CN1612048A

CN1612048A - Method for making printed circuit board

Info

Publication number: CN1612048A
Application number: CNA2004100862758A
Authority: CN
Inventors: 佐佐木义晴; 佐藤守正
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Holdings Corp; Fujifilm Corp
Priority date: 2003-10-30
Filing date: 2004-10-29
Publication date: 2005-05-04
Also published as: KR20050041982A; TW200522806A; JP2005136223A

Abstract

The invention is aimed to obtain a printed circuit board provided with a high-resolution metal wiring pattern. This manufacturing method of the printed circuit board consists of a process of preparing a photosensitive transfer sheet obtained by laminating a first photosensitive layer of low sensitivity and a second photosensitive layer of high sensitivity are laminated on a support body; and a board for forming the printed circuit board which has a through hole and whose surface is covered with a metal layer having a surface roughness of 0.01 to 0.40 [mu]m, a laminating process of pressing the photosensitive transfer sheet to the surface of the board so that a second photosensitive layer may contact with it, a process of irradiating the wiring pattern forming area of the board from the supporter side of a laminated body with light of a light quantity which hardens the second photosensitive layer and irradiating an area including the opening part of the through hole of the board with light of a light quantity which cures both of the first photosensitive layer and the second photosensitive layer to form a hard layer area, a lifting process of the supporter, a development process for melting and removing a photosensitive layer area which is not cured yet, an etching process of the metal layer, and a removing process of a cured layer.

Description

The manufacture method of printed circuit board (PCB)

Technical field

The present invention relates to a kind of manufacture method with printed circuit board (PCB) of through hole or via hole.

Background technology

Use is transcribed thin slice (also being called the dry film photoresist) in the photonasty that supporter upper strata pressure sensitivity photosphere forms, and it is known to make printed circuit board (PCB) by photolithographic techniques.Printed circuit board (PCB) with through hole for example can followingly be made.The printed circuit board (PCB) that at first has metal level on the surface forms with substrate (for example copper plate pressing plate) goes up the formation through hole, forms metal level at the through-hole wall position.Then, superimposed photonasty is transcribed thin slice on the metal level of substrate surface, so that its photographic layer and metal layer contacting, form the zone and contain in the zone of via openings portion at the circuit pattern of layer on surface of metal, with the pattern form of rayed regulation so that the photographic layer sclerosis.Peel photonasty then and transcribe the supporter of thin slice, remove circuit pattern and form hardened layer on the zone and the hardened layer on the via openings portion zone (being called the camouflage film) unhardened photographic layer zone in addition, make the metal level exposure of substrate surface.Metal level to exposure partly carries out etch processes then, removes hardened layer then, makes the printed circuit board (PCB) that the surface has the metallic circuit pattern.

As mentioned above, superimposed photonasty is transcribed thin slice on the metal level of substrate surface, and the pattern form of using up then regulation shines, and is peeling photonasty when transcribing the supporter of thin slice, preferably uses flexible transparent membrane as supporter.

In the manufacturing process of printed circuit board (PCB),, then in etching, produce the problem of circuit pattern broken string etc. during the strip hardened layer sometimes if the metal level and the adaptation between the hardened layer of substrate surface is insufficient.Therefore, for the metal level that improves substrate surface and the adaptation between the hardened layer, asperities processing (normally polishing) is carried out on the surface of the metal level of substrate surface.

In order to realize that photonasty transcribes the high resolving powerization of thin slice, effective method is the thickness that reduces photographic layer.Yet if reduce the thickness of photographic layer, in the hardened layer distortion of the marginal portion of through hole, the thickness attenuation has the damaged easily problem of hardened layer when making printed circuit board (PCB).Therefore at present the photonasty that can form following hardened layer is transcribed thin slice and develop, this hardened layer can form high-resolution pattern, and also is difficult to break as the camouflage film.

In patent documentation 1, disclose the photonasty that a kind of supporter is provided with following two-layer photographic layer alkali and transcribed thin slice, this first photographic layer is an alkali-soluble, it is mobile less that heating causes, can respond to radioactive ray, and then second photographic layer that is provided with in the above is alkali-soluble, and the flowability that heating causes is bigger, can respond to radioactive ray.In this patent documentation 1, it has illustrated that second photographic layer by photonasty being transcribed thin slice is embedded in the through hole, can protect the metal level of through hole.Yet, in the final operation of making printed circuit board (PCB),, therefore have the complicated problem of manufacturing process that makes printed circuit board (PCB) owing to must remove the hardening resin (hardening thing of second photographic layer) that is embedded in the through hole.

Patent documentation 1: the spy opens flat 8-54732 communique

Summary of the invention

Invent technical matters to be solved

Problem of the present invention is, provide a kind of photonasty that has a photographic layer that can form high-resolution hardened layer and high-intensity hardened layer (camouflage layer) by use to transcribe thin slice, be convenient to industrialization ground and make and have through hole or via hole and have the manufacture method of the printed circuit board (PCB) of high resolving power metallic circuit pattern.

Solve the method for this problem

The manufacture method of printed circuit board (PCB) of the present invention is made up of following operation:

(1) prepare to make following printed circuit board (PCB) and form the operation of using substrate: this substrate is on supporter, according to first photographic layer, the order lamination of second photographic layer forms photonasty and transcribes thin slice, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form this first photographic layer of relative low sensitivity, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form high sensitive relatively this second photographic layer: and cover metal level on substrate surface, the surfaceness that this metal level is represented with Ra is in the scope of 0.01 to 0.40 μ m.

(2) form with on the surface of substrate at printed circuit board (PCB), photonasty is transcribed thin slice to be crimped on the metal level, so that its second photographic layer and metal layer contacting, according to printed circuit board (PCB) form with the sequential layer of substrate, second photographic layer, first photographic layer and supporter suppress the lamination of photonasty lamination body.

(3) from the support side of photonasty lamination body, at least the circuit pattern that forms with substrate to printed circuit board (PCB) forms in the zone, with the pattern form that the rayed of the necessary light quantity of sclerosis second photographic layer is stipulated, form the circuit part exposure process in the hardened layer zone of predetermined pattern.

(4) peel off the supporter stripping process of supporter from photonasty lamination body.

(5) dissolving is removed in the unhardened zone of printed circuit board (PCB) formation with first photographic layer on the substrate and second photographic layer, so that the developing procedure of the metal level in the unhardened zone of this of substrate surface exposure.

(6) remove the etching work procedure of the metal level of exposure area with etching solution dissolving.

(7) hardened layer of removing hardened layer with substrate from printed circuit board (PCB) formation is removed operation.

The optimal way of manufacture method of the present invention is as follows.

(A) surfaceness of metal level is to handle by chemical polishing to be adjusted in the above-mentioned scope.

(B) used light is laser in (3) of above-mentioned operation.

Manufacture method with printed circuit board (PCB) of through hole or via hole of the present invention is made up of following operation:

(1) prepare to make following printed circuit board (PCB) and form the operation of using substrate: this substrate is on supporter, according to first photographic layer, the order lamination of second photographic layer forms photonasty and transcribes thin slice, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form this first photographic layer of relative low sensitivity, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form high sensitive relatively this second photographic layer: and cover the metal level with through hole or via hole on substrate surface, the surfaceness that this metal level is represented with Ra is in the scope of 0.01 to 0.40 μ m.

(2) form with on the surface of substrate at printed circuit board (PCB), photonasty is transcribed thin slice to be crimped on the metal level, so that its second photographic layer and metal layer contacting form the lamination that makes photonasty lamination body with the order lamination of substrate, second photographic layer, first photographic layer and supporter according to printed circuit board (PCB).

(3) circuit pattern that forms with substrate from the supporter side direction printed circuit board (PCB) of photonasty lamination body forms in the zone, with the pattern form that the rayed of the necessary light quantity of sclerosis second photographic layer is stipulated, form the circuit part exposure process in the hardened layer zone of predetermined pattern.

(4) from the support side of photonasty lamination body, in the zone of the opening portion that contains through-holes of printed circuit boards or via hole, with the pattern form that the rayed of harden simultaneously first photographic layer and the necessary light quantity of second photographic layer is stipulated, form the bore portion exposure process in the hardened layer zone of the open area that covers through hole or via hole.

(5) peel off the supporter stripping process of supporter from photonasty lamination body.

(6) dissolving is removed in the unhardened zone of printed circuit board (PCB) formation with first photographic layer on the substrate and second photographic layer, so that the developing procedure of the metal level in the unhardened zone of this of substrate surface exposure.

(7) remove the etching work procedure of the metal level of exposure area with etching solution dissolving.

(8) hardened layer of removing hardened layer with substrate from printed circuit board (PCB) formation is removed operation.

The optimal way of manufacture method of the present invention is as follows.

(B) used light all is laser in (3) of above-mentioned operation and (4).

The invention still further relates to a kind of photonasty lamination body, on the surface of printed circuit board (PCB) formation, cover metal level with substrate, the surfaceness that this metal level is represented with Ra is in the scope of 0.01 to 0.40 μ m, on this substrate according to second photographic layer, the order lamination of first photographic layer, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form high sensitive relatively this second photographic layer, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link forms this first photographic layer of relative low sensitivity by rayed polymerization sclerosis.

The optimal way of manufacture method of the present invention is as follows.

(B) support body layer is pressed on first photographic layer.

In addition, in this manual, " surfaceness that Ra represents " is meant the arithmetic average roughness of regulation in the JIS (JISB 0601-1994).

The invention effect

Used photonasty is transcribed thin slice by changing the exposure (exposure) of its light in implementing manufacture method of the present invention, can form the different hardened layer of thickness respectively.Transcribe thin slice if use this photonasty, then can have on printed circuit board (PCB) that through hole or via hole, surface have a metal level forms with substrate, form thicker high strength sclerosis layer respectively and have the thin high-resolution hardened layer that the circuit pattern that covers layer on surface of metal forms the thickness in zone with the thickness that covers this through hole or via hole.

Form on the zone at the circuit pattern of printed circuit board (PCB) formation with the layer on surface of metal of substrate surface, when forming the high-resolution hardened layer of above-mentioned thinner thickness, the surfaceness of the metal level of substrate surface is necessary for suitable value.This be because: to form the resolution of the hardened layer that forms on the zone at circuit pattern higher in order to make, and in exposure process, is subjected to the irreflexive influence on the layer on surface of metal of substrate surface to the light of photographic layer irradiation.Specifically, the irregular reference amount of light is big, and then circuit pattern forms near the photographic layer in the regional outside owing to irreflexive light hardens, and makes that consequently the resolution of the hardened layer after exposing reduces a little.Used printed circuit board (PCB) forms the surfaceness of the metal level of using substrate surface in the scope of 0.01 to 0.40 μ m in manufacture method of the present invention.Have the substrate of the metal level of this suitable surfaceness by use, owing to reduced the diffuse reflection of aforementioned light on layer on surface of metal, the metal level and the adaptation between the hardened layer of substrate surface can not reduce, and can form high-resolution hardened layer.In addition, the photonasty that use in the past has one deck photographic layer is transcribed in the manufacture method of printed circuit board (PCB) of thin slice, in order on through hole, to form the camouflage film of sufficient intensity, owing on the metal level of substrate surface, form the hardened layer of thinner thickness and low resolution, can not produce aforesaid because the problem that the caused resolution of the diffuse reflection of light reduces.

Therefore the hardened layer that the thickness that manufacture method of the present invention owing to used forms on the surface of the metal level of substrate surface is thicker and the high resolving power hardened layer of thinner thickness are convenient to industrialization ground and are made the printed circuit board (PCB) that has through hole or via hole and have high resolving power metallic circuit pattern.

The best mode that carries out an invention

The manufacture method of printed circuit board (PCB) of the present invention has the situation of printed circuit board (PCB) of through hole or via hole as representative example with manufacturing, describe with the accompanying drawing that adds.At first photonasty used in the manufacture method of the present invention being transcribed thin slice describes.Fig. 1 is the sectional view of the structure of the example that the preferred photonasty of using is transcribed thin slice in implementing manufacture method of the present invention.

The photonasty of Fig. 1 is transcribed thin slice 10 and is had the structure that the order lamination according to flexible and transparent film support body 11, first photographic layer 12, second photographic layer 13 and protective seam 14 forms.First photographic layer 12 and second photographic layer 13 are respectively by containing binder polymer, contain the monomer of vinyl unsaturated link and the photosensitive polymer combination of Photoepolymerizationinitiater initiater forms, and the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis.The principal character that the photonasty of using among the present invention is transcribed thin slice is: the susceptibility of second photographic layer 13 is higher with respect to first photographic layer 12.Here susceptibility is higher is meant: compare with first photographic layer 12, the sclerosis of second photographic layer 13 can be initiated with the exposure of less light.

The relation that used photonasty is transcribed between the hardening capacity of the exposure of light of thin slice and photographic layer among the present invention describes with reference to Fig. 2.What Fig. 2 represented is, the photonasty of Fig. 1 is transcribed thin slice when shining, the sensitivity curve schematic of the relation between the exposure of expression light and the hardening capacity of photographic layer when using up from flexible and transparent film support side.In Fig. 2, transverse axis is represented the exposure of light, and the longitudinal axis is represented the thickness of the photographic layer that hardens by the irradiation of light.The D of the longitudinal axis represents the thickness of second photographic layer, and E represents all thickness of photographic layer photographic layer that the thickness addition of the thickness of first photographic layer and second photographic layer obtains.

As shown in Figure 2, transcribe thin slice for photonasty used among the present invention, although from the light of flexible and transparent film support side irradiation is according to flexible and transparent film support body, first photographic layer, the order of second photographic layer is passed through then, the sclerosis of second photographic layer is owing to this less light quantity is initiated before first photographic layer.The light quantity S of sclerosis that causes second photographic layer is preferably at 0.1～10mJ/cm ²Scope in.The hardening capacity of second photographic layer increases along with the increase of light quantity, all sclerosis of the second last photographic layer.Harden the necessary light quantity A of second photographic layer preferably at 20mJ/cm ²Below (particularly preferably in 2～15mJ/cm ²Scope in).

After all sclerosis of second photographic layer, if continue to increase the light light quantity, then the sclerosis of first photographic layer is initiated.If further increase light quantity, then all sclerosis of first photographic layer.Harden the ratio A/B of necessary light quantity A of second photographic layer and sclerosis first photographic layer necessary light quantity B preferably in 0.01～0.5 scope.

Up to first photographic layer necessary light quantity C of when beginning sclerosis can be equivalent with making the second photographic layer necessary light quantity A that hardens, and is preferably greater than light quantity A.Make harden necessary light quantity A and the poor C-A between first photographic layer necessary light quantity C of when beginning sclerosis of second photographic layer be less than to make harden 10 times (particularly in 1～10 times the scopes) of exposure A of necessary light of second photographic layer, preferably at 100mJ/cm ²Scope in (particularly at 1～100mJ/cm ²Scope in).

Photonasty with above-mentioned sensitivity curve is transcribed thin slice can be by for example, and the content of Photoepolymerizationinitiater initiater that makes second photographic layer is more than first photographic layer, and the method two that perhaps adds sensitizer in second photographic layer obtains.Transcribe the material of thin slice and manufacture method write up in content described later for photonasty.

Below with reference to Fig. 3, the manufacture method with printed circuit board (PCB) of through hole or via hole of the present invention is described.

At first, the content that has illustrated according to Fig. 1 and Fig. 2, prepare to make following photonasty and transcribe thin slice: on supporter, according to first photographic layer, the order lamination of second photographic layer forms photonasty and transcribes thin slice, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form this first photographic layer of relative low sensitivity, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link forms high sensitive relatively this second photographic layer by rayed polymerization sclerosis.

Then, shown in Fig. 3 (A), prepare to make following printed circuit board (PCB) and form with substrate 21, this substrate has through hole 22, and its surface is covered by metal level 23, and the surfaceness that the metal level on aforesaid base plate surface is represented with Ra is in the scope of 0.01 to 0.40 μ m.The surfaceness of metal level 23 is preferably in the scope of 0.05 to 20 μ m.Form with substrate 21 as printed circuit board (PCB), can use the substrate that for example on insulating substrates such as copper plate pressing plate and glass epoxy, forms copper coating, perhaps form pattern at the layer on surface of metal of these substrates respectively, lamination interlayer dielectric thereon, and then form the substrate (laminated substrate) of copper coating again.Use substrate by the printed circuit board (PCB) formation of surfaceness in above-mentioned scope of using this metal level, can on the surface of this metal level, form the good and high-resolution hardened layer of adaptation.Printed circuit board (PCB) forms with the surfaceness of the metal level of substrate surface and the relation between the resolution of the hardened layer that this layer on surface of metal forms and is documented in the content described later.

Preferably the surfaceness of the metal level 23 of substrate surface is adjusted to above-mentioned scope by polishing.As the representative example of polishing, can enumerate polishing and handle, wash milled processed and chemical polishing processing.The preferred especially chemical polishing of polishing is handled.Below, be treated to example with chemical polishing, the surfaceness that makes metal level 23 is reached the preferred process condition metal explanation of above-mentioned scope.

Chemical polishing by appropriateness is handled, the oxide that forms at the layer on surface of metal of substrate or be removed attached to the oil of layer on surface of metal, and the polishing equably on the direction surperficial along it of the metal level of substrate surface.Therefore, the surface of metal level of substrate surface and the closing force between the hardened layer that forms are in the above improved and make it even.

It is to form on the surface of the metal level of using substrate at printed circuit board (PCB) that chemical polishing is handled, and this surface is contacted with the treating fluid of dissolving aforementioned metal, carries out polishing by it is partly dissolved.Usually after chemical polishing was handled, the washing printed circuit board (PCB) formed with substrate (pickling before washing sometimes), and is dry then.Treating fluid is handled to form layer on surface of metal with substrate with printed circuit board (PCB) and contact and be treated to example, can enumerate dip treating, spray processing.In spray is handled, treating fluid from nozzle that jet pipe is connected spray.Form about printed circuit board (PCB) and to handle write up with the chemical polishing of substrate and open flat 6-204661 number and the spy opens in each communique of flat 11-6083 number the spy.

As the example for the treatment of fluid used in the chemical polishing processing, can enumerate iron chloride class treating fluid and hydroperoxide kind treating fluid.4～168g/ liter), sulfuric acid concentration is 100g/ liter (allowed band: 50～200g/ liter), copper ion concentration is the treating fluid that 0～50g/ rises as the hydroperoxide kind treating fluid, preferably use concentration of hydrogen peroxide to be 8g/ liter (allowed band:.Hydroperoxide kind processing temperature also is preferably 30 ℃ (allowed bands: 25～40 ℃), and when adopting spray to handle, the pressure of jet pipe is preferably 0.2MPa (allowed band: 0.1～0.3MPa).The time that the spray woods is handled is preferably 25 seconds (allowed band: 20～40 seconds).

Then, shown in Fig. 3 (B), second photographic layer, the 13 usefulness backer rolls 31 of photonasty being transcribed thin slice 10 are laminated on the printed circuit board (PCB) formation usefulness surface of substrate 21 (lamination).Obtain thus forming the photonasty lamination body that constitutes with the order lamination of substrate 21, second photographic layer 13, first photographic layer 12 and flexible and transparent film support body 11 according to printed circuit board (PCB).The lamination that photonasty is transcribed thin slice can carry out under (30～180 ℃) under room temperature (15～30 ℃) or the heating.Particularly preferably in carrying out under 60～140 ℃ the heating.

In addition, also can use photonasty described later transcribe thin slice manufacturing usefulness, directly be coated in printed circuit board (PCB) according to the order of the second photosensitive polymer combination solution and the first photosensitive polymer combination solution and form with on the substrate, by drying, form the photonasty lamination body of the order lamination formation of using substrate, second photographic layer, first photographic layer with printed circuit board (PCB).

Then, shown in Fig. 3 (C), from the face of flexible and transparent film support body 11 sides of photonasty lamination body, make the photographic layer sclerosis with rayed.The circuit pattern that forms with substrate 21 to printed circuit board (PCB) forms on the zone, and the pattern form with the rayed regulation that makes the necessary light quantity of second photographic layer, 13 sclerosis forms the zone (circuit part exposure process) that circuit pattern forms the hardened layer 15 of usefulness.Form with the peristome of the path 22 of substrate and on every side at printed circuit board (PCB); shine with the light that makes first photographic layer 12 and the necessary light quantity of second photographic layer, 13 sclerosis respectively, the metal level that forms through hole is protected the zone (exposure process of bore portion) of the hardened layer 16 of usefulness.The exposure process of circuit part exposure process and bore portion can carry out respectively, preferably carries out simultaneously.Exposure can be undertaken by light is shone through photomask, perhaps by using the laser explosure device irradiating laser to carry out.As the light source that in exposure, uses, use can produce through flexible and transparent film support body 11 and used relatively Photoepolymerizationinitiater initiater as the electromagnetic wave of activity or wavelength 310～700nm (be preferably in 350～500nm) scopes from the ultraviolet to the visibility region in the light source of light.The fluorescent tube, the known light source of semiconductor laser lamp that for example (surpass) high-pressure mercury-vapor lamp, xenon lamp, carbon arc lamp, Halogen lamp LED, duplicating usefulness.Can also use electron ray or X ray in addition.

In exposure process the light of irradiation photographic layer on the surface of the metal level 23 of substrate surface by diffuse reflection.Near second photographic layer 13 that irreflexive light forms the outside of hardened layer 15 of usefulness circuit pattern is for example hardened slightly, and the resolution of hardened layer 15 is reduced.Used printed circuit board (PCB) forms the surfaceness of the metal level of using substrate surface in the scope of 0.01 to 0.40 μ m (preferably at 0.05 to 0.20 μ m) in the manufacture method of the present invention.Have the substrate of the metal level of this appropriate surfaceness by use, owing to reduced the diffuse reflection of the light on the aforementioned metal laminar surface, so the metal level of basic surface and not reduction of the adaptation between the hardened layer, can form high-resolution hardened layer.That is to say, the metal level 23 of substrate surface surfaceness if less than 0.01 μ m, then the adaptation of metal level 23 and hardened layer 15 is insufficient, if surfaceness surpasses 0.40 μ m, then the resolution of hardened layer 15 reduces.

Then, shown in Fig. 3 (D), peel flexible and transparent film support body 11 (supporter stripping process) from photonasty lamination body.

Then; shown in Fig. 3 (E); printed circuit board (PCB) formation is dissolved in suitable developer solution with the unhardened zone of first photographic layer 12 on the substrate 21 and second photographic layer 13 and is removed; and circuit pattern forms the hardened layer 15 of usefulness and the metal level of through hole protects the hardened layer 16 of usefulness to develop, and makes metal level 23 exposures (developing procedure) of substrate surface." dissolving is removed " in the unhardened zone of photographic layer also comprises the following meaning, and promptly the part in the unhardened zone of photographic layer is dissolved, and rest parts is removed with the form of stripping film.As the example of developer solution, can enumerate alkaline aqueous solution (for example aqueous sodium carbonate), contain the alkaline aqueous solution and the organic solvent of organic solvent.

Then, shown in Fig. 3 (F), remove the metal level 23 (etching work procedure) that exposes on the substrate surface with the etching solution dissolving.Form with forming circuit pattern 24 on the substrate 21 at printed circuit board (PCB) thus.When metal level 23 is under the situation about being formed by copper, can use ferrous chloride aqueous solution, stannous chloride aqueous solution and copper chloride solution as etching solution.

Then, shown in Fig. 3 (G), in strong alkaline aqueous solutions such as NaOH and potassium hydroxide, hardened layer 15,16 forms with stripping film 17 are removed (hardening thing is removed operation) from printed circuit board (PCB) formation with substrate.Thus, can produce printed circuit board (PCB) with through hole that its inner wall surface covered by metal level.

In addition, the present invention is not limited to have the manufacturing of the printed circuit board (PCB) of above-mentioned through hole or via hole.For example, with the above-mentioned photonasty lamination body of similarly making, the circuit pattern that forms with substrate at this printed circuit board (PCB) forms on the zone, with making the harden pattern form of rayed regulation of necessary light quantity of second photographic layer, similarly later on, development, Etched Printed Circuit plate by the peeling off of supporter, photographic layer form with the metal level of substrate, remove hardened layer then, can produce the printed circuit board (PCB) with high-resolution metallic circuit pattern (not having through hole or via hole).When making this printed circuit board (PCB), form on the zone in addition, zone by the circuit pattern that for example forms with substrate at above-mentioned printed circuit board (PCB), with making harden the simultaneously pattern form of rayed regulation of necessary light quantity of first photographic layer and second photographic layer, can produce the printed circuit board (PCB) that has above-mentioned high-resolution metallic circuit pattern and there is no need to become high-resolution metal layer pattern (not having through hole or via hole).

Below the photonasty of the structure of Fig. 1 is transcribed thin slice material and manufacture method be elaborated.Transcribing the multipolymer that the binder polymer that uses in the thin slice preferably has following character in photonasty, is soluble to alkaline aqueous solution promptly, perhaps by with contacting of alkaline aqueous solution at least can swelling.As the example that has the multipolymer of solubility or swelling with respect to alkaline aqueous solution, but can enumerate the carboxylic ethylenic copolymer that obtains by vinyl monomer copolymerization by the vinyl monomer that contains carboxyl and other copolymerization.

As the example of carboxylic vinyl monomer, can enumerate methacrylic acid, vinyl benzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, styrene sulfonic acid, 2-third rare acid amides-2-methyl propane sulfonic acid and the rare acyl group ethyl ester of mono phosphoric acid ester methyl-prop etc.Also can be with by the monomer of hydroxyl and the addition reaction of maleic anhydride or this cyclic acid anhydride of phthalic anhydride with 2-hydroxyethyl methacrylate etc.Perhaps also can use the monomer of acid anhydrides such as the maleic anhydride that contains as carboxyl precursor, itaconic anhydride.In addition, from copolymerization performance and composition and deliquescent angle, special therein preferable methyl acrylic acid.

But, can enumerate the vinyl unsaturated monomer that does not contain acidic-group (particularly carboxyl) as the example of the vinyl monomer of other copolymerization.Preferred especially and acidic-group does not have chemically reactive monomer.Preference such as methyl acrylic ester, cinnamate derivative, vinyl esters etc., maleic acid diester class, dimethyl ester class, itaconic acid diester class, the rare amide-type of methyl-prop, phenylethylene and vinyl ethers.As these monomers, for example can enumerate following compound.

As the example of methyl acrylic ester, can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, the just own ester of methacrylic acid, methacrylic acid 2-Octyl Nitrite, methacrylic acid acetoxyl group ethyl ester, phenyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid 2-(2-methoxy ethoxy) ethyl ester, cyclohexyl methacrylate, benzyl methacrylate, the diethylene glycol monomethyl ether methacrylate, the carbitol methacrylate, diglycol one phenyl ether methacrylate, triethylene glycol monomethyl ether methacrylate and triethylene glycol one ether methacrylate.

As the example of crotonates class, can enumerate butyl crotonate and the own ester of crotonic acid etc.As the example of vinyl esters, can enumerate vinyl acetate, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and vinyl benzoate.

As the example of maleic acid diester class, can enumerate dimethyl maleate, diethyl maleate and dibutyl maleate etc.As the example of dimethyl ester class, can enumerate dimethyl fumarate, DEF and dibutyl fumarate etc.As the example of itaconic acid diester class, can enumerate dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.

Example as the rare amide-type of methyl-prop, can enumerate the rare acid amides of methyl-prop, N-methyl third rare acid amides, N-ethyl-methyl third rare acid amides, the rare acid amides of N-propyl group methyl-prop, the rare acid amides of N-normal-butyl methyl-prop, the rare acid amides of N-tert-butyl group methyl-prop, N-cyclohexyl methyl third rare acid amides, the rare acid amides of N-(2-methoxy ethyl) methyl-prop, N, N-dimethyl methyl third rare acid amides, N, N-diethylmethyl third rare acid amides, N-phenyl methyl third rare acid amides, the rare acid amides of N-benzyl methyl-prop and the rare acyloxy morpholine of methyl-prop etc.

As the example of phenylethylene, can enumerate methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethylene styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromostyrene, 1-chloro-4-methyl-benzene, vinyl benzoic acid methyl esters and α-Jia Jibenyixi etc.As vinyl ethers, can enumerate methyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and methoxy ethyl vinyl ether etc.

Other can also use vinylpyridine, vinyl pyrrolidone, vinyl card azoles and the rare nitrile of methyl-prop etc.

These compounds can only use a kind of, also can use two or more simultaneously.As the example of particularly preferred copolymerisable monomer, can enumerate methyl methacrylate, methacrylic acid 2-Octyl Nitrite, benzyl methacrylate, styrene, α-Jia Jibenyixi, chlorostyrene, bromostyrene and hydroxy styrenes etc.

The content of repetitive that contains carboxyl in the carboxylic ethylenic copolymer is in the scope of 1～60 mole of % of all repetitives of multipolymer, preferably in the scope of 5～50 moles of %, in 1～40 mole of %.The molecular weight of carboxylic ethylenic copolymer is preferred in 1000～200000 scope, in 4000～100000 scope in the quality mean molecular weight.

In first photographic layer and second photographic layer, the content of the binder copolymer in the photographic layer is preferably in the scope of 5～96 quality %, in the scope particularly preferably in 40～80 quality %.

As the example that is fit to of the monomer that contains the vinyl unsaturated link, be the compound (the following polyfunctional compound that is also referred to as sometimes) that has 2 vinyl unsaturated double-bonds at least.For example as the example of this polyfunctional monomer, what can enumerate is the compound that is documented in special public clear 36-5093 communique, special public clear 35-14719 communique, the special public clear 44-28727 communique etc.As the example of the compound of putting down in writing in the above-mentioned communique (methyl acrylic ester, the rare amide-type of methyl-prop, allyl compound, vinyl ether compound, vinyl ester), can enumerate following compound.Example as esters of acrylic acid and methyl acrylic ester, can enumerate many esters of acrylic acids of polyvalent alcohol and many methyl acrylic esters (herein " many " are meant more than the dimethylacrylate) example as this polyvalent alcohol, can enumerate polyglycol, polypropylene glycol, polytetramethylene glycol, the polyoxygenated cyclohexene, polyoxygenated styrene, polyoxy heterocycle butane, PolyTHF, cyclohexanediol, the xylylene glycol, two-(beta-hydroxy ethoxy) benzene, glycerine, diglycerol, neopentyl glycol, trimethylolpropane, trihydroxy methyl one alkane, pentaerythrite, dipentaerythritol, sorbitan, D-sorbite, butylene glycol, butantriol, the 2-butene-1, the 4-glycol, 2-normal-butyl-2-ethyl-propylene glycol, 2-butine-1, the 4-glycol, 3-chloro-1, the 2-propylene glycol, 1, the 4-cyclohexanedimethanol, 3-cyclohexene-1, the 1-dimethanol, the naphthalane glycol, 2,3-two bromo-2-butene-1s, the 4-glycol, 2,2-diethyl-1, ammediol, 1,5-dihydroxy-1,2,3, the 4-tetralin, 2,5-dimethyl-2, the 5-cyclohexanediol, 2,2-dimethyl-1, ammediol, 2,2-diphenyl-1, ammediol, dodecanediol, the internal compensation erythrite, 2-ethyl-1, the 3-cyclohexanediol, 2-ethyl-2-(methylol)-1, ammediol, 2-ethyl-2-methyl isophthalic acid, ammediol, heptandiol, hexanediol, 3-hexene-2, the 5-glycol, hydroxy-benzyl alcohol, the hydroxyethyl resorcinol, the 2-methyl isophthalic acid, the 4-butylene glycol, 2-methyl-2, the 4-pentanediol, nonanediol, ethohexadiol, pentanediol, 1-phenyl-1,2-ethylene glycol, propylene glycol, 2,2,4,4-tetramethyl-1,3-encircles heptandiol, 2,3,5,6-tetramethyl-P-xylene-α, α '-glycol, 1,1,4,4-tetraphenyl-1, the 4-butylene glycol, 1,1,4,4-tetraphenyl-2-butine-1, the 4-glycol, 1,2,6-trihydroxy hexane, 1,1 '-two-beta naphthal, dihydroxy naphthlene, 1,1 '-methylene-two-beta naphthal, 1,2, the 4-benzenetriol, bis-phenol, 2,2 '-two (4-hydroxyphenyl) butane, catechol, the 4-chloro resorcinol, 3,4-dihydroxy hydrocinnamic acid, p-dihydroxy-benzene, the acrinyl allyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoic acid ester, phloroglucin, 1,2,3,-thrihydroxy-benzene, resorcinol, glucose, α-(1-amino-ethyl)-to hydroxy-benzyl alcohol, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, 3-amino-1, ammediol, N-(3-aminopropyl)-diethanolamine, N, N '-two-(2-hydroxyethyl) piperazine, 2, two (methylol)-2 of 2-, 2 ', 2 "-and nitrilotriethanol; 2, two (methylol) propionic acid of 2-; 1; two (methylol) urea of 3-; 1; two (the 4-pyridine radicals)-1 of 2-, 2-ethylene glycol, N-normal-butyl diethanolamine, 3-sulfydryl-1, the 2-propylene glycol, 3-piperidyl-1,2-propylene glycol 2-(2-pyridine radicals)-1, ammediol, triethanolamine, α-(1-amino-ethyl)-to hydroxy-benzyl alcohol and 3-amino-4-hydroxy phenylsulfone etc.

Among these esters of acrylic acids and methyl acrylic ester, as most preferred example, angle from easy acquisition, can enumerate glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethyleneglycol diacrylate, three four propylene glycol diacrylates that contract, ten-ten propylene glycol diacrylates contract, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate,-dipentaerythritol five acrylate contract, glycerol tri-acrylate,-two glycerine dimethylacrylates contract, 1, the ammediol diacrylate, 1,2,4-butantriol trimethyl acrylic ester, 1,4-cyclohexanediol diacrylate, 1,5 pentandiol diacrylate, neopentylglycol diacrylate and adduction the triacrylate etc. of trimethylolpropane of oxirane.

Example as acrylic amide and the rare amide-type of methyl-prop, except di-2-ethylhexylphosphine oxide third rare acid amides, can also enumerate ethylenediamine, diaminopropanes, diaminobutane, five methylene diamine, hexamethylene diamine, two (2-aminopropyl) amine, dimethylene triamine, five methylene diamine, eight methylene diamine and insert polyamine (for example phenylenediamine) that heteroatomic polyamine ethyl contains ring, xylylene amine, β-(4-aminophenyl) ethylamine, diaminobenzoic acid, diaminotoluene, diamino-anthraquinone, diamino-fluorene etc.) etc.

As allyl compound, can enumerate the diallyl ester of dicarboxylic acids such as phthalic acid, terephthalic acid (TPA), decanedioic acid, hexane diacid, glutaric acid, malonic acid and nitric acid; Anthraquinone disulfonic acid, benzenedisulfonic acid, 2, the 5-dihydroxy-to the allyl ester of disulfonic acid such as benzenedisulfonic acid, dihydroxy naphthylene disulfonic acid and naphthylene sulfonic acid; With diallyl acid amides etc.As the example of vinyl ether compound, can enumerate the polyvingl ether { for example ethylene glycol bisthioglycolate vinyl ether, 1,3,5-three-β-ethyleneoxy ethoxybenzene, 1,3-two-β-ethyleneoxy ethoxybenzene and glycerine trivinyl ether } of aforementioned polyvalent alcohol.As the example of vinyl esters, can enumerate succinic acid divinyl ester, hexane diacid divinyl ester, phthalic acid divinyl ester, terephthalic acid (TPA) divinyl ester, 1,3-benzenedisulfonic acid divinyl ester and 1,4-fourth disulfonic acid divinyl ester etc.As the example of distyryl compound, can enumerate divinylbenzene, to allyl styrene with to different acrylonitrile-styrol etc.

As the compound beyond the above-claimed cpd, as having of going for that compound among the present invention can enumerate, acrylic acid N-beta-hydroxyethyl-β-(the rare acid amides of methyl-prop) ethyl ester, N, two (Beta-methyl third rare acyloxy ethyl) the third rare acid amides of N-, allyl methacrylate etc. have the compound of vinyl unsaturated double-bonds different more than 2; And then can enumerate be, in the resultant of reaction that obtains by polyol compound that has 2 hydroxyls at least and the excessive slightly polyisocyanate compounds reaction that has 2 isocyanate group at least, the polyfunctional group urethane compound that has 2 vinyl unsaturated double-bonds at least that it is obtained with the compound reaction that has a hydroxyl and a vinyl unsaturated group at least.

These polyfunctional monomers can use separately or use simultaneously two or more.In first photographic layer and second photographic layer, the content of the polyfunctional monomer in the photographic layer is preferably in the scope of 5～90 quality %, in the scope particularly preferably in 15～60 quality %.

As Photoepolymerizationinitiater initiater, that can enumerate has, aromatic ketone, disclosed adjacent bunching ketone group in No. 2367660 instructions of United States Patent (USP) (PVC シ Na Le Port リケ Le De ニ Le) compound, the acyloin ether compound of in No. 2448828 instructions of United States Patent (USP), putting down in writing, in No. 2722512 instructions of United States Patent (USP), put down in writing with α-hydrocarbon substituted aromatic acyloin compound, the multinuclear quinone compounds of in No. 3046127 instructions of United States Patent (USP) and No. 2951758 communique, putting down in writing, the triarylimidazoles dipolymer of putting down in writing in No. 3549367 instructions of United States Patent (USP) is checked the combination of amino ketones, benzothiazole compound and the trihalomethyl-s-triaizine compounds put down in writing in the special public clear 51-48516 communique, trihalomethyl-s-triaizine compounds of in No. 4239850 instructions of United States Patent (USP), putting down in writing, the San halogen Jia oxadiazole compound of in No. 4212976 instructions of United States Patent (USP), putting down in writing.Special optimization aromatic ketone.

Preferred example as above-mentioned aromatic ketone, can enumerate benzophenone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, the 4-methoxy benzophenone, the 2-chlorobenzophenone, the 4-chlorobenzophenone, 4-bromine benzophenone, the 2-carboxyl benzophenone, 2-ethoxy carboxyl benzophenone, benzophenone tetrabasic carboxylic acid or its tetramethyl ester, 4-methoxyl-4 '-dimethylamino benzophenone, 4,4 '-dimethoxy-benzophenone, 4-dimethylamino benzophenone, 4-dimethylamino benzoylformaldoxime, anthraquinone, 2-tert-butyl group anthraquinone, 2-methylanthraquinone, phenanthrenequione, xanthone, thioxanthones, the 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, fluorenes, acridone and benzoin, benzoin ethers (benzoin methyl ether for example, the benzoin ethylether, the benzoin propyl ether, the benzoin isopropyl ether, the benzoin phenyl ether, benzyl dimethyl ketal), 4,4 '-two (dialkyl amino) benzophenone (for example 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (dicyclohexyl amine base) benzophenone, 4,4 '-two (diethylin) benzophenone, 4,4 '-two (dihydroxy ethyl amido) benzophenone).As particularly preferred example, can enumerate benzophenone.

In first photographic layer and second photographic layer, the content of the Photoepolymerizationinitiater initiater in the photographic layer is generally 0.1～10 quality %, preferred 0.5～5 quality %.When adjusting the susceptibility difference of first photographic layer and second photographic layer by Photoepolymerizationinitiater initiater when, the content of the Photoepolymerizationinitiater initiater of second photographic layer preferably is 1.5～10 times amount with respect to the content of the Photoepolymerizationinitiater initiater of first photographic layer, is preferably 2～5 times amount especially.

Can in transcribing the photographic layer of thin slice, photonasty add sensitizer.Sensitizer only is added in second photographic layer usually.

As sensitizer, can use the polynuclear aromatic same clan (for example pyrene, perylene, benzo [9,10] phenanthrene), cluck ton class (for example fluorescein, eosin, erythrosine, lotusin B, rose-red), cyanines class (for example thia carbon cyanines, oxygen thia carbon cyanines), part cyanines class (for example part cyanines, carbon part cyanines), thiazide (for example thionine, methylenum careuleum, toluidine blue), acridine (for example acridine orange, chloroflavin, acriflavine), anthraquinone class (for example anthraquinone), spiny dogfish terpene (ス Network アリウ system) class (for example spiny dogfish terpene) aptly.

With respect to all the components of photographic layer, the addition of sensitizer is in the scope of 0.05～30 quality %, preferably in the scope of 0.1～20 quality %, in the scope particularly preferably in 0.2～10 quality %.

The photographic layer that photonasty is transcribed thin slice can contain the lophine dipolymer.Example as the lophine dipolymer, can enumerate 2-(2 '-chlorphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(2 '-chlorphenyl)-4,5-two (3 '-methoxyphenyl) imidazole dimer, 2-(2 '-fluorophenyl)-4,5-diphenyl-imidazole dipolymer, 2-(2 '-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer and 2-(4 '-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer.

The photographic layer that photonasty is transcribed thin slice can contain organosulfur compound, superoxide, redox compounds, azo and diazo-compounds, photo-reduction pigment and the organic halogen compound of putting down in writing in " optical sensing system (Off イトセ Application シテイ Block システ system ズ) " the 5th chapter that for example Xiao Ke Sa (J. コ-サ-) is write etc.As organosulfur compound, can enumerate di-n-butyl disulfide, benzyl disulfide thing, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, benzenethiol, ethyl methenyl choloride sulfenic acids ester and 2-mercaptobenzimidazole.As the example of superoxide, can enumerate di-tert-butyl peroxide, benzoyl peroxide and methyl ethyl ketone peroxide etc.The redox compounds can be combined by superoxide and reductive agent, as its example, can enumerate ferrous ion and persulfuric acid ion, ferric ion and superoxide etc.As the example of azo and diazo-compounds, can enumerate α, α '-azoisobutyronitrile, 2-azo two-2-methylbutyronitrile and to the diazonium ion class of amino-diphenyl-amine.As the example of photo-reduction pigment, can enumerate rose-red, erythrosine, eosin, acriflavine, lactochrome and thionine etc.As the example of organic halogen compound, can enumerate 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorphenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-trisbromomethyl-5-phenyl-1,3,4-oxadiazole, 2-trisbromomethyl-5-(2-naphthyl)-1,3, the 4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxyl-styrene)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxy styryl)-1,3,4-oxadiazole, 2-trisbromomethyl-5-styryl-1,3, the 4-oxadiazole; Phenyl trisbromomethyl sulfone, p-nitrophenyl trisbromomethyl sulfone, to chlorophenyl trisbromomethyl sulfone; 2,4,6-three (trichloromethyl)-s-triazine, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-chlorophenyl)-4, two (the trisbromomethyl)-s-triazines of 6-.

Further, as the example of organic halogen compound, can also enumerate halogenated hydrocarbon, halohydrin compound, carbonyl halide compounds, halogenated ethers compound, halogenation ester compounds and halogenation amide compound.As the example of halogenated hydrocarbon, can enumerate tetrabormated hydrocarbon, iodoform, 1,2-ethylene dibromide, 1,1,2,2-tetrabromoethane, 1,1-pair (to chlorophenyl-2,2,2-trichloroethanes, 1,2-two bromo-1,1,2-trichloroethanes, 1,2,3-tribromopropane, 1-bromo-4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachloro trimethylene, chlordene cycloheptadiene and dibromo-cyclohexane etc.As the example of halohydrin compound, can enumerate 2,2,2-ethapon, ethobrom, 1,3-two chloro-2-propane, 1,1,1-three chloro-2-propane, two (iodo hexa-methylene) amido isopropyl alcohol, acetone-bromoform and 2,2,3-three chloro-1,4-butylene glycol etc.As the example of carbonyl halide compounds, can enumerate 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, perbrome-acetone, 1,1,3,3-tetrachloroacetone, 1,1,1-trichloroacetone, 3,4-two bromo-2-butanone and 1,4-two chloro-2-butanone-dibromo hexanones etc.As the example of halogenated ethers compound, can enumerate 2-bromo-ethyl-methyl ether, 2-bromoethyl ethylether, two (2-bromoethyl) ether and 1,2-Dichloroethyl ethylether etc.Example as the halogenation ester compounds, can enumerate the ester of halogenation carboxylic acid, the halogenation ester of carboxylic acid or the halogenation ester of halogenation carboxylic acid, their example as this, can enumerate bromoethyl acetate, ethyl trichloroacetate, trichloroacetic acid trichloro ethyl ester, acrylic acid 2, the homopolymer of 3-dibromo propyl ester and multipolymer, dibromo-propionic acid trichloro ethyl ester, alpha, beta-2-dibrom ethyl acrylate etc.Example as the halogenation amide compound, can enumerate chloroacetamide, acetbromamide, dichloro acetamide, trichloroacetamide, tribromoacetamide, three chloroethyl trichloroacetamides, 2-bromine isopropyl propionamide, 2,2,2-trichlorine propionamide, N-chlorine succinamide and N-bromine succinamide etc.In organic halogen compound preferably on the same carbon atom in conjunction with the halogenide of the halogen atom more than 2, particularly preferably on the same carbon atom in conjunction with the halogenide of the halogen atom more than 3.Organic halogen compound can use separately, also can use simultaneously two or more.Wherein particularly preferred organic halogen compound is a trisbromomethyl phenyl sulfone, 2, two (trichloromethyl) 6-Phenyltriazoles of 4-.With respect to all the components of photographic layer, the amount of organic halogen compound is generally in the scope of 0.001～5 quality %, preferably in the scope of 0.005～1 quality %.

Can also further transcribe and add thermal polymerization inhibitor in the thin slice to photonasty.Example as thermal polymerization inhibitor, can enumerate p-dihydroxy-benzene, tert-butyl catechol, pyrogallol, stannous chloride, chloranil, naphthylamines, the betanaphthol, 2 of p methoxy phenol, p-dihydroxy-benzene, alkyl or aryl replacement, 6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitro benzene, para-totuidine, methylene blue, organic copper and gaultherolin etc.The content of these thermal polymerization inhibitors is being in the scope of 0.001～5 quality % with respect to polyfunctional monomer preferably.

Transcribe in the photographic layer of thin slice in photonasty, for controlling diaphragm rerum natura (flexibility), can also add plastifier, as example, can enumerate repefral, dibutyl phthalate, diisopropyl phthalate, dioctyl phthalate, many octyl benzoates (phthalate such as オ Network チ Le カプリ-Le Off レ-ト), dicyclohexyl phthalate, phthalic acid tricosyl ester, butyl benzyl phthalate, diisooctyl phthalate, phthalic acid diaryl; Gluconate classes such as dimethyl glucose phthalic ester, ethyl phthalyl ethyl glucuronide acid esters, methyl phthalyl ethyl glucuronide acid esters, butyl phthalyl butyl glucose acid esters, triethylene glycol dieaprylate; Aliphatic diester classes such as phosphoric acid ester such as tricresol phosphate, triphenyl phosphate, diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, dibutyl maleate; Amide-types such as benzsulfamide, para toluene sulfonamide, N-normal-butyl acetamide; Triethyl citrate, glycerine triacetyl ester, butyl laurate etc.As plastifier, preferably use para toluene sulfonamide.

The photographic layer that photonasty is transcribed thin slice can contain colourless pigment.As the example of colourless pigment, can enumerate amido triarylmethane classes such as three (to dimethylaminophenyl) methane (rock crystal purple), three (to the diethylin phenyl) methane, three (to dimethylamino-o-methyl-phenyl-) methane, three (to diethylin-o-methyl-phenyl-) methane, two (to dimethylaminophenyls)-[to (2-amino-ethyl) methylamino phenyl] methane, methane, two (to dimethylaminophenyl)-2-quinolyl methane, three (dipropyl amino phenyl) methane; 3, two (the dimethylamino)-9-phenyl yanthines of 6-, 3-amino-6-dimethylamino-amido xanthines such as 2-methyl-9-(Chloro-O-Phenyl) xanthine; 3, two (dimethylamino)-9-(the adjacent ethoxy carbonyl phenyl) thioxanthenes, 3 of 6-, amido thioxanthene classes, 3 such as two (dimethylamino) thioxanthenes of 6-, two (dimethylamino)-9 of 6-, 10-dihydro-9-phenylacridine, 3, two (benzamido group)-9 of 6-, 10-dihydro-amidos-9 such as 9-methylacridine, 10-acridan class; 3, two (the amido phenoxazine classes such as dimethylamino) phenoxazine of 7-; 3, amido phenothiazine ketones such as two (dimethylamino) phenthiazones of 7-; 3, two (the diethylin)-5-hexyls-5 of 7-, amino dihydrophenazine classes such as 10-dihydrophenazine; Aminocarbonyl phenyl methane classes such as two (to dimethylaminophenyl) anilino-methane; 4-amino-4 '-dimethylamino diphenylamine, 4-amino-α, β-amido hydrocinnamic acid classes such as dicyano hydrocinnamic acid methyl esters; 1-(2-naphthyl)-hydrazine classes such as 2-phenyl hydrazine; 1, two (ethylamino-)-2 of 4-, amino such as 3-dihydro-anthraquinone-2,3-dihydroanthracene quinones; N, the N-diethyl-to phenethyl phenyl aminess such as phenethyl aniline; 10-acetyl group-3, two (dimethylamino) phenthiazones etc. of 7-contain the acyl derivative of the colourless pigment of alkaline NH; The colourless shape compound not hydrogeneous, that be oxidized to chromophore compound that obtains after the oxidation of three (4-diethylin-o-tolyl) ethoxy carbonyl methane etc.; Indigo white (colourless indigo-blue) pigment; The organic amine that is oxidized to color development shape of record in the United States Patent (USP) No. 3042515 and No. 3042517 (for example 4,4 '-ethylenediamine, diphenylamine, N, accelerine, 4,4 '-methylene diamine triphenylamine, N-vinylcarbazole), preferred especially rock crystal purple.With respect to all the components of photographic layer, the amount of above-mentioned colourless pigment is preferably in the scope of 0.01～10 quality %, in the scope particularly preferably in 0.05～5 quality %.

So that photographic layer is painted, giving its storage stability is purpose, transcribes in the thin slice in photonasty, can use dyestuff.Example as the dyestuff that is fit to, can enumerate brilliant green, eosin, ethyl violet, Erythrosin B, methyl green, amethyst violet, basic fuchsin, phenolphthalein, 1,3-diphenyl triazine, sodium alizarinsulfonate, thymolphthalein, methyl violet 2B, quinaldine red, rose-red, tropeolin G, thymol blue, xylenol blue, methyl orange, orange IV, diphenylthiocarbazone, 2, the 7-dichlorofluorescein, paramethyl red, Congo red, benzene assistant purple 4B, α-Nai Hong, Nile blue A, phenanthridines (Off エ Na セリ Application), methyl violet, the peacock green oxalates, paramagenta, oil blue #603 (manufacturing of Ao Lientuo (オリエ Application ト) chemical industry (strain)), rhodamine B and rhodamine 6G etc.Particularly preferred dyestuff is the peacock green oxalates.

In order to improve the adaptation between first photographic layer and second photographic layer or to improve second photographic layer and printed base plate forms with the adaptation between basic, in photographic layer, can use known so-called driving fit promoter.As the example of driving fit promoter, can enumerate benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholino methyl isophthalic acid-phenyl-triazole-2-thioketones, 3-morpholino methyl-5-phenyl-triazole-2-thioketones, 5-amido-3-morpholino methyl-thiadiazoles-2-thioketones and close 2-sulfydryl-5-methyl sulfo--thiadiazoles etc.As driving fit promoter, preferably use 3-morpholino methyl isophthalic acid-phenyl-triazole-2-thioketones.

Used photonasty is transcribed thin slice and for example can followingly be made among the present invention.

At first make above-mentioned various material dissolves or be distributed in the dissolving, prepare first photographic layer respectively and form first photosensitive polymer combination solution of usefulness and the second photosensitive polymer combination solution that second photographic layer forms usefulness.As the solvent of the first photosensitive polymer combination solution and the second photosensitive polymer combination solution, for example can enumerate alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, n-hexyl alcohol; Ketones such as acetone, MEK, methyl isopropyl Ketone, cyclohexanone, diisopropyl ketone; Ester classes such as ethyl acetate, butyl acetate, n-amyl acetate, Methylsulfate, ethyl propionate, repefral, ethyl benzoate; Arenes such as toluene, dimethylbenzene, benzene, ethylbenzene; Phenixin, triclene, chloroform, 1,1, halogenated hydrocarbons such as 1-trichloroethanes, ethlyene dichloride, single chlorobenzene; Tetrahydrofuran, ether, glycol monoethyl ether, ethylene glycol monoethyl ether, 1-methoxyl-ethers such as 2-propyl alcohol; Dimethyl formamide, dimethyl sulfoxide etc.In the first photosensitive polymer combination solution and the second photosensitive polymer combination solution, can also add adjuvant.

Then the first photosensitive polymer combination solution is coated on the flexible and transparent supporter, forms first photographic layer by drying.After forming first photographic layer, apply the second photosensitive polymer combination solution thereon by dry second photographic layer that forms.

The good material of preferably photopermeability as aforementioned flexible and transparent supporter.Perhaps wish it is the good material of surface smoothing.As the example of flexible and transparent supporter, can enumerate various plastic sheetings such as polyethylene terephthalate, poly-naphthoic acid glycol ester, polypropylene, tygon, cellulose triacetate, cellulose diacetate, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, polyvinyl chloride, polyvinyl alcohol (PVA), polycarbonate, polystyrene, cellophane, polyvinyl chloromethylated copolymer, polyamide, polyimide, trichloroactic acid vinyl ester copolymers, politef and poly-triclene.Further can also use the compound substance that forms by two or more materials.At above-mentioned preferred pet film in these.The thickness of supporter is generally 5～150 μ m, preferred 10～50 μ m.

Photonasty is transcribed thin slice can further be provided with protective film on second photographic layer.As the example of protective film, can use the material that is used for aforementioned supporter and paper or lamination tygon, polyacrylic paper.Special preferably polyethylene, polypropylene film.The thickness of protective film is generally 5～100 μ m, preferred 10～50 μ m.At this moment must satisfy the relation of A＞B between the adhesion B of the adhesion A of photo-sensitive resin and supporter and photoresist and protective film.As the example of the combination of supporter/protective film, can enumerate polyethylene terephthalate/polypropylene, polyethylene terephthalate/tygon, polyvinyl chloride/cellophane, polyimide/polypropylene etc.Except above-mentioned this supporter and protective film are selected from different material,, also can satisfy the relation of adhesion as the aforementioned by surface treatment is carried out on supporter and at least one side's of protective film surface.In order to improve the adhesion with photoresist, generally carry out the surface treatment of supporter, as its example, can enumerate that the laying of priming paint, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high frequency treatment with irradiation, glow discharge are handled, active plasma treatment with irradiation and laser radiation processing etc.In addition, the coefficient of static friction between supporter and the protective film also is important.Its coefficient of static friction is preferably 0.3～1.4, is preferably 0.5～1.2 especially.If 0.3 of less than is sliding excessively, the volume dislocation takes place when being rolled into tubular easily.If surpass at 1.4 o'clock, be difficult to be rolled into good tubular in addition.

In addition, also can carry out surface treatment to protective film.Surface treatment for reduce and photo-sensitive resin between adhesion carry out.Priming paint such as polysiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol (PVA) for example are set on the surface of protective film.The formation of priming paint be by, the coating liquid of above-mentioned polymkeric substance is coated in the surface of protective film after, carried out in dry 1～30 minute down at 30～150 ℃ (particularly 50～120 ℃).

Above-mentioned photonasty is transcribed thin slice and can be applicable to well in the manufacturing of the printed circuit board (PCB) with through hole or via hole.

Description of drawings

Fig. 1 is illustrated in the sectional view of structure that the preferred photonasty of using in the enforcement of manufacture method of printed circuit board (PCB) of the present invention is transcribed an example of thin slice.

Fig. 2 is for when using up support side when irradiation of transcribing thin slice from the photonasty of Fig. 2, represents the synoptic diagram of the sensitivity curve of the relation between the thickness of the exposure of light and hardened layer.

Fig. 3 is of the present invention to have the synoptic diagram of manufacturing process of the printed circuit board (PCB) of through hole.

Symbol description

10 photonasty are transcribed thin slice

11 supporters

12 first photographic layers

13 second photographic layers

14 protective films

15 circuit patterns form the hardened layer of usefulness

The hardened layer of the metal level protection usefulness of 16 through holes

17 stripping films

21 printed circuit board (PCB)s form uses substrate

22 through holes

23 metal levels

24 circuit patterns

31 backer rolls

The specific embodiment

[embodiment 1]

On the thick pet film (supporter) of 20 μ m, coating is by following component shape The first photosensitive polymer combination solution that becomes, drying forms the thick photosensitive layer of 25 μ m (first photosensitive layer).

[component of the first photosensitive polymer combination solution]

Methyl methacrylate/acrylic acid 2-Octyl Nitrite/benzyl methacrylate/methacrylic acid copolymer (copolymer forms (mol ratio): 55/11.7/4.5/28.8, weight average molecular weight: 90000, Tg:70 ℃)

15 mass parts

12 polypropyleneglycol diacrylates, 6.5 mass parts

Four polyethylene glycol dimethacrylates, 1.5 mass parts

4,4 '-two (diethylin) benzophenone 0.04 mass parts

Benzophenone 1.0 mass parts

Para toluene sulfonamide 0.5 mass parts

Peacock green oxalates 0.02 mass parts

3-morpholino methyl isophthalic acid-phenyl-triazole-2-thioketones 0.01 mass parts

Purple 0.2 mass parts of rock crystal

Trisbromomethyl phenyl sulfone 0.1 mass parts

MEK 30 mass parts

The second photosensitive polymer combination solution that is formed by following component in the coating of first photosensitive layer is then done Dry, form the thick photosensitive layer of 5 μ m (first photosensitive layer).

[component of the second photosensitive polymer combination solution]

Methyl methacrylate/acrylic acid 2-Octyl Nitrite/benzyl methacrylate/methacrylic acid copolymer (copolymer forms (mol ratio): 40/26.7/4.5/28.8, weight average molecular weight: 90000, Tg:50 ℃)

15 mass parts

12 polypropyleneglycol diacrylates, 6.5 mass parts

Four polyethylene glycol dimethacrylates, 1.5 mass parts

4,4 '-two (diethylin) benzophenone 0.4 mass parts

Benzophenone 3.0 mass parts

Para toluene sulfonamide 0.5 mass parts

Peacock green oxalates 0.02 mass parts

Purple 0.2 mass parts of rock crystal

Trisbromomethyl phenyl sulfone 0.1 mass parts

MEK 30 mass parts

On second photosensitive layer, the polyethylene film (protective film) that lamination 20 μ m are thick obtains photonasty and transcribes thin Film. Be ready to thus photonasty and transcribe thin slice. Photonasty is transcribed the susceptibility of thin slice by the knot of following method mensuration Fruit is that making the second photosensitive layer necessary light quantity A that hardens is 4mJ/cm², making the first photosensitive layer necessary light quantity C that begins to harden is 14mJ/cm², (difference between light quantity A and the light quantity C is 10mJ/cm²)。

[assay method of susceptibility]

From pet film (supporter) side, use high-pressure mercury-vapor lamp, use from 0.1mJ/cm²Beginning with 21/2 interval until 100mJ/cm²Till the irradiation photonasty of different light quantities transcribe the sensitization of thin slice Layer makes the photosensitive layer sclerosis. Peel then pet film, remove with the aqueous sodium carbonate dissolving Remove the exposed portion that is of photosensitive layer, hardened layer is developed, measure the thickness of this hardened layer. Then to the exposure of light And the mapping of the relation between the thickness of hardened layer obtains sensitivity curve. From the sensitivity curve that so obtains, read Go out the light quantity (light quantity A) when the thickness of hardened layer is 5 μ m, the light quantity (light when the thickness of hardened layer is 30 μ m Measure B) and the light quantity (light quantity C) when thickness surpasses 5 μ m.

[manufacturing of printed circuit board (PCB)]

The through hole, the surface that are ready to have diameter 3mm have the substrate of copper layer. Use the chemical polishing device, by spray The 8g/ liter), sulfuric acid (concentration: the 100g liter) and copper ion (concentration 1.9g/ liter) mist is with hydrogen peroxide (concentration: Be the treatment fluid of main component, chemical polishing carried out on the surface of the copper layer of this substrate processed, then dry. Process The temperature of liquid is 30 ℃, and nozzle exit pressure is 0.2MPa, and the processing time is 25 seconds. Measure the base after chemical polishing is processed The surface roughness (Ra) of the copper layer on plate surface is 0.12 μ m. In addition, the stop value during mensuration is 80 μ m. Produce thus copper-clad laminate (printed circuit board (PCB) forms and uses substrate).

To peel off then the photonasty of pet film (protective film) and transcribe of thin slice Two photosensitive laminates are combined on the copper-clad laminate, with the crimping of hot-roll lamination machine and make it not have bubble to enter, obtain with Copper-clad laminate, second photosensitive layer, first photosensitive layer and pet film (supporter) The photosensitive layer laminate of order lamination.

From the pet film of the photosensitive layer laminate that obtains, use the exposure device of the blue laser light source with 405nm, form on the zone at the circuit pattern of copper-clad laminate, with 4mJ/cm²Irradiation on the pattern form of regulation, on the other hand, on the opening portion and neighboring area thereof of the through hole of copper-clad laminate, with 4mJ/cm²Irradiation, make photosensitive layer exposure. After the exposure, peel poly-to benzene from the photosensitive layer laminate Dioctyl phthalate glycol ester film (supporter) is the carbon of 1 quality % to the second photosensitive layer surface spray concentration then Acid sodium aqueous solution, the unhardened zone that first photosensitive layer and second photosensitive layer are removed in dissolving obtains the hardened layer relief.

Hardened layer pattern on the copper-clad laminate is observed, formed hardened layer on the zone and logical at circuit pattern Do not find on the hardened layer on the opening portion of hole to peel off or the defective such as breakage. In addition, measure the thickness of hardened layer, The thin hardened layer that circuit pattern forms on the zone is 5 μ m, and the thin hardened layer on the via openings part is 30 μ m. In addition, the circuit pattern minimum that forms the hardened layer on the zone is differentiated live width and (spot, coarse etc. unusual do not occurred The width of the hardened layer pattern of the minimum of situation) is 20 μ m.

Contain then the etching solution of iron chloride in the surface spray coating of copper-clad laminate, dissolving is removed and is not hardened The copper layer on the exposure area that layer covers, the concentration of spraying then is that the sodium hydrate aqueous solution of 2 quality % is removed firmly Change a layer relief, the surface that obtains having through hole has the printed circuit board (PCB) of the copper layer of circuit pattern shape. Use visual sight Examine the through hole of the printed circuit board (PCB) that obtains, the copper coating of through-hole wall does not note abnormalities.

[embodiment 2]

The through hole, the surface that are ready to have diameter 3mm have the substrate of copper layer. Use the chemical polishing device, by spray Mist take hydrogen peroxide (concentration: the 4g/ liter), sulfuric acid (concentration: the 50g liter) and copper ion (concentration 1g/ liter) as The treatment fluid of main component carries out chemical polishing to the surface of the copper layer of this substrate and processes, and is then dry. Treatment fluid Temperature be 30 ℃, nozzle exit pressure is 0.2Mpa, the processing time is 25 seconds. Measure the substrate after chemical polishing is processed The surface roughness (Ra) of the copper layer on surface is 0.05 μ m. In addition, the stop value during mensuration is 80 μ m. By This produces copper-clad laminate (printed circuit board (PCB) forms and uses substrate). Except using the copper-clad laminate of as above making In addition, all the other form the hardened layer pattern according to the method same with embodiment 1 at copper-clad laminate.

Hardened layer pattern on the copper-clad laminate is observed, formed hardened layer on the zone and logical at circuit pattern Do not find on the hardened layer on the opening portion of hole to peel off or the defective such as breakage. In addition, circuit pattern forms on the zone The minimum of hardened layer to differentiate live width be 20 μ m. Then with embodiment 1 similarly, by etched copper, remove then Remove the hardened layer relief, obtain printed circuit board (PCB). The through hole of the printed circuit board (PCB) that obtains with visualization, through-hole wall Copper coating do not note abnormalities.

[embodiment 3]

The through hole, the surface that are ready to have diameter 3mm have the substrate of copper layer. Use the chemical polishing device, by spray The 15g/ liter), sulfuric acid (concentration: the 200g liter) and copper ion (concentration 4g/ liter) mist is with hydrogen peroxide (concentration: Be the treatment fluid of main component, chemical polishing carried out on the surface of the copper layer of this substrate processed, then dry. Process The temperature of liquid is 30 ℃, and nozzle exit pressure is 0.2MPa, and the processing time is 25 seconds. Measure the base after chemical polishing is processed The surface roughness (Ra) of the copper layer on plate surface is 0.20 μ m. In addition, the stop value during mensuration is 80 μ m. Produce thus copper-clad laminate (printed circuit board (PCB) forms and uses substrate). Except using the copper facing lamination of as above making Beyond the plate, all the other form the hardened layer pattern according to the method same with embodiment 1 at copper-clad laminate.

Hardened layer pattern on the copper-clad laminate is observed, formed hardened layer on the zone and logical at circuit pattern Do not find on the hardened layer on the opening portion of hole to peel off or the defective such as breakage. In addition, circuit pattern forms on the zone The minimum of hardened layer to differentiate live width be 25 μ m. Then with embodiment 1 similarly, by etched copper, remove then Remove the hardened layer relief, obtain printed circuit board (PCB). The through hole of the printed circuit board (PCB) that obtains with visualization, through-hole wall Copper coating do not note abnormalities.

[embodiment 4]

The through hole, the surface that are ready to have diameter 3mm have the substrate of copper layer. Use the chemical polishing device, by spray The 25g/ liter), sulfuric acid (concentration: the 200g liter) and copper ion (concentration 6g/ liter) mist is with hydrogen peroxide (concentration: Be the treatment fluid of main component, chemical polishing carried out on the surface of the copper layer of this substrate processed, then dry. Process The temperature of liquid is 30 ℃, and nozzle exit pressure is 0.2Mpa, and the processing time is 25 seconds. Measure the base after chemical polishing is processed The surface roughness (Ra) of the copper layer on plate surface is 0.30 μ m. In addition, the stop value during mensuration is 80 μ m. Produce thus copper-clad laminate (printed circuit board (PCB) forms and uses substrate). Except using the copper facing lamination of as above making Beyond the plate, all the other form the hardened layer pattern according to the method same with embodiment 1 at copper-clad laminate.

Hardened layer pattern on the copper-clad laminate is observed, formed hardened layer on the zone and logical at circuit pattern Do not find on the hardened layer on the opening portion of hole to peel off or the defective such as breakage. In addition, circuit pattern forms on the zone The minimum of hardened layer to differentiate live width be 30 μ m. Then with embodiment 1 similarly, by etched copper, remove then Remove the hardened layer relief, obtain printed circuit board (PCB). The through hole of the printed circuit board (PCB) that obtains with visualization, through-hole wall Copper coating do not note abnormalities.

[embodiment 5]

The through hole, the surface that are ready to have diameter 3mm have the substrate of copper layer. Use the chemical polishing device, by spray The 30g/ liter), sulfuric acid (concentration: the 200g liter) and copper ion (concentration 8g/ liter) mist is with hydrogen peroxide (concentration: Be the treatment fluid of main component, chemical polishing carried out on the surface of the copper layer of this substrate processed, then dry. Process The temperature of liquid is 30 ℃, and nozzle exit pressure is 0.2MPa, and the processing time is 25 seconds. Measure the base after chemical polishing is processed The surface roughness (Ra) of the copper layer on plate surface is 0.40 μ m. In addition, the stop value during mensuration is 80 μ m. Produce thus copper-clad laminate (printed circuit board (PCB) forms and uses substrate). Except using the copper facing lamination of as above making Beyond the plate, all the other form the hardened layer pattern according to the method same with embodiment 1 at copper-clad laminate.

Hardened layer pattern on the copper-clad laminate is observed, formed hardened layer on the zone and logical at circuit pattern Do not find on the hardened layer on the opening portion of hole to peel off or the defective such as breakage. In addition, circuit pattern forms on the zone The minimum of hardened layer to differentiate live width be 50 μ m. Then with embodiment 1 similarly, by etched copper, remove then Remove the hardened layer relief, obtain printed circuit board (PCB). The through hole of the printed circuit board (PCB) that obtains with visualization, through-hole wall Copper coating do not note abnormalities.

[comparative example 1]

The through hole, the surface that are ready to have diameter 3mm have the substrate of copper layer. Use the chemical polishing device, by spray The 55g/ liter), sulfuric acid (concentration: the 300g liter) and copper ion (concentration 8g/ liter) mist is with hydrogen peroxide (concentration: Be the treatment fluid of main component, chemical polishing carried out on the surface of the copper layer of this substrate processed, then dry. Process The temperature of liquid is 40 ℃, and nozzle exit pressure is 0.25MPa, and the processing time is 40 seconds. After the mensuration chemical polishing is processed The surface roughness (Ra) of the copper layer of substrate surface is 0.50 μ m. In addition, the stop value during mensuration is 80 μ m. Produce thus copper-clad laminate (printed circuit board (PCB) forms and uses substrate). Except using the copper facing lamination of as above making Beyond the plate, all the other form the hardened layer pattern according to the method same with embodiment 1 at copper-clad laminate.

Hardened layer pattern on the copper-clad laminate is observed, formed hardened layer on the zone and logical at circuit pattern Do not find on the hardened layer on the opening portion of hole to peel off or the defective such as breakage. In addition, circuit pattern forms on the zone The minimum of hardened layer to differentiate live width be 80 μ m. Then with embodiment 1 similarly, by etched copper, remove then Remove the hardened layer relief, obtain printed circuit board (PCB). The through hole of the printed circuit board (PCB) that obtains with visualization, through-hole wall Copper coating do not note abnormalities.

Claims

1. the manufacture method of a printed circuit board (PCB), it comprises following operation:

(1) make following printed circuit board (PCB) and form the operation of using substrate: this substrate is on supporter, according to first photographic layer, the order lamination of second photographic layer forms photonasty and transcribes thin slice, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form this first photographic layer of relative low sensitivity, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form high sensitive relatively this second photographic layer: and cover metal level on substrate surface, the surfaceness that this metal level is represented with Ra is in the scope of 0.01 to 0.40 μ m;

(2) form with on the surface of substrate at printed circuit board (PCB), photonasty is transcribed thin slice to be crimped on the metal level, so that its second photographic layer and metal layer contacting form the lamination that makes photonasty lamination body with the order lamination of substrate, second photographic layer, first photographic layer and supporter according to printed circuit board (PCB);

(3) from the support side of photonasty lamination body, at least the circuit pattern that forms with substrate to printed circuit board (PCB) forms in the zone, with the pattern form that the rayed of the necessary light quantity of sclerosis second photographic layer is stipulated, form the circuit part exposure process in the hardened layer zone of predetermined pattern;

(4) peel off the supporter stripping process of supporter from photonasty lamination body;

(5) dissolving is removed in the unhardened zone of printed circuit board (PCB) formation with first photographic layer on the substrate and second photographic layer, so that the developing procedure of the metal level in the unhardened zone of this of substrate surface exposure;

(6) remove the etching work procedure of the metal level of exposure area with etching solution dissolving; And

2. the manufacture method of claim 1 record, wherein the surfaceness of metal level is to handle by chemical polishing to be adjusted in the above-mentioned scope.

3. the manufacture method of the printed circuit board (PCB) of claim 1 record is characterized in that light used in the operation (3) is laser.

4. manufacture method with printed circuit board (PCB) of through hole or via hole, it comprises following operation:

(1) make following printed circuit board (PCB) and form the operation of using substrate: this substrate is on supporter, according to first photographic layer, the order lamination of second photographic layer forms photonasty and transcribes thin slice, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form this first photographic layer of relative low sensitivity, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form high sensitive relatively this second photographic layer: and cover the metal level with through hole or via hole on substrate surface, the surfaceness that this metal level is represented with Ra is in the scope of 0.01 to 0.40 μ m;

(3) circuit pattern that forms with substrate from the supporter side direction printed circuit board (PCB) of photonasty lamination body forms in the zone, with the pattern form that the rayed of the necessary light quantity of sclerosis second photographic layer is stipulated, form the circuit part exposure process in the hardened layer zone of predetermined pattern;

(4) from the support side of photonasty lamination body, in the zone of the opening portion that contains through-holes of printed circuit boards or via hole, with the pattern form that the rayed of harden simultaneously first photographic layer and the necessary light quantity of second photographic layer is stipulated, form the bore portion exposure process in the hardened layer zone of the open area that covers through hole or via hole;

(5) peel off the supporter stripping process of supporter from photonasty lamination body;

(6) dissolving is removed in the unhardened zone of printed circuit board (PCB) formation with first photographic layer on the substrate and second photographic layer, so that the developing procedure of the metal level in the unhardened zone of this of substrate surface exposure;

(7) remove the etching work procedure of the metal level of exposure area with etching solution dissolving; And

5. the manufacture method of claim 4 record, wherein the surfaceness of metal level is to handle by chemical polishing to be adjusted in the above-mentioned scope.

6. the manufacture method of the printed circuit board (PCB) of claim 1 record is characterized in that used light is laser in operation (3) and the operation (4).

7. photonasty lamination body, on the surface of printed circuit board (PCB) formation, cover metal level with substrate, the surfaceness that this metal level is represented with Ra is in the scope of 0.01 to 0.40 μ m, on this substrate according to second photographic layer, the order lamination of first photographic layer, second photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link is by rayed polymerization sclerosis, form high sensitive relatively this second photographic layer, first photographic layer is by containing binder polymer, contain that the photosensitive polymer combination of the monomer of vinyl unsaturated link and Photoepolymerizationinitiater initiater forms, the monomer that contains the vinyl unsaturated link forms this first photographic layer of relative low sensitivity by rayed polymerization sclerosis.

8. the photonasty lamination body of claim 7 record, wherein the surfaceness of metal level is to handle by chemical polishing to be adjusted in the above-mentioned scope.

9. the photonasty lamination body of claim 7 record, wherein support body layer is pressed on first photographic layer.