CN101106869A - Method for manufacturing printed board - Google Patents
Method for manufacturing printed board Download PDFInfo
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- CN101106869A CN101106869A CNA2007101273129A CN200710127312A CN101106869A CN 101106869 A CN101106869 A CN 101106869A CN A2007101273129 A CNA2007101273129 A CN A2007101273129A CN 200710127312 A CN200710127312 A CN 200710127312A CN 101106869 A CN101106869 A CN 101106869A
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Abstract
The invention provides a producing method of a printed circuit board. The producing method of the printed circuit board can produce a fine circuit. The method can produce the printed circuit board with a short procedure and a low cost, and configurate a conductive layer at the hole portion reliably when producing the multi-layer distribution board with the hole such as through hole. The producing method of the printed circuit board has following steps: a resist forming procedure for configurating the pattern plating including forming a hole on the insulated substrate, setting a first metal conductive layer, jetting the material used for forming a resist layer to the surface of the first metal conductive layer in the electrostatic mode and solidifying it; a resist removing procedure for removing the resist layer for plating including plating the laminated unit of the resist layer for the pattern plating, forming a second metal conductive layer in a pattern shape; an etching procedure of the first metal conductive layer removing the areas outside the forming portion of the second metal conductive layer.
Description
Technical field
The present invention relates to a kind of manufacture method of printed circuit board (PCB), particularly, the present invention relates to the manufacture method of the circuit substrate of a kind of application false add (semiadditive) method, the printed circuit board (PCB) that can form the conductive layer of pattern-like, semiconductor device etc. with high meticulous and thickness sufficient.
Background technology
As the method for making circuit substrate, known have subtract (subtractive) method, add (additive) method, half add.Utilizing subtraction to form under the situation of fine circuits, owing to exist the edge fusion of metal conducting layer to cause that groove attenuates etc., so be disadvantageous to fine circuits.On the other hand, though addition is favourable to fine circuits, owing to apply the whole metal conducting layers of formation with electroless plating, so there is the high problem of manufacturing cost.Though the half add operation is many, can use can high speed operation plating, so, can preferentially use as the fine circuits manufacture method.
Enumerate an example of utilizing half add to make the process of circuit substrate.At first, at insulating properties substrate 1 (Figure 1A) the first thin metal conducting layer 2 (Figure 1B) is set.Then, circuit not formation portion form plating resist layer 3 (Fig. 1 C).Then, utilize electroplating processes, the surface of the part of exposing at first metal conducting layer 1 forms second metal conducting layer 4 (Fig. 1 D).Then, remove this resist layer 3 (Fig. 1 E), the first thin metal conducting layer 1 under this resist layer is removed in etching, obtains being formed with the substrate (Fig. 1 F) of the circuit 5 of the pattern-like that is made of first metal conducting layer and second metal conducting layer.
The formation of plating resist layer is used stencil printing, is had the photo-fabrication of the exposure imaging operation of using photosensitive material, ink-jet method, electro-deposition photoresist method etc.Wherein, stencil printing can be made cheaply, but can not corresponding densification, and purposes is defined.Photo-fabrication can be preferentially used in corresponding densification.As photo-fabrication, typically use the method for minus (photo-crosslinking type) or eurymeric (photolysis type) photoresist.But photo-fabrication is owing to the process, exposure process, the developing process that need to be suitable for to substrate photosensitive material at least, so there are the many shortcomings of operation.
Though ink-jet method operation simple (simple), but because the characteristic of the anticorrosive additive material of ejection, the ink-jet recording of common applied heat mode, piezoelectricity mode, utilize these methods, although can utilize stencil printing to form highdensity pattern, but because pattern exploring degree is than photo-fabrication difference, so the example that is not practical.
But, along with small-sized, the multifunction of in recent years electronic instrument, circuit substrate also is being pushed into aspect the miniaturization of densification or Wiring pattern, as the means that realize such condition, can enumerate the multiple stratification of circuit substrate.Promptly, the circuit substrate that stacked a plurality of wiring layer forms forms the hole that is commonly called open-work 21, through hole 22, space (interstitial) through hole 23 with the shape shown in Fig. 2 A, shown in Fig. 2 B, by cover or fill the pore that is called as through hole, non-through hole (following they are generically and collectively referred to as " hole ") of inwall with metal conducting layer, carry out the conducting of each interlayer.
Fig. 3 is the skeleton diagram of expression from the top inspection hole.31 formation on every side is called as the metal conducting layer of terminal pad (land) 32 in the hole.Terminal pad has various kinds such as circle, ellipse, abnormity, but from the use easness of occupied area or design surface, uses circular mostly.In addition, for corresponding densification, need the hole of no terminal pad (landless) or narrow and small terminal pad width.
Then, use half add, an example of process that manufacturing is had the circuit substrate in hole describes.At first, prepare insulating properties substrate 1 (Fig. 4 A), form hole 6 (Fig. 4 B) therein, at insulating properties substrate 1 thin first metal conducting layer 2 (Fig. 4 C) is set then with hole 6.Then, circuit not formation portion form plating resist layer 3 (Fig. 4 D).Utilize electroplating processes then, the surface of the part of exposing at first metal conducting layer 1 forms second metal conducting layer 4 (Fig. 4 E).Then, remove this resist layer 3 (Fig. 4 F), the first thin metal conducting layer 1 under this resist layer 3 is removed in etching, obtains being formed with the substrate (Fig. 4 G) of the circuit 5 of the pattern-like that is made of first metal conducting layer and second metal conducting layer.Half add is owing to utilize electroplating processes also 6 inside are provided with second metal conducting layer 5 in the hole, thus must be in the hole 6 parts do not form the state of plating resist layer.
For so not part in the hole forms the plating resist, under the situation of the minus of stating in the use (photo-crosslinking type) dry film photoresist, thereby need carry out shading to hole and terminal pad portion does not make minus (photo-crosslinking type) dry film photoresist crosslinked, and remove unreacted dry film photoresist, do not form the plating resist layer in hole portion and terminal pad portion.In this operation, the perforate processing in hole or the contraposition of exposure process become very important, particularly in the hole of desired no terminal pad of high-density circuit substrate and narrow and small terminal pad width, become must be very high contraposition precision, under the situation of narrow and small terminal pad width, if hole and the dislocation of terminal pad generation same distance then all can not form the hole that has narrow and small terminal pad in whole peripheries.
In addition, under the situation in the situation in the hole of the no terminal pad of manufacturing, the hole of small-bore, if the light shielding part dislocation, then light shielding part departs from the hole, so it is crosslinked that the minus of hole portion (photo-crosslinking type) dry film photoresist takes place, thereby do not remove the plating resist layer (for example with reference to patent documentation 1) of hole portion.
In fact because the very little method variation of flexible, the photomask for use in exposure of the precision of perforate processing, substrate etc., so there is the limit in contraposition precision.In addition, the diameter in the hole that forms on the high-density circuit substrate is multiple, and hole count is also extremely many, is very difficult so whole holes are accurately located.Thereby, the high-density circuit substrate not only needs not have the hole of terminal pad or narrow and small terminal pad width, and be under the situation of narrow and small terminal pad width, thereby that minus (photo-crosslinking type) dry film photoresist is taken place is crosslinked for the shading of carrying out hole portion reliably, then the terminal pad width must be designed big (for example with reference to patent documentation 2).Under the situation in the hole of no terminal pad, for thereby the shading of carrying out reliably in the portion of hole does not make the generation of minus (photo-crosslinking type) dry film photoresist crosslinked, then must design light shielding part less, so plating solution becomes and be difficult to invade in the hole, thereby do not carry out plating.
As the method that forms the plating resist layer, in described patent documentation 2, also put down in writing the method for using the electro-deposition photoresist.This is a kind of electro-deposition coated method of utilizing, and electro-deposition photoresist layer similarly is set containing on the metal conducting layer of porose inwall, then by exposing, develop by photomask, the method for plating resist layer is set.
The electro-deposition photoresist comprises minus (photo-crosslinking type) and eurymeric (photolysis type).Under the situation for eurymeric (photolysis type), thereby need expose photoresist is decomposed, if be the open-work of cylindrical shape, then can not be to exposing in the hole, can not fully decompose inner electro-deposition photoresist, so can not be used as the plating resist layer.If be the through hole of cone-shaped, only use the photomask of the pattern that does not have terminal pad, the hole of no terminal pad can be formed, but the electro-deposition photoresist of inside, hole can not be fully decomposed.
In addition, make under the situation in hole of narrow and small terminal pad width, use is designed to photomask that terminal pad portion is exposed, but with in above-mentioned minus (photo-crosslinking type) dry film photoresist, illustrate identical, contraposition precision existing problems, so have the problem of the location dislocation of terminal pad, can not form the hole that has narrow and small terminal pad in whole peripheries.Thereby, the terminal pad width must be strengthened, thereby narrow and smallization of terminal pad can not be tackled.
On the other hand, under the situation for minus (photo-crosslinking type) electro-deposition photoresist, inside, hole does not need to expose, so as the photomask that only uses the pattern that does not have terminal pad, the means that form the hole of no terminal pad are effective, but when being the through hole of cone-shaped,, can not remove the inwall in hole and the plating resist layer of whole bottom surface because light is partly invaded.Thereby, under the situation of the circuit substrate of open-work and through hole coexistence, can not remove the plating resist layer in the whole holes that are present in circuit substrate.
In addition, use minus (photo-crosslinking type) electro-deposition photoresist to make under the situation in hole of narrow and small terminal pad width, use is designed to photomask that terminal pad portion is exposed, but with in above-mentioned minus (photo-crosslinking type) dry film photoresist, illustrate identical, contraposition precision existing problems are so exist the problem of the location dislocation of terminal pad.
Like this, in the manufacture method of present resist, existence can not be tackled the problem of narrow and smallization of terminal pad, need to use the advantage of having given play to half add resist manufacture method and use the circuit formation method of this resist.
Patent documentation 1: the spy opens flat 10-178031 communique
Patent documentation 2: the spy opens flat 7-7265 communique
Summary of the invention
Consider described in the past problem points and the problem of the present invention that proposes is, provide a kind of manufacturing that can tackle fine circuits, can also be with short operation, the low-cost manufacture method of making the printed circuit board (PCB) of printed circuit board (PCB).Be not subjected to when a kind of multi-layered wiring board that has hole such as through hole in manufacturing particularly is provided the aligning accuracy of the shape in hole or exposure process influence, can form the manufacture method of the printed circuit board (PCB) of conductive layer reliably at bore portion.
The inventor etc. concentrate on studies in order to solve described problem, found that by be suitable for the electrostatic means ink jet recording method in the formation of pattern platedresist, can solve described problem, so that finish the present invention.
That is, the present invention is as described below.
＜1〉a kind of manufacture method of printed circuit board (PCB), it has at least: utilize the electrostatic means ink-jet, resist layer formed with material be ejected in the first metallic conduction laminar surface that the duplexer that first metal conducting layer forms is set on the insulating properties substrate, and make this resist layer formation material cured, form pattern and electroplate the resist formation operation of using resist layer; Electroplate with the duplexer of resist layer being formed with this pattern plating, form the electroplating work procedure of second metal conducting layer with pattern-like; Remove to electroplate and remove operation with the resist of resist layer; The etching work procedure of first metal conducting layer in the zone beyond the formation portion of established second metal conducting layer is removed in etching.
＜2〉according to＜1〉described manufacture method, wherein, the thickness of described first metal conducting layer is 0.1～20 μ m.
＜3〉according to＜1〉described manufacture method, wherein, described resist layer forms and contains polymer, dispersant, charged conditioning agent with material in carrier fluid.
＜4〉according to＜3〉described manufacture method, wherein, described charged conditioning agent is the polymer compound with carboxylic acid group.
＜5〉according to＜1〉described manufacture method, wherein, the dried thickness of formed described resist layer is 1～100 μ m.
＜6〉a kind of manufacture method of printed circuit board (PCB), it has at least: after the insulating properties substrate formed through hole and/or non-through hole, the metal conducting layer that first metal conducting layer is set formed operation; Utilize the electrostatic means ink-jet, resist layer is formed be ejected in the first metallic conduction laminar surface, and make this resist layer formation material cured, form the pattern plating and use the resist of resist layer to form operation with material; Electroplate with the duplexer of resist layer being formed with this pattern plating, form the electroplating work procedure of second metal conducting layer with pattern-like; Remove to electroplate and remove operation with the resist of resist layer; The etching work procedure of first metal conducting layer in the zone beyond the formation portion of established second metal conducting layer is removed in etching.
＜7〉according to＜6〉described manufacture method, wherein, the thickness of described first metal conducting layer is 0.1～20 μ m.
＜8〉according to＜6〉described manufacture method, wherein, described resist layer forms and contains polymer, dispersant, charged conditioning agent with material in carrier fluid.
＜9〉according to＜8〉described manufacture method, wherein, described charged conditioning agent is the polymer compound with carboxylic acid group.
＜10〉according to＜6〉described manufacture method, wherein, the dried thickness of formed described resist layer is 1～100 μ m.
Utilize the manufacture method of printed circuit board (PCB) of the present invention, owing to use half add, form with the ink-jet method resist of electrostatic means, thus can tackle fine circuits manufacturing, can also be with short operation, the low-cost printed circuit board (PCB) of making.Be not subjected to when particularly having the multi-layered wiring board in hole such as through hole in manufacturing the contraposition precision of the shape in hole or exposure process influence, can form conductive layer at bore portion reliably.
Description of drawings
Figure 1A～Fig. 1 F is that expression utilizes half add to make the summary sectional view of an example of the process of circuit substrate.
Fig. 2 A is the summary sectional view of the shape of expression open-work, through hole, space through hole.
Fig. 2 B is the summary sectional view of expression with the state of the peristome inwall shown in the metal conducting layer coverage diagram 2A
Fig. 3 is the skeleton diagram that the periphery that is illustrated in the peristome in hole such as open-work forms the state of terminal pad (metal conducting layer).
Fig. 4 A～Fig. 4 G is that expression utilizes half add to be manufactured on the summary sectional view of an example of process that the insulating properties substrate is provided with the circuit substrate in hole.
Fig. 5 is the concept map of ink gun of representing can be used to form in the present invention the electrostatic ink-jet recording apparatus of platedresist layer.
Embodiment
Following with reference to accompanying drawing, according to process sequence manufacture method of the present invention is elaborated.
At this, the example that uses the insulating properties substrate that has formed the hole is described, even but under the situation of using the insulated substrate that does not have the hole, also can similarly carry out with reference to " formation in hole " operation.
Fig. 4 A～Fig. 4 G is a mode as circuit substrate manufacturing method of the present invention, represents to have the sectional view of manufacture method of the circuit substrate in hole according to process sequence.At this, be that example describes with the through hole, even but non-through hole also can be used the same method with following explanation, make circuit substrate.In addition, even integrated (buildup) substrate of open-work (through hole) and through hole (via hole) coexistence, also can be with identical method manufacturing.
＜on the insulating properties substrate, form after through hole and/or the non-through hole, the metal conducting layer that first metal conducting layer is set forms operation 〉
At first, prepare insulation base substrate 1 (Fig. 4 A), form hole 6 (Fig. 4 B) therein.
As the insulating properties substrate that uses among the present invention, the representative substrate that comprises paper base material phenolic resin or glass baseplate epoxy resin, polyimide film, organic polymer film etc.These insulating properties substrates for example can use the insulating properties substrate of the needs of record in " printed circuit technique brief guide " (the printed circuit industry of civic organization Japan can be compiled, and 1987 publish, Nikkan Kogyo Shimbun's distribution).
Then, thin first metal conducting layer 2 (Fig. 4 C) is set forming on the insulating properties substrate in hole 6.
The method that first metal conducting layer 2 is set on the insulating properties substrate 1 in the present invention is not particularly limited, for example can enumerates and on substrate surface, adhere to the deposited catalyst of electroless plating or its precursor, utilize electroless plating to apply the method that method forms metallic film; The method of conductive layer as thin as a wafer such as bonded metal paper tinsel on the insulating properties substrate; Thereby etch processes this conductive layer of the plywood of bonded metal conductive layer becomes method of film etc., can be suitable for any one method wherein.
At this, as forming the conductive metal of using in first metal conducting layer,, be generally copper or contain the alloy of copper from the viewpoint of electrical conductance, but be not limited thereto, can also use metals such as gold, silver, chromium, lead, tin, zinc or contain alloy of these metals etc.
The thickness of first metal conducting layer that will form can suitably be selected according to purposes, is preferably usually about 0.1～20 μ m.
＜utilize the electrostatic means ink-jet, first metallic conduction laminar surface ejection resist layer is formed with material and it is solidified, form the resist that pattern electroplates with resist layer and form operation
Then, form plating resist layer 3 (Fig. 4 D) in the zone that does not form circuit.Utilize the ink-jet method of the following electrostatic means that describes in detail to form plating resist layer 3.
The plating resist layer contain the plating resist layer remove in the liquid be soluble, in electroplate liquid insoluble resin.
The invention is characterized in,, use the electrostatic means ink-jet recording apparatus for the zone at needs forms this plating resist layer 3.As the ink-jet recording apparatus of operable electrostatic means among the present invention, for example can use the spy to open the ink-jet recording apparatus of putting down in writing in the flat 10-230608 communique.Fig. 5 is the concept map of the ink gun of operable electrostatic ink-jet recording apparatus among expression the present invention.
This ink gun 50 possesses head substrate 52, black liquid guider (guide) 54, insulating properties substrate 56, control electrode 58, electrode base board 60, DC (bias) potential source 62, pulse voltage source 64 partially.
On insulating properties substrate 56, be formed for spraying the ejiction opening (through hole) 66 of black liquid.In the orientation of this ejiction opening 66, extend head substrate 52 is set, the black liquid guider 54 of configuration on the head substrate 52 of the position of corresponding ejiction opening.China ink liquid guider 54 connects ejiction opening 66, and fore-end 54a is more outstanding to top than the surface with opposition sides head substrate 52 sides insulating properties substrate 56.
Containing charged to some extent and voltage that apply to control electrode 58 is the black liquid Q of the particulate (look material particle) of identical polar, cycling mechanism by not shown black liquid, make its in this China ink liquid runner 68 for example from figure the right side circulate to the left, supply with black liquid to each ejiction opening 66.
In so electrostatic ink mist recording, recording medium P preferably utilizes the Charging system of charged device of gate charges (scorotron) etc., charged be under the high-tension state opposite with control electrode, be held in the insulating barrier 61 of the electrode base board 60 of ground connection.
In so electrostatic ink mist recording, do not applying under the state of voltage to control electrode 58, repulsion between the enclosed pasture gravitation between the look material particle in bias voltage that compound opposite electrode causes and the black liquid, the viscosity of black liquid (decentralized medium), surface tension, charged particle, the fluid pressure that black liquid is supplied with etc., China ink liquid becomes the crescent-shaped of slightly upwards swelling from ejiction opening (nozzle) 66, reaches balance.
In addition, under the effect of this coulomb gravitation etc., look material particle generation swimming, move to crescent-shaped, that is, black liquid becomes the state that has been concentrated.
If apply ((ON) opened in ejection) voltage to control electrode 58, then bias voltage and driving voltage are overlapping, the result, and black liquid Q is drawn to recording medium P (opposite electrode) side draught, forms approximate cone shape so-called Taylor's circular cone (Taylor cone).
Begin to apply after the control electrode, along with effluxion, the balance that acts between the surface tension of enclosed pasture gravitation and decentralized medium of look material particle is destroyed, and formation is called as the diameter that drags horizontal hair and counts elongate ink liquid fluid column about μ m～tens of μ m.And then, along with effluxion,, dragging the front end division of horizontal hair as institute's announcements in No. 4314263 specification of United States Patent (USP) etc., the drop O quilt of black liquid sprays to recording medium P, attracts to circle in the air.
In electrostatic ink-jet, usually by to 58 modulation of each control electrode, apply pulse voltage, make ejection ON/OFF (ON/OFF), the black liquid drop of modulation ejection carries out the ejection of black liquid drop of the request formula (on-demand) of corresponding record image.
(the plating resist layer forms and uses material)
At this, the resist layer formation that is used to form resist layer is elaborated with material.
The resist layer that is used to form the plating resist layer forms preferably to use with material and disperse the product that contains the composition of polymer, dispersant, charged conditioning agent and make its granulating gained in carrier fluid.
Carrier fluid is preferably high resistivity, particularly has 10
10The liquid of the dielectric resistance that Ω cm is above.If use the low carrier fluid of resistivity, then between adjacent control electrode, produce and conduct, so be not suitable in the present invention.
In addition, the dielectric constant of carrier fluid (dielectric resistance liquid) is preferably below 5, more preferably below 4, and then is preferably below 3.5.Dielectric constant by making decentralized medium is in this scope, and electric field can act on the particle of carrier fluid effectively, so preferred.
As such carrier fluid, the halogen of aliphatic hydrocarbon, ester ring type hydrocarbon or aromatic hydrocarbon and these hydrocarbon of preferred illustration straight chain shape or branch-like replaces body, silicone oil etc.
As an example, can be used alone or as a mixture hexane, heptane, octane, isooctane, decane, isodecane, decahydronaphthalene, nonane, dodecane, Permethyl 99A, cyclohexane, cyclooctane, cyclodecane, toluene, dimethylbenzene, mesitylene, ISOPARC, ISOPARE, ISOPARG, ISOPARH, ISOPARL, ISOPARM (ISOPAR; The trade name of EXON company), SHELLSOL70, SHELLSOL71 (SHELLSOL; The trade name of SHELLOIL company), ア system ス コ OMS, ア system ス コ 460 solvents (ア system ス コ; The trade name of SPIRITS company), KF-96L (trade name of SILICON company of SHIN-ETSU HANTOTAI) etc.
The content that the whole relatively resist layer of carrier fluid forms with material is preferably 20～99 quality %.Content by making carrier fluid can make Dispersion of Particles in carrier fluid more than 20 quality % well, by making them below 99 quality %, can make the content abundance of particle.
Carrier fluid is preferably high resistivity, particularly has 10
10The liquid of the dielectric resistance that Ω cm is above.If use the low carrier fluid of resistivity, then between adjacent control electrode, produce and conduct, so be not suitable in the present invention.
In addition, the dielectric constant of carrier fluid (dielectric resistance liquid) is preferably below 5, more preferably below 4, and then is preferably below 3.5.Dielectric constant by making decentralized medium is in this scope, and electric field can act on the particle of carrier fluid effectively, so preferred.
Form with in the material at resist layer, the state with particulate in carrier fluid contains as the polymer that solidifies and form the material of resist.
As polymer, for example can enumerate ethylidene ether modification thing, Merlon of rosin based, rosin modified phenol resin, alkyd resins, (methyl) acrylic acid series polymeric compounds, polyurethane, polyester, polyamide, polyethylene, polybutadiene, polystyrene, polyvinyl acetate, polyvinyl alcohol etc.
Wherein, from the viewpoint of granuloplastic easy degree, preferable weight-average molecular weight is 2,000～1000, in 000 the scope and the polymer of polydispersity (weight-average molecular weight/number-average molecular weight) in 1.0～5.0 scope.And then, from the viewpoint of the easy degree of described photographic fixing, any one polymer in 40 ℃～120 ℃ scope of preferred softening point, vitrifying point or fusing point.
At this, as polymer especially preferably use contain the construction unit shown in following general formula (1)～(4) at least any one and with the polymer of at least a combined polymerization gained of the construction unit that contains acid groups such as (methyl) acrylic acid.
[changing 1]
General formula (1)
General formula (2)
General formula (3)
General formula (4)
In the described formula, R
11Expression hydrogen atom or methyl, R
12The alkyl of expression carbon number 1～30.X
11The expression oxygen atom or-N (R
13)-, be at this, R
13The alkyl of expression hydrogen atom or carbon number 1～30.R
21The alkyl of expression hydrogen atom or carbon number 1～20.R
31, R
32, R
412 yuan of alkyl representing 1～20 of carbon number respectively.Wherein, R
12, R
21, R
31, R
32, R
41Alkyl in, also comprise ehter bond, amino, hydroxyl or halogenic substituent.
The polymer that contains the construction unit of general formula (1) expression can obtain corresponding free radical polymerization monomer generation radical polymerization by utilizing known method.
As the free radical polymerization monomer that uses, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid 2-b hexyl, (methyl) dodecylacrylate, (methyl) stearyl acrylate acid esters, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid benzyl ester, (methyl) esters of acrylic acid and N-methyl (methyl) acrylamides such as (methyl) acrylic acid 2-hydroxyl ethyl ester, N-propyl group (methyl) acrylamide, N-phenyl (methyl) acrylamide, N, (methyl) acrylic amides such as N-dimethyl (methyl) acrylamide.
The polymer that contains the construction unit of general formula (2) expression can obtain corresponding free radical polymerization monomer generation radical polymerization by utilizing known method.As the free radical polymerization monomer that uses, for example can enumerate ethene, propylene, butadiene, styrene, 4-methyl styrene etc.
The polymer that contains the construction unit of general formula (3) expression can obtain corresponding dicarboxylic acids or acid anhydrides and glycol generation dehydrating condensation by utilizing known method.
As the dicarboxylic acids and the acid anhydrides that use, for example can enumerate succinyl oxide, adipic anhydride, sebacic anhydride, isophthalic acid, terephthalic acids, 1,4-phenylenediacetic Acid, diglycolic acid etc.In addition, as the glycol that uses, can enumerate ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butanediol, 1,6-hexylene glycol, 1,10-decanediol, 2-butene-1,4-glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-benzene dimethanol, diethylene glycol etc.
The polymer that contains the construction unit of general formula (4) expression can be by utilizing known method to make the corresponding carboxylic acid generation dehydrating condensation with hydroxyl or utilizing known method that the cyclic ester generation ring-opening polymerisation of the corresponding carboxylic acid with hydroxyl is obtained.As the pigment with hydroxyl or its cyclic ester that use, can enumerate 6 hydroxycaproic acid, 11-hydroxyl hendecanoic acid, hydroxybenzoic acid, 6-caprolactone etc.
At least any one the polymer that contains the construction unit shown in general formula (1)～(4) be preferably any one that contain the construction unit shown in general formula (1)～(4) at least, with the product of at least a combined polymerization of the construction unit that contains acid group such as (methyl) acrylic acid.In addition, these polymer can use or make up two or more uses separately.
Polymer phase is preferably 0.1～40 quality % to the content that whole resist layers form with material.Content by making polymer is more than 0.1 quality %, and the amount of polymer is sufficient and can obtain sufficient fixation performance, by making them below 40 quality %, can form particle well simultaneously.
In addition, in carrier fluid, disperse (granulating) aforesaid particle, and in order to control the precipitation of the particle in particle diameter and the composite inhibiting, and then preferably use dispersant.As preferred dispersing agent, can enumerate cithrols such as sorbitan fatty acid esters such as anhydrosorbitol monooleate ester or poly(ethylene oxide) distearate is the surfactant of representative.In addition, for example can also enumerate the copolymer, rosin, BYK-160,162,164,182 (the polyurethane series polymer of BYK corporate system), EFKA-401,402 (acrylic acid series polymeric compounds of EFKA corporate system), ソ Le ス パ one ス 17000,24000 (the polyester based polymer of ZENECA corporate system) etc. of copolymer, (methyl) acrylic acid series polymeric compounds, polyethylene and (methyl) acyclic compound of the copolymer of styrene and maleic acid and amine modifier, styrene and (methyl) acyclic compound.In addition, form the viewpoint of the long-time storage stability of using material from resist layer, dispersant is preferably weight average molecular weight 1,000～1000, the interior and polymer of polydispersity (weight-average molecular weight/number-average molecular weight) in 1.0～7.0 scope of 000 scope.And then, most preferably use graft polymers or block polymer.
The polymer that especially preferably uses as dispersant is for containing the graft polymers of the component of polymer that contains as grafted chain at least by the component of polymer of any one formation at least of the construction unit of following general formula (5) and (6) expression with the construction unit of following general formula (7) expression at least.
[changing 2]
General formula (5)
General formula (6)
General formula (7)
In the described formula, R
51Expression hydrogen atom or methyl, R
52The alkyl of expression carbon number 1～10.X
51The expression oxygen atom or-N (R
53)-, be at this, R
53The alkyl of expression hydrogen atom or carbon number 1～10.R
61The alkoxyl that the alkyl of expression hydrogen atom or carbon number 1～20, halogen atom, hydroxyl or carbon number are 1～20.R
71Expression hydrogen atom or methyl, R
72The alkyl that the expression carbon number is 4～30.X
71The expression oxygen atom or-N (R
73)-, be at this, R
73The alkyl of expression hydrogen atom or carbon number 1～30.Wherein, R
52, R
72Alkyl in, also comprise ehter bond, amino, hydroxyl or halogenic substituent.
Described graft polymers can be by preferably making the free radical polymerization monomer generation polymerization of corresponding general formula (7) in the presence of chain-transferring agent, end to the polymer that obtains imports polymerism functional group, and then obtains with the free radical polymerization monomer generation combined polymerization of corresponding general formula (5) or (6).
Free radical polymerization monomer as corresponding general formula (5), for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid benzyl ester, (methyl) esters of acrylic acid and N-methyl (methyl) acrylamide of (methyl) acrylic acid 2-hydroxyl ethyl ester, N-propyl group (methyl) acrylamide, N-phenyl (methyl) acrylamide, N, (methyl) acrylic amides such as N-dimethyl (methyl) acrylamide.
As the free radical polymerization monomer of corresponding general formula (6), for example can enumerate styrene, 4-methyl styrene, chlorostyrene, methoxy styrene etc.
And then, as the free radical polymerization monomer of corresponding general formula (7), for example can enumerate (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid 2-b hexyl, (methyl) dodecylacrylate, (methyl) stearyl acrylate acid esters etc.As the concrete example that can be used as these graft polymers that dispersant preferably uses in the present invention, can enumerate the polymer of representing with following structural formula ([BZ-1]～[BZ-6]).
[changing 3]
[BZ-1]
[BZ-2]
[BZ-3]
[changing 4]
[BZ-4]
[BZ-5]
[BZ-6]
Contain contain the construction unit shown in general formula (5) and (6) at least any one component of polymer and the graft polymers of polymerization composition that the construction unit shown in the general formula (7) is contained as grafted chain at least, also can only have the construction unit shown in general formula (5) and/or (6) and the general formula (7), also can have other constituents.The preferred ratio of components that contains the component of polymer of grafted chain and component of polymer in addition is 10: 90～90: 10.In this scope, can obtain good particle and form property, obtain the particle diameter of needs easily, therefore preferred.These polymer may be used alone, can also be used in combination two or more as dispersant.
The content that the whole relatively resist layers of dispersant form with material is preferably 0.01～30 quality %.Content by making dispersant can obtain good particle and form property in this scope, can obtain the particle diameter that needs.
Polymer preferably uses dispersant to make it disperse and contain with coating of particles in carrier fluid, for the carried charge of controlling particle and then preferred and use charged conditioning agent.
As preferred charged conditioning agent as used herein; can enumerate the aphthenic acids zirconates; the slaine of organic carboxyl acids such as octenoic acid zirconates; the ammonium salt of organic carboxyl acids such as stearic acid tetramethyl ammonium; pelopon A; the slaine of organic sulfonic acids such as dioctyl phthalate sulfosuccinic acid magnesium salts; the ammonium salt of organic sulfonic acids such as toluenesulfonic acid 4-butyl ammonium; the polymer that on the side chain of polymer that contains the carboxylic acid group that the copolymer of styrene and maleic anhydride is carried out modification with amine etc., has the carboxylic acid group; the polymer that on the side chain of copolymer of the tetramethyl ammonium of methacrylic acid stearyl ester and methacrylic acid etc., has carboxylate anion's base; the polymer that on the side chain of copolymer of styrene and vinylpyridine etc., has nitrogen-atoms; at butyl methacrylate and N-(2-methacryloxyethyl)-N; N has the polymer of ammonium etc. on the side chain of the copolymer of N-trimethyl ammonium p-toluenesulfonyl acid (ト シ ラ one ト) salt etc.
Compare with low-molecular-weight compound, charged conditioning agent is polymer compound more preferably, especially preferably contains carboxylic acid group's polymer.Wherein, particularly utilize have can become the macromolecular compound that non-water-soluble matchmaker is obtained as the copolymer of construction unit, with the reaction of uncle's ammoniate and parahelium compound for soluble at least a above monomer and maleic anhydride and also have half maleic acid acid amides composition and the maleic amide composition as the polymer of repetitive, can be preferably as charged conditioning agent illustration.
As in the polymer of charged conditioning agent, can form to non-water-soluble matchmaker for the monomer of polymer soluble is meant can polymerization the ester class etc. of olefines, cyclenes hydro carbons, phenylethylene, vinyl ethers, allyl ethers, vinyl carboxylates class or unsaturated carboxylic acids such as allyl ester class, methacrylic acid or acrylic acid.
If further specify, monomer can be enumerated the substituent olefines of having of total carbon atom number 3～40 (for example 1, the 3-allylidene, butylene, vinylidene chloride, ω-phenyl-1-propylene, allyl alcohol, hexene, octene, the 2-ethyl hexene, decene, laurylene, tetradecene, hexadecylene, octadecylene, docosene, eicosylene, the own ester of 10-undecenoic acid etc.), the cyclenes hydro carbons of total carbon atom number 5～40 (cyclopentene for example, cyclohexene, two rings [2,2,1]-heptene-2,5-cyano group two rings [2,2,1]-heptene-2 etc.), total carbon atom number 8～40 have substituent phenylethylene (styrene for example, the 4-methyl styrene, 4-n-octyl ethene, 4-methyl hydroxy styrenes etc.), the fatty group substituted ethylene base ether of total carbon atom number 1～40 or allyl ethers are [as fatty group, can enumerate and to have substituent alkyl (methyl for example, ethyl, butyl, hexyl, octyl group, decyl, dodecyl, cetyl, octadecyl, docosyl, chloroethyl, the 2-ethylhexyl, 4-methoxyl group butyl etc.), can have substituent aryl radical (benzyl for example, phenethyl etc.), can have substituent cycloalkyl (cyclopenta for example, cyclohexyl etc.) or can have substituent alkenyl (2-pentenyl for example, 4-propyl group-2-pentenyl, oleyl, inferior oil base etc.)], the vinyl acetate with substituent aliphatic carboxylic acid of total carbon atom number 2～40 or allyl ester class (acetic acid for example, valeric acid, caproic acid, capric acid, laurate, ten alkanoic acids, hexadecylic acid, stearic acid, oleic acid, sorbic acid, linoleic ester class etc.), the vinyl acetate of the aromatic carboxylic acid of carbon number more than 6 or allyl ester class (benzoic acid for example, benzoic acid 4-butyl ester, benzoic acid 2, the 4-butyl ester, the ester class of benzoic acid 4-hexyl hydroxy ester etc.) or acrylic acid, methacrylic acid, maleic acid, the total carbon atom number 1～32 of unsaturated carboxylic acids such as crotonic acid have a substituent fatty group ester class (methyl for example, ethyl, propyl group, hexyl, decyl, the 2-ethoxy, N, N-dimethyl aminoethyl etc.) etc.
For having these monomers and maleic anhydride copolymer, represent preferred concrete example in following (1)～(22) with the construction unit that constitutes this copolymer as construction unit.But, do not limited by following example.
[changing 5]
[changing 6]
[changing 7]
The aforesaid copolymer that contains maleic anhydride can be according to known method manufacturing in the past.For example, works " polymer handbook (Polymer Handbook) " such as the good flat sennit in little field " The modern industry chemistry the 16th volume; on the macromolecule industrial chemistry I " 281 pages (towards the distribution of storehouse bookstore), J.Brandrup the 2nd edition (2nd, Edition), John Wiley﹠amp; Sons, institute's write up among the New York, known documents such as the 2nd chapter etc.
As mentioned above, at this, the polymer that preferably uses as charged conditioning agent is the described copolymer of maleic anhydride and the reactant of amino-compound of containing.As amino-compound, can use the parahelium compound shown in uncle's ammoniate shown in uncle's ammoniate shown in the following general formula (8) or the following general formula (8) and the following general formula (9).
General formula (8) R
81NH
2
General formula (9) R
91R
92NH
In described general formula (8) and (9), R
81, R
91And R
92Expression fatty group, ester ring type alkyl, aromatic series base or heterocyclic radical, the R of general formula (9)
91And R
92Can be identical or different.Preferred expression carbon number 1～32 have a substituent alkyl (methyl for example, ethyl, propyl group, butyl, hexyl, octyl group, decyl, dodecyl, myristyl, cetyl, octadecyl, docosyl, chloroethyl, cyanoethyl, 4-butoxy propyl group, the 2-ethylhexyl, N, N-butyl aminopropyl etc.), carbon number 3～32 have a substituent alkenyl (pi-allyl for example, the 2-pentenyl, 4-propyl group-2-pentenyl, the decene base, oil base, inferior oil base etc.), carbon number 7～36 have a substituent aryl radical (benzyl for example, phenethyl etc.), carbon number 5～32 have a substituent ester ring type alkyl (cyclopenta for example, cyclohexyl, two rings [2,2,1]-heptyl, cyclohexenyl group etc.), carbon number 6～38 have a substituent aryl (phenyl for example, tolyl, 4-butyl propyl group, the 4-decyl phenyl, 4-butoxy phenyl etc.) or the heterocyclic radical of atomicity more than 5 (furyl for example, thenyl etc.).Under the situation of general formula (9), R
91And R
92Can also can contain hetero-atom (for example morpholinyl etc.) at carbon atom by closed loop at ring.
Concrete example as preferred amino-compound, can enumerate ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, dodecyl amine, tetradecylamine, cetylamine, octadecane amine, docosane amine, 2 ethyl hexylamine, 3,3-dimethylamylamine, allylamine, hexamethyleneamine, laurylene amine, tetradecene amine, hexadecylene amine, octadecenyl amine, 2-nonyl-2-butenylamine, allylamine, cyclo-hexylamine, benzylamine, 4-n-octyl aniline etc.
In addition, as being preferably used as the having in monomer and the maleic anhydride polymer as the copolymer of construction unit and the reactant between the amino-compound of charged conditioning agent, macromolecular compound comprises half maleic acid acid amides composition and maleic amide composition.Such polymer in macromolecular compound the maleic anhydride composition and the high molecular weight reactive of uncle between the ammoniate in as half maleic acid amide copolymer, can the part of half maleic acid acid amides composition be become the maleic amide composition by further carrying out dehydration closed-loop reaction, easily make.
Promptly, reaction between maleic anhydride and the amino-compound does not take place, and under following reaction temperature, in the organic solvent that can dissolve the two, [for example can enumerate hydro carbons (decane for example, ISOPARG, ISOPARH, SHELLSOL71, cyclohexanol, benzene, toluene, dimethylbenzene etc.), ketone (methyl ethyl ketone for example, hexone etc.), ethers (dioxane for example, oxolane, anisoyl etc.), halogenated hydrocarbon (chloroform, dichloroethylene, methyl chloroform etc.), dimethyl formamide or methyl-sulfoxide etc., be used alone or as a mixture], mix each compound.
Make its 60～200 ℃ of temperature, be preferably under 100～180 ℃, react 1～80 hour, be preferably 3～15 hours.When carrying out this reaction,, then can promote reaction if catalytic amount uses organic base (for example triethylamine, dimethylaniline, pyridine, morpholine etc.) or inorganic or organic acid (for example sulfuric acid, methanesulfonic acid, benzene sulfonic acid etc.).Perhaps, also can be also with common dehydrating agent (for example phosphorus pentoxide, two ring carboxyl imidodicarbonic diamide etc.).
As mentioned above, the reactant that utilizes this reaction to obtain is the macromolecular compound that contains half maleic acid acid amides composition and maleic amide composition in the polymer, the mass ratio of the content of half maleic acid acid amides and maleic amide is 10: 90～90: 10, is preferably 30: 70～70: 30.In addition, constitute polymer, can form non-water-soluble matchmaker to the monomer segment of polymer soluble and the maleic anhydride mass ratio between partly is 10: 90～99.5: 0.5, be preferably 70: 30～30: 70.The molecular weight of macromolecular compound is 1000～500,000, is preferably 5000～50,000.
At this, the electric charge that utilizes charged conditioning agent to give particle can be positive charge or negative electrical charge.The whole relatively resist layer formation of charged conditioning agent uses the component of material preferably in the scope of 0.0001～10 quality %.In this scope, can easily resist layer formation be adjusted in the scope of 10nS/m～300nS/m with conductivity of electrolyte materials.
In addition, the resist layer that uses in the ink jet recording method of the present invention forms uses material, except compositions such as aforesaid carrier fluid, polymer, dispersant, charged conditioning agents, can also contain the various compositions such as surfactant that are useful on control surface tension force according to purpose.
For example, such resist layer forms can be by being scattered in the carrier fluid polymer and dispersant and granulating with material, thereby and in carrier fluid, add charged conditioning agent and make its generation electric charge, prepare.Ink-jet recording apparatus shown in the utilization, the resist layer that preparation is obtained form use material, sprays with the substrate shape that has described hole 6, is formed with first metal conducting layer 1.The resist layer of per 1 point (dot) when the ejection condition for example sprays forms the spray volume with material, and the exploring degree of pattern that can be is as required suitably selected.
The resist layer that is suitable on first metal conducting layer 1 forms and is removed solvent with material, solidifies, and forms resist layer 3.The resist layer that has been ejected forms and also can solidify at normal temperatures with material, but as required, can utilize conventional methods such as infrared ray exposure, injection Wen Feng to implement drying process.
Dried thickness at the resist layer 3 of this formation is preferably about 1～100 μ m.
＜electroplate and to electroplate being formed with pattern with the duplexer of resist layer, form the electroplating work procedure of second metal conducting layer with pattern-like 〉
Like this, after forming plating resist layer 3, utilize electroplating processes, the surface of the part of exposing at first metal conducting layer 1 forms second metal conducting layer 4 (Fig. 4 E).
Second metal conducting layer can utilize the galvanoplastic to first metal conducting layer to form.
Electroplating processes can be used known method in the past.In addition, the metal that uses in the plating as this operation can be enumerated copper, chromium, nickel, gold, silver, tin, zinc etc., from the viewpoint of electrical conductance, and preferably copper, gold, silver, more preferably copper.
The metal that uses in second metal conducting layer that utilizes electroplating processes to form can be identical or different with the metal that uses in the formation of first metal conducting layer, and from the viewpoint of the homogeneity of circuit, be preferably identical.
On first metal conducting layer of first metal conducting layer in can a coverage hole, can be the state of filler opening also, the two all can.
Thickness to second metal conducting layer is not particularly limited, and according to purposes and difference, can wait and controls by regulating metal concentration that plating contains in bathing or current density.In addition, be used for the thickness under the situation of common electric distribution etc., from the viewpoint of electrical conductance, be preferably more than the 0.5 μ m, more preferably more than the 3 μ m.
＜remove to electroplate and remove operation with the resist of resist layer
Form after second metal conducting layer, remove described resist layer 3 (Fig. 4 F).
Plating resist layer among the present invention is removed the solution that liquid is meant dissolving plating resist layer, uses the matched liquid of composition with the plating resist layer that uses.
In the plating resist layer, use under the situation of resin of alkali-soluble, can usefully use aqueous alkali, for example can use the aqueous solution of silicate base slaine, alkali metal hydroxide, phosphoric acid and inorganic alkaline compounds such as carbonic acid alkali metal salt, phosphoric acid and ammonium carbonate salts, organic basic compounds such as ethanolamines, ethylenediamine, propane diamine class, trien, morpholine etc.These aqueous solution are owing to the dissolubility of control plating resist layer, so need to regulate concentration, temperature, injection pressure etc.Preferably remove after liquid handles, utilize acid treatment, washing to handle unnecessary the carrying out that stops the dissolving of plating resist layer with the plating resist layer.
The etching work procedure of first metal conducting layer in the zone beyond the formation portion of established second metal conducting layer is removed in＜etching 〉
Then, the remaining first thin metal conducting layer 1 after removing this resist layer 3 is removed in etching, obtains being formed with the substrate (Fig. 4 G) of the circuit 5 of the pattern-like that is made of first metal conducting layer and second metal conducting layer.
As long as can dissolving, the etching solution that uses in the etching of first metal conducting layer among the present invention removes first metal conducting layer.For example, can use common etching solutions such as alkaline ammoniacal liquor, sulfuric acid-hydrogen peroxide, copper chloride, persulfate, iron chloride.In addition, as device or method, for example can usage level spray device or methods such as etching, dipping etching.Their concrete condition is recorded in " printed circuit technique brief guide " (the printed circuit industry of civic organization Japan can be compiled, and publishes Nikkan Kogyo Shimbun's distribution in 1987).
In addition, the multilayer board after the etch processes preferably cleans with aqueous alkali or water in order to remove etching solution.
The metal conducting layer of the pattern-like that obtains like this has thickness sufficient, according to the pattern formation of high-resolution.The manufacture method of printed circuit board (PCB) of the present invention is a kind of simple method, can forms the circuit of the meticulous electrical conductance of height, so be of wide application.
[embodiment]
The present invention will be described below to utilize embodiment.
At glass baseplate epoxy resin base plate (area 340mm * 510mm, base material thickness 0.1mm) opens the open-work of 0.15mm Φ, the hangover of implementing then to disappear is handled, carry out electroless plating and apply processing, on the surface that comprises open-work inside, the non-cathode copper plating layer of 0.5 μ m is set, as first metal conducting layer.
Then, in order to form the plating resist layer, prepare material shown below.
-resist layer formation material-
Polymer [AP-1] 20g
Dispersant [BZ-2] 7.5g
Charged conditioning agent [CT-1] 0.6g
Carrier fluid ISOPARG (EXON company (strain) system) 391g
Described resist layer forms has following structural formula with the polymer that uses in the material [AP-1] dispersant [BZ-2], charged conditioning agent [CT-1].
[changing 8]
[AP-1]
[BZ-2]
[CT-1]
In addition, polymer [AP-1], dispersant [BZ-2] and charged conditioning agent [CT-1] are as described below synthetic.
＜polymer [AP-1] 〉
By using known polymerization initiator, methyl methacrylate, butyl methacrylate and methacrylic acid polymerization reaction take place are obtained.Weight average molecular weight is 15,000, and polydispersity (weight-average molecular weight/number-average molecular weight) is 2.7.Vitrifying point (mid point (midpoint)) is 51 ℃, and utilizing the softening point of straingauge (strain gauge) method is 46 ℃.
＜dispersant [BZ-2] 〉
In the presence of 2 mercapto ethanol; make methacrylic acid stearate generation radical polymerization, and then, by making itself and methacrylic acid anhydride reactant; and had the polymer (weight average molecular weight is 7,600) of the methacrylic acid stearate of methacryl endways.By making this polymer and styrene generation radical polymerization, obtain BZ-2.Weight average molecular weight is 110,000.
＜charged conditioning agent [CT-1] 〉
React by the copolymer that makes 1-cetylamine and 1-octadecylene and maleic anhydride and to obtain.Weight average molecular weight is 17,000.
As described below, use described each material, obtain containing the resist layer formation material of particle.
At first, polymer [AP-1] 20g is joined into the desk-top kneader PBV-0.1 of the river chamber of commerce (strain) system, heter temperature is set at 100 ℃, after heating 2 hours, carry out coarse crushing with TRIOSCIENCE (strain) system TRIOBLENDER, and then grinding (sample mill) with the science and engineering of pulling together (strain) system SK-M10 type sample, to carry out micro mist broken.Make institute's (strain) system paint shaker (paint shaker) with the smart mechanism of Japan, be about the bead of 3.0mm with dispersant [BZ-2] 7.5g, ISOPARG75g and diameter, the pre-dispersed micro mist that obtains minces.Remove after the bead,, be about the zirconia ceramics pearl of 0.6mm with diameter with the system TypeKDL DYNO MILL of SHINMARU ENTERPRISES company (strain); with interior temperature remain on 25 ℃ following 5 hours; and then 45 ℃ following 5 hours, with 2, the rotating speed of 000rpm disperses (granulating).Remove the zirconia ceramics pearl from the dispersion liquid that obtains, heating ISOPARG316g and charged conditioning agent [CT-1] 0.6g obtain resist layer and form with material [EC-1].
With similarly above-mentioned, use LCR instrument (meter) (peace rattan electric (strain) corporate system AG-4311) and liquid electrode (Kawaguchi's motor is made the corporate system LP-05 of institute's (strain) type), measure resist layer with the condition that applies voltage 5V, frequency 1kHz and form [EC-1] conductivity under 20 ℃ of using material, the result is 100nS/m for the conductivity of whole black liquid.In addition, use miniature high-speed cooling centrifuge (tomy Seiko (strain) corporate system SRX-201), under the condition of 20 ℃ of rotary speed 14500rpm, temperature, formation is carried out centrifugation in 30 minutes with material to resist layer, make solids precipitation, similarly measure the conductivity of supernatant then, the result is 30nS/m for the conductivity of supernatant.
That is, the conductivity of particle becomes 70nS/m, and the ratio of the conductivity of the relative supernatant of conductivity of particle is 2.3.In addition, with similarly above-mentioned, use the automatic particle size distribution device CAPA-700 of ultracentrifugation formula (the hole field makes institute's (strain) system), utilize ultracentrifugation, measure the volume mean diameter of particle, the result is 0.7 μ m.In addition, resist layer formation is 1.2mPas with the viscosity of material.
Use possesses described resist layer and forms the ink-jet recording apparatus that forms with material [EC-1] and ink gun 50 shown in Figure 5, as switch (switch), make the first ejection electrode (not shown) be varied to 2 states of ground state (closing (OFF)) and high impedance (high impedance) state (opening (ON)), make second the ejection electrode 58 be varied to 0V (pass) and+600V (opening) 2 states, in addition, surface to recording medium P gives-current potential of 1600V, be spaced apart 500 μ m between the fore-end 54a of China ink liquid guider 54 and the glass baseplate epoxy resin base plate P that is provided with first conductive layer, carry out the ejection that resist layer forms the usefulness droplets of materials.At this, in above-mentioned condition, the first ejection electrode with the second ejection electrode 58 when opening, ejection resist layer formation droplets of materials O.
The live width of plating resist layer is that the deviation of 50 μ m, width is 4 μ m.
After first metal conducting layer of affirmation open-work inside exposes fully, carry out the cathode copper plating, on first metal conducting layer, forming thick as second metal conducting layer is the cathode copper plating layer of 12 μ m.Then, use the 3 quality % sodium hydroxide solutions (30 ℃, 35 seconds) of pH13, wash-out is removed the plating resist layer.
And then, with etching solution (30 ℃ are sprayed and press: 2.0kg/cm of sulfuric acid-hydrogen peroxide system
2) handle, remove first metal conducting layer that exposes.Use the microscopic examination circuit substrate, the result is for also having formed metal conducting layer equably in open-work inside.
Forming the needed operation of this metal conducting layer is 7 operations.
(comparative example 1)
At glass baseplate epoxy resin base plate (area 340mm * 510mm, base material thickness 0.1mm) opens the open-work of 0.15mm Φ, the hangover of implementing then to disappear is handled, carry out electroless plating and apply processing, on the surface that comprises open-work inside, the non-cathode copper plating layer of 0.5 μ m is set, as first metal conducting layer.
Use the dry film laminating machine, minus (photo-crosslinking type) the dry film photoresist that thermo-compressed is commercially available then by photomask, uses to have sintering high-pressure mercury lamp light supply apparatus (the ユ ニ レ Star Network URM300 that attracts attachment mechanism, Ushio motor system), carry out 30 seconds ultraviolet exposures.Photomask uses is conductor width and is spaced apart 60 μ m, in order to make through-hole part fully by shading, and the terminal pad diameter is designed to the photomask of 0.3mm Φ.Then, carry out alkali cleaning by aqueous sodium carbonate (the liquid temperature is 35 ℃) and take off with 1 quality %, and circuit not formation portion form the plating resist layer.
Then, carry out the cathode copper plating, it is second metal conducting layer of 12 μ m that the surface of the part of exposing at first metal conducting layer forms thick.Then, handle, remove the photoresist layer with 40 ℃ 3 quality % sodium hydroxide solutions.Then, etching solution (30 ℃ are sprayed and press: 2.0kg/cm that is with sulfuric acid-hydrogen peroxide
2) handle, etching first metal conducting layer obtains circuit substrate.With the circuit substrate that microscopic examination obtains, the result is the broken string etc. that arrives unconfirmed on circuit substrate.
Using the photoresist method to form the needed operation of metal conducting layer distribution is 9 operations.
(comparative example 2)
At glass baseplate epoxy resin base plate (area 340mm * 510mm, base material thickness 0.1mm) opens the open-work of 0.15mm Φ, the hangover of implementing then to disappear is handled, carry out electroless plating and apply processing, on the surface that comprises open-work inside, the non-cathode copper plating layer of 0.5 μ m is set, as first metal conducting layer.
Use the dry film laminating machine, minus (photo-crosslinking type) the dry film photoresist that thermo-compressed is commercially available then by photomask, uses to have sintering high-pressure mercury lamp light supply apparatus (the ユ ニ レ Star Network URM300 that attracts attachment mechanism, Ushi motor system), carry out 30 seconds ultraviolet exposures.Photomask uses is that the pattern width of circuit formation portion is 50 μ m, for its binding and have only the not exposure of central portion of open-work, and the shading area of through-hole part is designed to the photomask of 0.08mm Φ.Then, carry out alkali cleaning by aqueous sodium carbonate (the liquid temperature is 35 ℃) and take off with 1 quality %, and circuit not formation portion form the plating resist layer.Observe the plating resist layer, results verification is because bad in the contraposition of exposure process, and the aperture area of the dry film photoresist of the hole portion of open-work diminishes.
Then, carry out the cathode copper plating, it is second metal conducting layer of 12 μ m that the surface of the part of exposing at first metal conducting layer forms thick.Then, handle, remove the photoresist layer with 40 ℃ 3 quality % sodium hydroxide solutions.Then, etching solution (30 ℃ are sprayed and press: 2.0kg/cm that is with sulfuric acid-hydrogen peroxide
2) handle, etching first metal conducting layer obtains circuit substrate.With the circuit substrate that microscopic examination obtains, found that inside, hole metal conducting layer uneven thickness one the position and do not have the position of the metal conducting layer in the hole.
In addition, using the photoresist method to form the needed operation of metal conducting layer distribution is 9 operations.
By being suitable for manufacture method of the present invention, make at open-work and do not produce defective and densification becomes possibility, and process is short, be possible so make printed circuit board (PCB) cheaply with high meticulous distribution.
Claims (10)
1. the manufacture method of a printed circuit board (PCB), it comprises at least: utilize the electrostatic means ink-jet, resist layer formed with material be ejected in the first metallic conduction laminar surface that the duplexer that first metal conducting layer forms is set on the insulating properties substrate, and make this resist layer formation material cured, form pattern and electroplate the resist formation operation of using resist layer; Electroplate with the duplexer of resist layer being formed with this pattern plating, form the electroplating work procedure of second metal conducting layer with pattern-like; Remove to electroplate and remove operation with the resist of resist layer; The etching work procedure of first metal conducting layer in the zone beyond the formation portion of established second metal conducting layer is removed in etching.
2. manufacture method according to claim 1, wherein,
The thickness of described first metal conducting layer is 0.1～20 μ m.
3. manufacture method according to claim 1, wherein,
Described resist layer forms and contains polymer, dispersant, charged conditioning agent with material in carrier fluid.
4. manufacture method according to claim 3, wherein,
Described charged conditioning agent is the polymer compound with carboxylic acid group.
5. manufacture method according to claim 1, wherein,
The dried thickness of formed described resist layer is 1～100 μ m.
6. the manufacture method of a printed circuit board (PCB), it has at least: after the insulating properties substrate formed through hole and/or non-through hole, the metal conducting layer that first metal conducting layer is set formed operation; Utilize the electrostatic means ink-jet, resist layer is formed be ejected in the first metallic conduction laminar surface, and make this resist layer formation material cured, form the pattern plating and use the resist of resist layer to form operation with material; Electroplate with the duplexer of resist layer being formed with this pattern plating, form the electroplating work procedure of second metal conducting layer with pattern-like; Remove to electroplate and remove operation with the resist of resist layer; The etching work procedure of first metal conducting layer in the zone beyond the formation portion of established second metal conducting layer is removed in etching.
7. manufacture method according to claim 6, wherein,
The thickness of described first metal conducting layer is 0.1～20 μ m.
8. manufacture method according to claim 6, wherein,
Described resist layer forms and contains polymer, dispersant, charged conditioning agent with material in carrier fluid.
9. manufacture method according to claim 8, wherein,
Described charged conditioning agent is the polymer compound with carboxylic acid group.
10. manufacture method according to claim 6, wherein,
The dried thickness of formed described resist layer is 1～100 μ m.
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| KR101141358B1 (en) * | 2010-07-29 | 2012-05-03 | 삼성전기주식회사 | Printed circuit board and fabricating method thereof |
| CN103476197B (en) * | 2013-07-22 | 2016-04-27 | 北大方正集团有限公司 | A kind of manufacture method of printed circuit board and printed circuit board |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08288618A (en) * | 1995-04-19 | 1996-11-01 | Sankyo Kasei Co Ltd | Formation of parts for three-dimensional circuit and parts for three-dimensional circuit |
| JP2003058077A (en) * | 2001-08-08 | 2003-02-28 | Fuji Photo Film Co Ltd | Substrate for microfabrication, fabrication method therefor and image-like thin-film forming method |
| JP2003197812A (en) * | 2001-12-28 | 2003-07-11 | Seiko Epson Corp | Wiring base board and manufacturing method thereof, semiconductor device and manufacturing method thereof, circuit base board and electronic instrument |
| JP2004025700A (en) * | 2002-06-27 | 2004-01-29 | Shashin Kagaku Co Ltd | Inkjet printing device for substrate, and printing process therefor |
-
2006
- 2006-07-11 JP JP2006190082A patent/JP2008021700A/en not_active Abandoned
-
2007
- 2007-07-02 CN CNA2007101273129A patent/CN101106869A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102469691A (en) * | 2010-11-10 | 2012-05-23 | 三星电机株式会社 | Printed circuit board and method of manufacturing the same |
| CN103019055A (en) * | 2011-09-27 | 2013-04-03 | 富士施乐株式会社 | Liquid developer, developer cartridge, process cartridge, image forming apparatus, and image forming method |
| CN102573286A (en) * | 2011-12-05 | 2012-07-11 | 友达光电股份有限公司 | Multilayer circuit board and electrostatic discharge protection structure |
| CN112235951A (en) * | 2020-10-20 | 2021-01-15 | 盐城维信电子有限公司 | Method for manufacturing circuit boards with different copper thicknesses |
| CN112235951B (en) * | 2020-10-20 | 2021-09-21 | 盐城维信电子有限公司 | Method for manufacturing circuit boards with different copper thicknesses |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008021700A (en) | 2008-01-31 |
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