the exposure, support 10 and unexposed portion removed developed, form the solidfied material layer (corrosion-resisting pattern) 24 (Fig. 3 (d)) that is patterned.So, can obtain to have formed the 2nd multilayer board 200 that possesses surface resin layer 60 and solidfied material layer (corrosion-resisting pattern) 24 on the substrate 80 in turn at circuit.Solidfied material layer (corrosion-resisting pattern) 24 plays that the circuit pattern 50 that carries out electroless plating is exposed to the open air, and lining and be not suitable for adhering to the effect of the resistance plated film in the zones such as circuit pattern 51 of metal due to the plating.This solidfied material layer (corrosion-resisting pattern) 24 can at random carry out the back thereafter and solidify.

In the 3rd step shown in Figure 4, surface resin layer 60 and solidfied material layer (corrosion-resisting pattern) 24 as mask, are carried out the Ni electroless plating for the 2nd multilayer board 200, form nickel coating 55a (Fig. 4 (e)) on maskless circuit pattern 50 surfaces.Then, replace gold-platedly, on nickel coating, form Gold plated Layer 55b (Fig. 4 (f)).So, only, peel off solidfied material layer (corrosion-resisting pattern) 24, obtain the printed circuit board (PCB) 300 (Fig. 4 (g)) of the reliability excellence of installing component in the processing of will partly implement metal-plated.

Fig. 2 and the 1st multilayer board 100 shown in Figure 3, for example make as follows: on circuit forms with substrate 40, photosensitive element 1 is laminated into the mode that this photographic layer 20 and circuit formation are connected airtight with substrate 40, by method, form the step of patterned surface resin layer 60 to develop behind the image shape irradiation active ray; Surface resin layer 60 is carried out the step that etching or plating form circuit pattern 50 as mask.

In above-mentioned the 1st step, after diaphragm 30 is removed,, make photosensitive element 1 stacked by photographic layer 20 limit heating edge are crimped onto on the surface resin layer 60.At this moment, with regard to the viewpoint of connecting airtight property and compliance with under reduced pressure stacked for good.More specifically speech when stacked so that photographic layer 20 is heated to 70～130 ℃ for good, crimping pressure with 0.1～1.0MPa about (1～10kgf/cm ²About) be good.If photographic layer 20 is heated to 70～130 ℃ in this way, in advance circuit has not been formed necessity that basal plate preheating is handled though have, improve more for making stackability, also can carry out the thermal pretreatment that circuit has formed substrate.

Aspect the light source of active ray 92, can use known light source, for example carbon arc lamp, mercury vapor arc lamp, high-pressure mercury-vapor lamp, xenon lamp etc. can be launched the light source of ultraviolet ray, visible light etc. effectively.Mask pattern 90 is minus or the eurymeric mask patterns that are called as former figure.

Development after the exposure can be carried out wet developing, dry process development etc. corresponding to the developer solution of photosensitive polymer combination by alkaline aqueous solution, water system developer solution, organic solvent etc., and unexposed portion is removed.The mode of developing then has impregnation method, alr mode, spray pattern, hairbrush, beating etc., and high pressure spray pattern most preferably, because sharpness is improved.

The developer solution aspect with regard to safety, stable, viewpoint that operability is good, is good to use alkaline aqueous solution etc.The alkali aspect of alkaline aqueous solution, can use for example alkali hydroxide metals such as oxyhydroxide of lithium, sodium or potassium, carbonic acid alkaline metal such as the carbonate of lithium, sodium, potassium or ammonium or supercarbonate, alkali metal phosphates such as potassium phosphate, sodium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate etc.Visualization way then has impregnation method, alr mode, spray pattern, hairbrush, beating etc., and high pressure spray pattern most preferably, because sharpness is improved.

Alkaline aqueous solution more specifically, is good with the thin solution of 0.1～5 quality % sodium carbonate, the thin solution of 0.1～5 quality % sal tartari, the thin solution of 0.1～5 quality % NaOH, the thin solution of 0.1～5 quality % sodium tetraborate etc.In addition, the pH of alkaline aqueous solution is good with 9～11 scope, and its temperature can be adjusted to the development that conforms with photographic layer.

In alkaline aqueous solution, can sneak into surfactant, defoamer, be used to promote a small amount of organic solvent that develops etc.Aspect the employed alkaloid substance of this situation, except described material, can exemplify borax or sodium metasilicate, tetramethyl ammonium hydroxide, monoethanolamine, ethylenediamine, Diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propane diol, 1,3-diamino-propanol-2, morpholine etc.The pH of developer solution is preferably in the sufficient scope of the development that can make resist and reduces as far as possible, is good with pH8～12, and is better with pH9～10.

Above-mentioned organic solvent aspect can exemplify for example tri acetylacetonate alcohol, acetone, ethyl acetate, the alkoxyethanol with alkoxy of carbon number 1～4, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether.These can be used alone or in combination of two or more kinds.The concentration of organic solvent is good with 2～90 quality % usually, and this temperature can be adjusted to and conforms with development.In addition, in sneaking into the water system developer solution of organic solvent, also can add surfactant, defoamer etc. on a small quantity.

Separately the organic solvent that uses is the developer solution aspect, for example can exemplify 1,1,1-trichloroethanes, N-Methyl pyrrolidone, N, dinethylformamide, cyclohexanone, methyl isobutyl ketone, gamma-butyrolacton.These organic solvents for preventing to catch fire, are good to add water in the scope of 1～20 quality %.In addition, can be as required also with the developing method more than 2 kinds.

Processing aspect after the development can be passed through about 60～250 ℃ heating or 0.2～10mJ/cm as required ²About exposure solidfied material layer (corrosion-resisting pattern) is further solidified.

Then there is electroless nickel plating the electroless plating aspect.On electroless nickel plating, can carry out the metal-plated of gold, silver, palladium, platinum, rhodium, copper, tin etc.

The removing of solidfied material layer (corrosion-resisting pattern) behind the electroless plating for example, undertaken by using to peel off than the stronger aqueous solution of alkaline aqueous solution alkalescence that is used to develop.Aspect strong alkaline aqueous solution, can use for example 1～10 quality % sodium hydrate aqueous solution, 1～10 quality % potassium hydroxide aqueous solution etc.Peel off the mode aspect, can exemplify impregnation method, spray pattern etc.

Embodiment

Below, exemplify embodiment and specified with regard to the present invention.But the present invention is defined in these embodiment.

Embodiment 1～8 and comparative example 1～4

(synthesizing of binder polymer 1)

Methacrylic acid, methyl methacrylate and styrene with 28: 60: 12 ratio copolymerization of mass ratio, are obtained the multipolymer (binder polymer 1) of weight-average molecular weight 60000,124 ℃ of glass temperatures, acid number 68mgKOH/g.This binder polymer 1 is dissolved into non-volatile composition (Gu forming part) in methyl cellosolve/toluene (6: 4, mass ratio) be 50 quality %, obtains the solution of binder polymer 1.

(synthesizing of binder polymer 2)

With methacrylic acid 130g, methyl methacrylate 170g, ethyl acrylate 100g and styrene 100g, 3.0g mixes with azoisobutyronitrile as comonomer, modulates solution α.In the flask that possesses stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, add the complex 500g of 3: 2 methyl cellosolve of mass ratio and toluene, the limit is blown into the nitrogen limit and stirs, and is heated to 85 ℃.Therein after dripping solution α in 4 hours, stir at 85 ℃ and to carry out insulation in 2 hours simultaneously.

And then, will in the complex 150g of 3: 2 methyl cellosolve of mass ratio and toluene, dissolve the solution of azoisobutyronitrile 0.5g, be added drop-wise in the flask through 10 minutes., cool off after 5 hours 85 ℃ of insulations while stirring for the solution after dripping, obtain the solution of binder polymer 2.The non-volatile composition of the solution of binder polymer 2 (Gu forming part) is 50.0 quality %, and the weight-average molecular weight of binder polymer 2 is 100000.

In addition, weight-average molecular weight is to measure by gel permeation chromatography (GPC) method, uses the calibration curve conversion of polystyrene standard to derive.The condition determination of GPC as shown below.

(GPC condition determination)

Pump: the L-6000 of Hitachi type [Hitachi Ltd.'s system]

Post: GelpackGL-R420+GelpackGL-R430+GelpackGL-R440 (amounting to 3) (being Hitachi Chemical Co., Ltd.'s system, trade name)

Eluent: tetrahydrofuran

Measure temperature: room temperature

Flow: 2.05mL/ branch

Detecting device: the L-3300 of Hitachi type RI[Hitachi Ltd. system]

The mixing ratio of table 1 and table 2 expression (A) composition, (B) composition, (C) composition and other interpolation composition.Shown in table 1 and table 2, mix (A) composition and other adjuvant composition, dissolving (B) composition reaches (C) composition in this potpourri, obtains the solution of photosensitive polymer combination.

(table 1)

(table 2]

1: as the solid quality that forms part

2: the bisphenol A polyethenoxy dimethylacrylate: Xin Zhong village chemical industry Co., Ltd. system trade name (in the compound of general formula (1), R ¹Be methyl, X ¹And X ²Be ethylidene, the mean value of p+q is about 10)

3: the bisphenol A polyethenoxy dimethylacrylate: Xin Zhong village chemical industry Co., Ltd. system trade name (in the compound of general formula (1), R ¹Be methyl, X ¹And X ²Be ethylidene, the mean value of p+q is about 30)

4: ethoxylated trimethylolpropane triacrylate: Nippon Kayaku K. K's goods name (in the compound of general formula (2), R ³, R ⁴And R ⁵Be hydrogen atom, X ³, X ⁴And X ⁵Be ethylidene, the mean value of k+m+n is about 9)

5: nonyl phenyl polyethylene glycol acrylate: Toagosei Co., Ltd's goods name (in the compound of general formula (3), R ⁶Be hydrogen atom, X ⁶Be ethylidene, the mean value of r is about 4)

6: nonyl phenyl polyethylene glycol acrylate: Xin Zhong village KCC goods name (in the compound of general formula (3), R ⁶Be hydrogen atom, X ⁶Be ethylidene, the mean value of r is about 8)

7: polypropyleneglycol diacrylate: Xin Zhong village KCC goods name: Xin Zhong village KCC goods name

8: trimethylolpropane triacrylate: Xin Zhong village KCC goods name

(making of photosensitive element)

Solution with the photosensitive polymer combination of embodiment 1～8 and comparative example 1～4; be uniformly coated on the thick polyethylene terephthalate thin film (mist degree: 1.7% of 16 μ m; trade name GS-16; Teijin Ltd's system) on; in 100 ℃ hot air convection formula dryer, after dry 10 minutes, obtain photosensitive element with the protection of tygon system diaphragm.The dried thickness of photographic layer is 50 μ m.

(circuit has formed the making of substrate)

The two sides copper-surfaced epoxy resin plywood of the vertical horizontal 20cm thickness of 12.5cm 1.6mm (Hitachi Chemical Co., Ltd.'s system, trade name: the copper foil surface of single face MCL-E-61), stay periphery 1cm, form corrosion-inhibiting coating with predetermined pattern.The Copper Foil of the part that do not covered by corrosion-inhibiting coating is given etching remove, form the circuit pattern of have metal terminal (pad) or distribution.Residual corrosion-inhibiting coating is peeled off, obtained circuit and formed substrate.The back side gives comprehensive etching, becomes the state that expose to the open air on the glass epoxy resin surface.

(formation of surface resin layer)

Formed the circuit face of substrate at the circuit of gained, with photoresist (Taiyo Ink Manufacturing Co., Ltd's system, trade name: PSR-4000), stay periphery 1cm and coating comprehensively, at 80 ℃ through 30 minutes dryings.Thereafter, see through exposure tool, (Oak makes Co., Ltd. of institute system, trade name: HMW-590), make blanket exposure except that the installation welding disk of wanting plating to use exposure machine.With unexposed portion with 1 quality % aqueous sodium carbonate (30 ℃) through 60 seconds spray developings, photoresist on the welding disk is removed, formed pattern, thereafter, by carrying out heat curing in 1 hour, formed at circuit and formed surface resin layer (soldering-resistance layer) on the substrate 150 ℃ of heating.

(formation of solidfied material layer (corrosion-resisting pattern))

Formed the two sides of substrate at the circuit that possesses surface resin layer, photographic layer (photosensitive polymer combination layer) with embodiment 1～8 and comparative example 1～4 gained photosensitive element, in pressure 0.4MPa, 110 ℃ of temperature, laminate speed 1.5m/ minute laminated, and stacked.In the stacked photographic layer, except the circuit pattern that will carry out electroless plating processing, make blanket exposure, form solidfied material layer (corrosion-resisting pattern) at 1 quality % aqueous sodium carbonate (30 ℃) through 80 seconds spray developings.

For photosensitive element that obtains as mentioned above and multilayer board, carry out evaluating characteristics in accordance with the following methods.In table 3 and its evaluation result of table 4 expression.

(anti-plating)

Will be at the multilayer board of embodiment 1～8 and comparative example 1～4 gained, in Pro Select SF (Japanese Atotech Co., Ltd. system, trade name),, carry out ungrease treatment in 50 ℃ of dippings 5 minutes.After room temperature is cleaned 1 minute with flowing water, in 30 ℃ of dippings 1 minute, carry out soft etch processes at Micro Etch SF (Japanese Atotech Co., Ltd. system, trade name)., after 1 minute flowing water cleans, in 5% sulfuric acid solution, flooded 1 minute in room temperature, carry out cleanup acid treatment in room temperature.

Thereafter, with multilayer board, electroless plating with catalyst solution Auro Tech 1000 (Japanese Atotech Co., Ltd. system, trade name) in room temperature dipping 90 seconds, give activate.After 2 minutes flowing water cleans, in Ni-P plating solution Auro Tech HP (Japanese Atotech Co., Ltd. system, trade name),, carry out electroless nickel plating in room temperature in 83 ℃ of dippings 40 minutes.

In room temperature after 2 minutes flowing water cleans, at Auro Tech CS4000 (Atotech Co., Ltd. system, Auro Teeh CS4000:150mL/L, potassium auricyanide: 1.47g/L, Auro Tech SF:1mL/L) in, in 85 ℃ the dipping 10 minutes, carry out the substituted type electroless gold plating.As aftertreatment, then wash, 85 ℃ of dryings 15 minutes.

For such multilayer board that forms plating layer, judge that according to following benchmark range estimation whether solidfied material layer (corrosion-resisting pattern) breaks and expand (especially around the welding disk), estimates anti-plating.Evaluation result is shown in table 3 and table 4.In addition, the evaluation of plating is meant that the situation of crack-free and expansion is for good.

Determinating reference

A: all crack-free and expansions comprehensively; B: some breaks and expands; C: break comprehensively and expand

(fissility)

Two sides copper-surfaced epoxy resin plywood (Hitachi Chemical Co., Ltd.'s system at the vertical horizontal 5cm thickness of 4cm 1.6mm, trade name: single face MCL-E-61), (Taiyo Ink Manufacturing Co., Ltd's system PSR-4000) was coated comprehensively, 80 ℃ of dryings 30 minutes with photoresist.

For the plywood that has been coated with above-mentioned photoresist, carry out blanket exposure through clathrate exposure tool (mask pattern) 90 shown in the 5th figure.Clathrate exposure tool (mask pattern) 90 has a plurality of shielding portion 90a that cover active ray, with the hyalomere 90b that sees through active ray.The horizontal stroke of shielding portion 90a (A of the 5th figure) is that 2.6mm, vertical (B of the 5th figure) are 0.8mm, separate 0.45mm interval (C of the 5th figure) and side by side.(Oak makes Co., Ltd. of institute system, trade name: HMW-590) to use exposure machine when exposure.

After the exposure, with unexposed portion with 1 quality % aqueous sodium carbonate (30 ℃) through 60 seconds spray developings.Then give heat curing through heating in 1 hour, on above-mentioned plywood, form surface resin layer (soldering-resistance layer) at 150 ℃.On this surface resin layer, be formed with the peristome that a part of copper of above-mentioned plywood exposes to the open air.

On the plywood two sides that possesses above-mentioned surface resin layer, with the photographic layer of embodiment 1～8 and comparative example 1～4 photosensitive element, the condition laminated at pressure 0.4MPa, 110 ℃ of temperature, laminate speed 1.5m/ minute, stacked.For stacked photographic layer, become 8.0 energy exposure with remaining lattice number after the development in Stouffer 21 rank exposure guide rules and carry out blanket exposure, form the solidfied material layer.So, obtain the evaluation plywood that the solidfied material layer covers the plywood upper and lower surface that possesses above-mentioned surface resin layer.

For this evaluation plywood, sprayed 80 seconds with 1 quality % aqueous sodium carbonate (30 ℃), carry out the plating processing with the method that above-mentioned anti-plating evaluation is same., impregnated in the 3 quality % sodium hydrate aqueous solutions of heating to 50 ℃, measure the solidfied material layer, estimate fissility from the time that the plywood that possesses above-mentioned surface resin layer is peeled off thereafter.Evaluation result is shown in table 3 and table 4.About the evaluation of fissility, the time, short more explanation was good more.

(resist is peeled off residual)

Use the above-mentioned evaluation plywood after fissility is estimated,, observe the bond area of the solidfied material layer of failing to peel off fully and adhering at the sidewall (horizontal 2.6mm indulges the high 30 μ m of 0.8mm) of surface resin layer (soldering-resistance layer) peristome.When observing bond area, use SEM (the system SE-2100 of tester Service Co., Ltd of Hitachi).Obtain sidewall area (2.6mm * 0.8mm * 30 μ m) with above-mentioned peristome divided by the value of the bond area of gained, the mean value of the value that will obtain for the above-mentioned peristome of selecting at random in 5 places is as the ratio of solidfied material layer residue (resist residue).By the ratio of gained resist residue, estimate resist in the mode of following benchmark and peel off residual.Evaluation result is shown in table 3 and table 4.In addition, resist residue is saved your breath bright good more more.

Benchmark

A: resist residue does not reach 10%

B: resist residue is more than 10% but does not reach 50%

C: resist residue is more than 50%

(plating solution contaminative)

With embodiment 1～8 and comparative example 1～4 gained photosensitive element 0.5m ², PET film and polyethylene film are peeled off after, in Ni-P plating solution Auro Tech HP (Japanese Atotech Co., Ltd. system, trade name),, carry out electroless nickel plating and handle in 83 ℃ of dippings 5 hours.

Use this plating treating fluid, carry out and the identical processing of above-mentioned anti-plating evaluation method, be determined at the Ni-P plating thickness (separating out thickness) of separating out on the substrate from ungrease treatment to electroless nickel plating for test base.Using new Ni-P plating solution Auro Tech HP to be used as blank group to substitute the plating treating fluid, is that 100 o'clock the relative value of separating out thickness is estimated the plating solution contaminative with the thickness of separating out of blank group.Evaluation result is shown in table 3 and table 4.In addition, the plating solution contaminative can be tried to achieve by following formula.

Plating solution contaminative (%)=each sample separate out thickness (μ m)/blank group separate out thickness (μ m)

(sensitivity)

Photographic layer in the photosensitive element that embodiment 1～8 and comparative example 1～4 are obtained, the condition lower floor at pressure 0.4MPa, 110 ℃ of temperature, laminate speed 1.5m/ minute is pressed on above-mentioned copper-surfaced plywood, gives stacked.On the gained duplexer, place Stouffer 21 rank exposure guide rules as minus, (Oak makes Co., Ltd. of institute system, 201GX) to use the exposure machine with high-pressure mercury-vapor lamp, with above-mentioned same development conditions under, with the required exposure energy (mJ/cm of 8.0 lattice that solidify 21 rank exposure guide rules ²) the evaluation sensitivity.Evaluation result is shown in table 3 and table 4.In addition, the low more explanation sensitivity of exposure energy is high more.

(table 3)

(table 4)

By table 3 and table 4 as can be known, the photosensitive polymer combination of embodiment 1～8 is good aspect anti-plating, fissility and the plating solution contaminative when forming solidfied material layer (corrosion-resisting pattern).In addition, these photosensitive elements are also good aspect the shape compliance of surface resin layer.

Claims (7)

1. photosensitive polymer combination, it is for containing (A) binder polymer, (B) have the optical polymerism compound and (C) photosensitive polymer combination of Photoepolymerizationinitiater initiater of polymerisable ethene unsaturated group, it is characterized by, (B) composition contains the system of bisphenol-A shown in the following general formula (1) (methyl) acrylate compounds, the acrylate compounds of oxyalkylated trihydroxy methyl-propane three (methyl) shown in the following general formula (2), nonyl phenyl shown in the following general formula (3) gathers alkane glycol (methyl) acrylate compounds

In the formula (1), X ¹And X ²The alkylidene of representing carbon number 2～6 independently of one another, R ¹And R ²Represent hydrogen atom or methyl independently of one another, p and q represent to satisfy the positive integer of p+q=4～40; In the formula (2), X ³, X ⁴And X ⁵The alkylidene of representing carbon number 2～6 independently of one another, R ³, R ⁴And R ⁵Represent hydrogen atom or methyl independently of one another, k, m and n represent to satisfy the positive integer of k+m+n=3～30; In the formula (3), X ⁶The alkylidene of expression carbon number 2～6, R ⁶Expression hydrogen atom or methyl, r represents 1～20 integer.

2. photosensitive polymer combination according to claim 1 is characterized by, and (C) composition contains 2,4,5-triarylimidazoles dipolymer.

3. photosensitive polymer combination according to claim 1, it is characterized by, (A) composition and (B) when the total amount of composition is 100 mass parts, (A) amount of composition is 40～80 mass parts, (B) amount of composition is 20～60 mass parts, and (C) amount of composition is 0.1～20 mass parts.

4. a photosensitive element is characterized by, and possesses support and the photographic layer that contains each described photosensitive polymer combination in the claim 1～3 that is arranged on this support.

5. photosensitive element according to claim 4 is characterized by, and this photographic layer is 5～75% to the ultraviolet transmitance of wavelength 365nm.

6. the manufacture method of a printed circuit board (PCB) is characterized by, and possesses the following step,

The 1st step: formed substrate and formed on the face of this surface resin layer side of the 1st multilayer board of the surface resin layer that forms on the substrate the stacked photographic layer that is shaped in advance that contains each described photosensitive polymer combination in the claim 1～3 at this circuit possessing circuit; Described circuit has formed substrate to have circuit and forms with substrate and be formed at this circuit and form with the circuit pattern on the substrate; Described surface resin layer is so that the form that described circuit pattern exposes to the open air is formed at described circuit and has formed on the substrate;

The 2nd step: behind the established part irradiation active ray of described photographic layer, develop, form the solidfied material layer that is patterned, obtain to have formed the 2nd multilayer board that possesses described surface resin layer and described solidfied material layer on the substrate successively at described circuit;

The 3rd step: carry out electroless plating for described the 2nd multilayer board, on described circuit pattern, form plating layer.

7. manufacture method according to claim 6 is characterized by, and the part that described solidfied material layer is patterned into described circuit pattern exposes to the open air, at the described plating layer of comprehensive formation of the exposed portion of described circuit pattern.

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