CN1224565A - Thick-film conductor circuit and production method therefor - Google Patents

Abstract

A thick-film conductor circuit wherein a zinc-containing layer is formed from the surface of a conductor made of a copper, or a thick-film conductor circuit having a rectangular sectional shape in the direction of width of the conductor and having rounded corners (R) at both lower end edge portions. This circuit is formed by using an aluminum plate treated with a zinc-containing basic solution as a conductive substrate, applying a specific liquid photosensitive resin composition to the conductive substrate, exposing a portion, where a resin pattern is to be formed, to high energy rays, dissolving or dispersing and removing an unexposed portion of the photosensitive resin composition by a developing solution to form a desired resin pattern on the conductive substrate, forming a conductor by electrolytic plating by applying a voltage to the conductive substrate while it is immersed in a plating solution, and removing the conductive substrate.

Description

Thick-film conductor circuit and manufacture method thereof

Technical field

The present invention relates to be suitable in the electronic unit or circuit block field of miniaturization day by day, multifunction, as microminiature and high performance small-sized plane motor coil, perhaps thick-film conductor circuit and the manufacture method of using in the manufacturing of light read-write as used high-speed data fetch unit in CD, MD and DVD thereof with the connection member of accurate coil, the circuit substrate that comprises LSI fine and closely woven cabling parts on every side and the display device that becomes more meticulous day by day etc.Particularly relate to comprise the minimum wiring pitch less than 100 microns part, can be with high density and freely set thick-film conductor circuit and manufacture method thereof resistance, that reliability is high.

Background technology

So-called high density and low resistance, the high again thick film circuit of while reliability, when requiring the cloth string pitch little, the sectional area of conductor is big, and in other words, it is high that conductor height is wanted, and wants the chemical stability of conductor in addition, for example non-oxidizability, corrosion resistance height.

For example, the constantly IC of high performance and LSI (large scale integrated circuit) etc. in the last few years, when requiring high performance, number of pins constantly increases, and the pitch of pin narrows down day by day.In addition, as seeing in the LCD, during the requirement that height becomes more meticulous grew to even greater heights, the bar number of reading scan line has had tremendously to be increased, and simultaneously, wiring has at interval also become extremely narrow, the assembling of the IC that control the shows difficulty that becomes.In such technological trend, between the parts that wiring is differed widely at interval, for example have that narrow pin pitch IC, LSI etc. and motherboard (wiring is big at interval on manufacture method) couple together high density and the requirement of the link of low-resistance different pitch just surging.In addition, for such parts, the document that has is defined as it " connector (interposer) " (79～86 pages of Nikkei worker レ Network ト ロ ニ Network ス 1995.1.16 (No.626)).In the present invention, it is defined as different pitch connecting wiring parts.Desired performance of different pitch connecting wiring parts or the like, in the paper of the 6th microelectronics discussion, as described in 43～46 pages, have and report the increase of having found along with the cloth line resistance, the phenomenon of signal pulse decay, report are also said, if the control that high meticulous liquid crystal display is used further becomes big with the cloth line resistance between IC and the crystal liquid substrate, then the S/N ratio will reduce, and it is unstable that image will become.The result is, and is low for different pitch connecting wiring part requirement cloth line resistances, and the cloth string pitch is little and have a high reliability.

As the means of the chemical stability of improving conductor, in the past, in order to prevent copper corrosion, the zinc also lower than copper normal potential was plated on the copper surface.But, if use this galvannealing, because the plating condition, in other words, temperature in the composition of electroplate liquid, the concentration of impurities, the electroplating work procedure, current density etc. are very big to the rerum natura influence of the film that generated, so, must cautiously carry out the management of electroplate liquid and operation.In addition, have antiseptic effect in order to make the zinc film, just need cover thickly, still, it is low that zinc and copper are compared conductivity, if therefore increase the thickness of zinc, the ratio of zinc increased, and then generation made conductivity reduce such problem.Particularly in frequency applications, because increasing, conductive surface resistance will become problem, so the also noble metal of plated with gold etc. on conductive surface sometimes.In being decided to be such high density of purpose of the present invention and surface area is big concerning the sectional area of conductor conductor circuit, also do not find and can suppress the zinc film thinly, conductivity is reduced, can suppress the means of the corrosion and the oxidation of copper again.

In addition, as the manufacture method of highdensity thick-film conductor circuit, copper-surfaced substrate, photoetching and the etching such method that combines that makes is arranged as everybody knows.But the thick-film conductor circuit that obtains with such method is when the etching of Copper Foil, and it is extremely difficult suppressing lateral erosion, and along with densification, the reliability of conductor will descend.In addition, along with conductor height becomes big, it is more remarkable that this phenomenon will become, so the thickness of the Copper Foil of common employed copper-surfaced substrate is about 18～35 microns, wiring density also can't accomplish 20/more than the mm.

As other the manufacture method of thick-film conductor circuit, for example, have Japanese kokai publication sho 52-137666 communique, spy and open disclosed method of in the resin figure, filling the inventive thick film paste material in the clear 57-162489 communique, with open the spy that disclosed inventive thick film paste and the positive photoetching rubber of making mixes in the clear 55-41729 communique, carry out the method that exposure is developed.But, the thick-film conductor circuit that obtains with these methods or in electric conductor, produce pore, or can cause because of the short circuit between conductor produce defective, and then produce the problem of the deterioration of the circuit characteristic that the increase because of conductor resistance causes.

In Japanese kokai publication sho 59-198792 communique, disclosing a kind of is substrate with the conductive board, after photoresist is carried out lamination and exposure repeatedly, with the manufacture method of developing and electroplating the thick-film conductor circuit that carries out.If use this method, though can expect to access the high photoresist figure of aspect ratio, can access low-resistance conductor circuit, but but exist complex procedures, the stagger importing of the defective that forms and of the position during because of the lamination exposure because of many problems of the circuit reliability aspects such as short circuit of the defective circuit that produces of resin shape.

In addition, open in the clear 60-161605 communique, disclose and a kind of conductive board and photoetching are made up, the forming method of the fine pattern circuit that carries out with the anisotropy metallide Japanese kokai publication sho 56-94690 communique, spy.In the method, with electroplating initial width control conductor design, and conductor shape be sphere, and the manufacture method of pretending to low-resistance figure conductor is unfavorable.

Have, the applicant opens in the flat 6-260740 communique the spy again, and disclosing a kind of is substrate processing method using same purpose, that improve the adaptation of photoresist and conductive board with the photoresist figure that obtains big aspect ratio.But the thick-film conductor circuit that obtains with this method can not form predetermined zinc atom and contain layer on the part of conductor top layer, exist some problems aspect non-oxidizability.

Print routing field for these, in the last few years, the exploitation in the micromachine field of medical treatment, transducer etc. developed very soon.As the manufacture method of micromachine is applied to the application examples of going in the manufacturing of figure conductor Microelectronic Engineering 4 (1986) p.35 with Proc.IEEE Solid-State Sensor ﹠amp; Among Actuator Workshop June (1988) P1, proposed a kind of usefulness and made the PMMA photoresist and the synchronous manufacture method of the miniature coils implemented of X-ray lithography (LIGA) technology that combines of radiating light.Use this method, though can use the extremely high low-resistance thick film figure of high density fabrication conductor, x-ray source is very expensive, thereby exists aspect industrial production and be difficult to low price, the problem of the limited size of operable substrate etc.

Replace LIGA technology, the Micropicture formation technology of having used the photonasty pi is at Transducers ' 93, Yokohama, june (1993), 7th Solid-State Sensor ﹠amp; Actuatorp60 etc. go up open.These technology, though be that silicon substrate is used photoetching and electroplated the technology that forms miniature gears or comb electrode,, but industrialness ground and make the technology of high density low resistance conductor figure cheaply openly.

Contrast with the formation technology of these Micropicture conductors, the applicant discloses a kind of manufacture method with thick film Micropicture of high aspect ratio in the special fair 5-81897 communique of Japan, open the liquid light-sensitive resin that discloses the cementability between a kind of raising and the electrically-conductive backing plate in the flat 6-283830 communique again the spy.But, in these communiques in the disclosed photosensitive polymer combination, also exist the problem of the residual residue that photoresist is arranged in the not exposure part of photosensitive polymer combination in photo-mask process etc.

Below, employed in the present invention photosensitive polymer combination is described and the difference between the disclosed photosensitive polymer combination in the fair 5-81897 communique of spy.This photosensitive polymer combination is characterised in that the light transmission of sense of control photosensitive resin composition.Use the method for polymerization initiator control exposure to contrast separately with the described photosensitive polymer combination of the fair 5-81897 communique of spy, the present invention is a kind of method of controlling light transmission simultaneously with polymerization initiator and light absorber.

Give one example, have the photosensitive polymer combination of 70% light transmission, using polymerization initiator separately, can make the photoresist figure no matter perhaps use simultaneously under any situation of polymerization initiator and light absorber.But, using under the situation of polymerization initiator separately, owing to increase its addition, so resolution, development will significantly descend, for example, in the high density graph below 100 microns, will produce the evils of residue in the part of exposure not, photographic fog (fogging) etc.If use polymerization initiator and light absorber simultaneously, the photopolymerization reaction in the time of then can controlling exposure can also be adjusted light transmission simultaneously, can make the high highdensity figure below 100 microns.In fact, in the combination of the polymerization initiator of the inhibition effect of performance development residue and photographic fog etc. and light absorber, must be by the light transmission amount of suppression that light absorber produced greater than 15%.

Fig. 5 shows photosensitive polymer combination of the present invention and the thickness of disclosed photosensitive polymer combination and the relation between the light transmission in the embodiment of the fair 5-81897 communique of spy.As seen from the figure, the described photosensitive polymer combination of special fair 5-81897 communique, because its light transmission is high more a lot of than the present invention, thus can obtain the thick photoresist figure of thickness, otherwise but, but can not obtain the highdensity figure below 100 microns.In addition, the described photosensitive polymer combination of special fair 5-81897 communique though light transmission will be reduced to below 75% when the thickness thickening, in this case, residue and photographic fog that exposure is not partly located but can occur.

In addition, prepolymer is also different in the present invention and special fair 5-81897 communique.In other words, the present invention uses the compound of representing with following chemical formula (1) and chemical formula (2) simultaneously in as the dicarboxylic acids composition of the raw material of prepolymer, and, adopt the way of the proportioning of specific these compounds, that has found up to now fully not expection can satisfy high image dissection definition, good development and the photosensitive polymer combination of anti-plating bath simultaneously.And then, adopt again with specific ratio preparation to have the way of the compound of the composition of representing by following chemical formula (3), find simultaneously to become more obvious than above-mentioned action effect.

Chemical formula (1)

Chemical formula (2)

(R ₁, R ₂Expression-COOH or-CH ₂COOH, R ₃, R ₄Expression-H or-CH ₃)

Chemical formula (3)

HOOC-(CH ₂) _n-COOH????(n=3～8)

Photosensitive polymer combination of the present invention, because the reactivity of prepolymer is than higher, so have some too late than long preservation stability with other prepolymer, though be the material of generally not inquired into, but as making the photosensitive polymer combination that thick-film conductor circuit is used, discovery is a kind of exceedingly useful resin.

Disclosure of an invention

The inventor etc., based on such technology trend, the result who studies with keen determination repeatedly, find method as the chemical stability that improves conductor circuit, employing is provided with the way that contains the zinc layer near conductive surface, in the non-oxidizability that improves conductor top layer part significantly, do not increase conductor resistance, realized purpose of the present invention.In other words, feature of the present invention is as follows.

1. thick-film conductor circuit is characterized in that: be in 5 microns the zone apart from the surface of conductors degree of depth that constitutes by copper, exist thickness and be 0.1～5 micron contain the zinc layer, zinc atom is 3～20 atom % to the ratio of copper atom.

2. above-mentioned 1 described thick-film conductor circuit is characterized in that: the cross sectional shape on the Width of conductor is rectangular, and two marginal portions have fillet R in the lower end.

3. thick-film conductor circuit, it is characterized in that: the cross sectional shape on the Width of conductor is rectangular, and two marginal portions have fillet R in the lower end.

4. any one described thick-film conductor circuit in above-mentioned 1～3 is characterized in that: the minimum wiring pitch of conductor contains the part below 100 microns, and the aspect ratio of conductor is greater than 1.2, and the height of conductor is greater than 20 microns.

5. the manufacture method of a thick-film conductor circuit, it is characterized in that: use when containing the aluminium sheet that the zinc alkaline solution handled as conductive board, the photosensitive polymer combination of liquid is coated onto on this conductive board, with high-energy ray the part that should form the resin figure is implemented exposure, then, with the not exposure part of developing and removing this photosensitive polymer combination with liquid dissolving or dispersion, on conductive board, form after the desirable resin figure, the limit powers up flanging conductive board is dipped in the electroplate liquid, after having formed conductor, remove conductive board with electrolytic plating method.

6. the manufacture method of a thick-film conductor circuit, comprise: the photosensitive polymer combination of liquid is coated onto on this conductive board, with high-energy ray the part that should form the resin figure is implemented exposure, then, with the not exposure part of developing and removing this photosensitive polymer combination with liquid dissolving or dispersion, on conductive board, form after the desirable resin figure, the limit powers up flanging conductive board is dipped in the electroplate liquid, formed after the conductor with electrolytic plating method, remove the operation of conductive board, it is characterized in that:

This liquid light-sensitive resin composition contains prepolymer, co-polymerized monomer, Photoepolymerizationinitiater initiater and light absorber with ethene unsaturated group, and,

Prepolymer is that number-average molecular weight that the condensation with dicarboxylic acids composition and diol component obtains is 500～5000 unsaturated polyester resin, the dicarboxylic acids composition, full mol ratio with this dicarboxylic acids composition is 1, calculate with mol ratio, compound (a) with composition of representing with following chemical formula (1) is 0.1～0.4, calculate with mol ratio, the compound (b) with composition of representing with following chemical formula (2) is 0.1～0.4

Chemical formula (1)

Chemical formula (2)

(R ₁, R ₂Expression-COOH or-CH ₂COOH, R ₂, R ₄Expression-H or-CH ₃)

The co-polymerized monomer composition has 3 acryloyl groups or methacryl at least in a molecule; and; between the carbon atom of this acryloyl group or the combination of methacryl institute, have carbon atom and/or the oxygen atom below 15 and make at least a compound of institute's combination; 100 weight portions with respect to this prepolymer contain 1～30 weight portion

In addition, the molar absorption coefficient that contains 0.1～10 weight % at light absorption maximum place is the Photoepolymerizationinitiater initiater of 5～1000l/molcm, when containing the light absorber of 0.01～1 weight %,

Light transmission is 15～75%.

7. the manufacture method of above-mentioned 6 described thick-film conductor circuits is characterized in that: conductive board is with containing the aluminium sheet that the zinc alkaline solution was handled.

8. the manufacture method of above-mentioned 6 described thick-film conductor circuits is characterized in that: in the composition beyond the composition of representing with the chemical formula (1) and the chemical formula (2) of dicarboxylic acids composition, be the dicarboxylic acids composition with following chemical formula (3) expression more than 75% mole

Chemical formula (3)

HOOC-(CH ₂) _n-COOH????(n=3～8)

9. the manufacture method of above-mentioned 7 described thick-film conductor circuits is characterized in that: in the composition beyond the composition of representing with the chemical formula (1) and the chemical formula (2) of dicarboxylic acids composition, be the dicarboxylic acids composition with following chemical formula (3) expression more than 75% mole

Chemical formula (3)

HOOC-(CH ₂) _n-COOH????(n=3～8)

10. any one described thick-film conductor circuit in above-mentioned 2 to 4 is characterized in that: insulating barrier is the hardening thing of the described photosensitive polymer combination of claim 6 between conductor.

11. the manufacture method of above-mentioned 6 described thick-film conductor circuits is characterized in that: the diffusion reflection surface rate of the conductive board in the wavelength photoreceptor zone of liquid light-sensitive resin is less than 20%.

12. the manufacture method of above-mentioned 7 described thick-film conductor circuits is characterized in that: the diffusion reflection surface rate of the conductive board in the wavelength photoreceptor zone of liquid light-sensitive resin is less than 20%.

13. a planar coil is characterized in that: the cross sectional shape of conductor be rectangle coil pattern toward each other, and make the top and bottom conducting and in the planar coil that constitutes, coil-conductor is any one the described thick film conductor in above-mentioned 1 to 4 by through hole.

14. different pitch connecting wiring parts is characterized in that: in the wired circuit of the different parts of connecting wiring pitch, the employed conductor that connects up is any one the described thick film conductor in above-mentioned 1 to 4.

The simple declaration of accompanying drawing

Fig. 1 is the profile of thick-film conductor circuit of the present invention.

Fig. 2 has been to use the top schematic view of the different pitch connecting wiring parts of thick-film conductor circuit of the present invention.

Fig. 3 has been to use the top schematic view of the planar coil of thick-film conductor circuit of the present invention.

Fig. 4 is the coil-conductor expansion profile partly of the planar coil of Fig. 3.

Fig. 5 shows the thickness in the employed photosensitive polymer combination and the relation between the light transmission in the manufacture method of the thick-film conductor circuit of employed photosensitive polymer combination and existing (special fair 5-81897 communique) in the manufacture method of thick-film conductor circuit of the present invention.

The preferred version that is used to carry out an invention

The feature of thick-film conductor circuit of the present invention is: in the zone that apart from the surface of conductors degree of depth that constitutes by copper is 5 microns, exist thickness and be 0.1～5 micron contain the zinc layer, zinc atom is 3～20 atom % to the ratio of copper atom.

The zinc layer that contains of the present invention, for example adopt to use with what 0.1～5 micron thickness covered the metal aluminum substrate top and contain the zinc layer, the way of handling through metallide in copper-contained electroplating liquid afterwards is present in until in the top layer part till 5 microns of the degree of depth of copper plating film with 0.1～5 micron thickness.The covering of zinc on aluminium base for example adopts the way that aluminium base is dipped into (zincate solution) in the treatment fluid that contains alkali composition, zinc ion to carry out, and can also adopt the way of treatment conditions of the composition, treatment temperature, processing time etc. of change treatment fluid to adjust the amount of this zinc film.In addition, it is desirable to, turn to purpose, adopt the zinc film that was once covering with the aqueous solution of nitric acid dissolving, and be dipped into the way in the zincate solution once more, implement to form the processing of zinc film etc. once again with miniaturization, the homogeneous of the zinc film on aluminium base surface.In addition, form firmly to the covering of aluminium base top, can also make the aluminium surface roughening with the grinder of polishing rolling (buff roll) grinder, abrasive blasting machine etc. in order to make zinc.

Electrolytic copper plating among the present invention can be used cupric pyrophosphate plating, copper sulphate plating or use existing copper facing technology such as cupric pyrophosphate plating and copper sulphate plating simultaneously, but, in order to make zinc atom be present in the surface of copper coating rather than stripping in electroplate liquid, must under the state that adds voltage, put in the electroplate liquid to substrate.Knock down under the situation of going in the electroplate liquid at making alive not, will the displacement reaction of zinc and copper takes place, because in electroplate liquid, zinc atom can not be present in the prescribed depth (being called the diffusion structure) of surface conductor layer with predetermined containing ratio to zinc with stripping, the oxidation of conductor circuit suppresses effect and will reduce.

Top layer part in the present invention includes zinc cathode copper figure, can adopt the way of removing aluminium base after plating to make.As the means of removing, can peel off or with the method for carrying out etching with mechanicalness.

The thickness that contains the zinc layer of the top layer part among the present invention is 0.1～5 micron, and in addition, the average containing ratio of the zinc atom that exists in this layer is 3～20 atom % to copper atom.Also thinner at the thickness that contains the zinc layer than 0.1 micron, perhaps under the average situation of containing ratio less than 3 atom %, the effect that suppresses the oxidation of copper disappears, surpassed in addition under 5 microns the situation, perhaps surpassed under the situation of 20 atom %, do not seen the further increase of the effect that suppresses oxidation at average containing ratio.

In addition, figure 1 illustrates the profile of conductor of the present invention, still, as shown in the figure, the cross sectional shape of conductor 1 on its Width (left and right directions among the figure) is rectangular, and there is fillet R in two edges in the lower end.The above-mentioned zinc layer that contains is present in the top layer part till 5 microns of the degree of depth of conductor 1.In addition, in figure, label 2 is a photosensitive polymer combination, and label 3 is a bonding agent.In addition, label 4 is the insulating properties substrate, can duplicate (transfer printing) conductor 1.

As mentioned above, two lower edge part A places at conductor 1 have in the conductor circuit of fillet R, the electric field of conductor edge is concentrated and is obtained relaxing, for example, the root that electromigration that takes place between conductor under hot and humid environment or cell reaction etc. become short circuit by phenomenon suppressed, the reliability of conductor circuit is improved.In addition, when on two marginal portions of conductor, existing fillet R, owing to will increase surface area,, cementability can be improved, the reliability under the high temperature hot environment can be improved by leaps and bounds under the first-class situation of duplicating conductor circuit of insulating properties substrate 4.

Angle circle R shown here means that under the cross sectional shape of conductor 1 the corner part of two the end A in lower end has curvature.Concrete definition can be used in the conductor thickness (a) of core of Width of conductor 1 and the difference definition between the conductor thickness (b) of two end A.Though can not correctly determine to relax the radius of curvature that electric field is concentrated, the value of (a-b) is about 2～20 microns usually.

The manufacture method of thick-film conductor circuit of the present invention is as follows.

Adopt following way to make thick-film conductor circuit: the liquid light-sensitive resin composition is coated onto on the conductive board, with high-energy ray the part that should form figure is implemented exposure, then, with the not exposure part of developing and removing this photosensitive polymer combination with liquid dissolving or dispersion, on conductive board, form after the desirable resin figure, form conductor with electrolytic plating method, remove conductive board.

In the present invention, as conductive board, it is desirable to use the substrate that constitutes by aluminum or aluminum alloy.In addition, for ease of explanation, aluminium base comprises aluminium alloy base plate here.

As the method for removing aluminium base, for example can use with the aqueous solution of acid, alkali, salt etc. and carry out corroding method, grind the method that eliminates, carry out method that mechanicalness peels off or method that these methods are combined etc.For example, want to remove aluminium base with corrosion, can be with 1～30% hydrochloric acid, under the situation of copper base, can corrode with the ammonium persulfate aqueous solution of about 25% ferric chloride in aqueous solution or 10% and remove.In addition, in order to improve the intensity of thick-film conductor circuit, also can be before or after removing conductive board, insulating material is bonded on the face with the opposite side of conductive board of thick-film conductor circuit.In addition, also can adopt form by a plurality of circuit of insulating material lamination.

In addition, can also be as required before the thick film conductor graph copying is to the insulated substrate, perhaps after duplicating and having removed conductive board, remove the resin visuals.Afterwards, also can on the part of having removed the resin figure, fill other resin as required, for example fill the high resin of thermal endurance etc.

As the conductive board that will use, the diffusion reflection surface rate that it is desirable in the wavelength photoreceptor zone of aforesaid liquid photosensitive polymer combination is lower than 20%.Here the surface reflectivity of Ding Yi substrate is the diffuse reflectance in the wavelength photoreceptor zone of employed liquid light-sensitive resin composition.When the diffusion reflection surface rate of substrate had surpassed 20%, because the scattered reflection change of incident light on substrate surface is big, so bottom (from the near part of the substrate surface) sclerosis of the not exposure of resin figure part, the result was or produces photographic fog, perhaps is left residue.In addition, the value of diffusion reflection surface rate can be with the spectrophotometer with integrating sphere, with the diffusion reflection surface rate of the standard white plate of barium sulfate in contrast (100%) measure.As the surface treatment method of conductive board, used the surface grinding means of physical property in the past always, but arrived approximately 40% with the diffusion reflection surface rate of the resulting substrate of this method greatly, can not get desirable resin figure.

Adopt separately the way that makes up with the surface treatment of the surface treatment of chemical or existing physical grinding and chemical, can obtain the substrate surface diffuse reflectance is controlled to substrate below 20%, can more stably obtain desirable resin figure.

Concrete method for processing surface of substrate can be different because of substrate, but, for example under the situation of aluminium base, can use the aluminium base surface preparation of MBV method, EW method, ア ロ ジ ソ method, trbasic zinc phosphate method, permanganimetric method, chlorination iron processes, zincate processing (zinc displacement plating processing) method etc. rightly.In addition, under the situation of copper base, can also utilize melanism processing etc.

So particularly carried out aluminium base that zincate handles because and the closing force between the photo-hardening of the photosensitive polymer combination of the present invention part high being suitable for use.

Also have, diffuse reflectance can be according to treatment conditions, and for example the composition of treatment fluid, treatment temperature, processing time etc. are adjusted.

In addition, the hardening thing electrical insulating property of aforesaid liquid photosensitive polymer combination is fine, also can be used as permanent resist and uses in the insulating barrier (for example part of the photosensitive polymer combination of representing with label 2 in Fig. 1) between conductor.

The prerequisite composition of the liquid light-sensitive resin composition of Shi Yonging is prepolymer, monomer component, Photoepolymerizationinitiater initiater and light absorber in the present invention.Under the situation of the photosensitive polymer combination that will use as liquid, the control of thickness is extremely easy, in addition, because development is good, so can obtain the high resin figure of aspect ratio, in addition owing to little, so the shape of hardening resin is steep anxious rectangular shape in the diffuse reflection of resin inside.

Prepolymer of the present invention is that number-average molecular weight that the condensation with dicarboxylic acids composition and diol component obtains is 500～5000 unsaturated polyester resin, the dicarboxylic acids composition, full mol ratio with this dicarboxylic acids composition is 1, calculate with mol ratio, compound (a) with composition of representing with following chemical formula (1) is 0.1～0.4, calculate with mol ratio, the compound (b) with composition of representing with following chemical formula (2) is 0.1～0.4

Chemical formula (1)

Chemical formula (2)

(R ₁, R ₂Expression-COOH or-CH ₂COOH, R ₂, R ₄Expression-H or CH ₃)

In other words, prepolymer of the present invention is that the ratio of the compound of the unsaturated group with different reaction speeds with appointment combined, when the resin figure forms, crosslinked action by means of the unsaturated group of the fast compound of reaction speed (a), make the exposure part have peel strength in the low exposure region that photographic fog does not take place, secondly, by means of the crosslinked action of the unsaturated group of the slow compound of reaction speed (b), further improve peel strength and and substrate between adaptation.The result is to be the big hardening of resin figure of aspect ratio of resin figure with the figure of narrow pitch formation thick film.

This prepolymer can be made of following such composition.In other words, can make the end of itaconic acid and so on have the dicarboxylic acids composition of chemical formula (1) expression of unsaturated group, and fumaric acid, maleic acid, mesaconic acid, citraconic acid, the dicarboxylic acids composition of representing with chemical formula (2) between 2 carboxyls of glutaconate and so on unsaturated group, as required, make and do not have adipic acid, binary acid or its acid anhydrides composition of the dicarboxylic acids of the unsaturated group of phthalic acid and so on etc., has ether below 5 with alkyl diol or in molecule in conjunction with any alcohol component in the glycol of (key) or 2 yuan of pure compositions constituting by these mixture, in blanket of nitrogen, decompression is dehydration polycondensation (esterification) down, makes to have desirable unsaturated prepolymer in conjunction with concentration and number-average molecular weight.

The mol ratio that makes the full dicarboxylic acids composition of this prepolymer is 1, it is 0.1～0.4 that the mol ratio of the unsaturated group composition of compound (a) it is desirable to, if still less than this, crosslinked just insufficient in the photoresist operation then, the inclination of the resin figure that the reduction that takes place because of mechanical strength of resin is caused, topple over, in addition, after electroplating work procedure in, will produce oozing out of resinous principle.When higher,, cause when producing crack etc., be not easy to produce photographic fog on the exposure part then because the crosslinked flexibility that too much will make resin reduces than above-mentioned mol ratio.In addition, the mol ratio of the unsaturated group composition of compound (b) it is desirable to 0.1～0.4, if also littler than this value, the cross-linking reaction after then resin forms can not be carried out fully, with take place and resin between closing force reduce, the oozing out etc. of resinous principle.In addition, if also bigger than this value, the flexibility of resin figure is reduced, crack etc. takes place, be unfavorable.

Even if the combination of the concentration of such unsaturated group, prepolymer is reactive high, not necessarily can satisfy the long preservation stability as photosensitive polymer combination, but, the inventor etc., adopt this reactivity of applying in a flexible way energetically, simultaneously, specify the way of the proportioning of above-mentioned each composition, find that (this prepolymer) is exceedingly useful as the composition that narrow pitch high aspect ratio figure forms with photosensitive polymer combination.

In addition, within the compound (a) of dicarboxylic acids composition, compound (b) composition in addition, account for mol ratio and be the composition more than 75%, it is desirable to have compound (c) with the composition of following chemical formula (3) expression.

Chemical formula (3)

HOOC-(CH ₂) _n-COOH????(n=3～8)

For example, be 0.25 in the mol ratio of compound (a), the mol ratio of compound (b) is under 0.25 the situation, the meaning is within remaining 0.5, more than 75%, promptly is the composition of compound (c) more than 0.375.Adopt the way with such straight chained alkyl dicarboxylic acids, in the viscosity that reduces the photoresist group, development property also can be improved significantly.As the example of compound (c), can enumerate glutaric acid, adipic acid and decanedioic acid etc.Existing unsaturated polyester resin, reactive in general low, in order to strengthen the intensity after the sclerosis, commonly to use aromatic dicarboxylic acid, but, employings such as the inventor improve reactive way with compound (a), compound (b), in the time of intensity after making it to keep hardening, without this aromatic dicarboxylic acid, and replace with straight chained alkyl dicarboxylic acids composition, these 3 characteristics of resolution, development and anti-plate contaminative have been found to satisfy, as electroplating with the very good photosensitive polymer combination of resistance plating agent.

The number-average molecular weight of this prepolymer it is desirable in 500～5000 scope.Molecular weight less than 500 situation under, or shrink excessive or sensitivity low excessively, aspect practical, be unfavorable.In addition, under 5000 the situation of surpassing, then viscosity uprises, and it is defective to be easy to that development takes place.Used the photosensitive polymer combination of this prepolymer, owing to needn't just can be used as the photosensitive polymer combination of liquid in use with dilutions such as solvents, so from the viewpoint of viscosity, system film, these practical aspects of development, molecular weight is even more ideal in 800～3000 scope.Number-average molecular weight can adopt the temperature, pressure, the way of time that change polycondensation reaction to control.Measure number-average molecular weight, carry out titration with the KOH titer and ask acid value, then, the method for calculating from the molar concentration of unreacted carboxyl is easily.

In a molecule, have 3 acryloyl groups or methacryl at least among the present invention; and between the carbon atom of this acryloyl group or the combination of methacryl institute, be combined with the carbon atom below 15 and/or the co-polymerized monomer of oxygen atom; for form 20/more than the mm, promptly pitch such high density below 50 microns and thickness are photoresist figure more than the 20 microns composition that is absolutely necessary.In other words, photoresist figure height is big to the ratio (aspect ratio) of the size of Width, and in order to prevent to topple over or tilt, it is necessary keeping the intensity of figure for the crosslink density after the increasing photopolymerization.

On the other hand, on the not exposure part of conductive board, electroplate for implementing, must remove photosensitive polymer combination with developer solution, can not remove because of entering of the scattering of exposure system and the light that reflects to form makes that the degree of photosensitive polymer combination is big more then can not carry out polymerization or crosslinked more with developer solution.Promptly must strengthen visuals and exposure crosslink density partly poor not, so at least one composition is necessary for the co-polymerized monomer that has 3 acryloyl groups or methacryl in a molecule at least within the monomer component.In addition; under the situation of the co-polymerized monomer that uses the acryloyl group only have below 2 or methacryl; even if or use atomicity (carbon atom between the carbon atom of the acryloyl group of co-polymerized monomer of the acryloyl group have more than 3 or methacryl or the combination of methacryl institute; oxygen atom) is monomer more than 16; can not obtain implementing the crosslink density of enough resin figures required for the present invention, or the figure deliquescing is toppled over or adjacent pattern between be close together mutually and can not get desirable figure.

From above viewpoint; in the present invention; in a molecule; at least have 3 acryloyl groups or methacryl; and between the carbon atom of this acryloyl group or the combination of methacryl institute, be combined with below 15 the monomer that it is desirable to be combined with carbon atom below 7 and/or the oxygen atom composition that is absolutely necessary.

The acryloyl group that this monomer has or the number of methacryl are 3 in a molecule at least; if but this number is greater than necessary number; the reactive group number of participating in light reaction is also restricted; contribution to sclerous reaction is few; on the contrary can be remaining as semi-harden resinous principle residue (scum) on exposure part substrate surface, after electroplating work procedure in cause the big problem of the defective grade of plating.The desirable scope of the acryloyl group that this monomer has or the number of methacryl is 3 to 10.

Monomer component can detect with liquid chromatogram or gas-chromatography in addition.

Here the said meaning that has carbon atom below 15 and/or oxygen atom between the carbon atom of acryloyl group or the combination of methacryl institute is as follows.

At first, the carbon atom of so-called acryloyl group or the combination of methacryl institute is the carbon atom of hydroxyl one side of joining by ester bond and acrylic or methacrylic acid.The carbon atom that combines with hydroxyl that the meaning that is referred to as the carbon atom of this hydroxyl one side refers to when being attached to ester hydrolysis to be produced.That is, what say is the shortest between this carbon atom, does not comprise during the number number that this carbon atom has been combined with 15 each the following carbon atom or the meaning of oxygen atom.Be under 0 the situation, to mean that corresponding carbon atom has carried out combination to each other at this number, do not comprise that corresponding carbon atom is the situation of same carbon atom.In addition, several rules of the atom number between corresponding carbon atom are decided to be within the corresponding carbon atom more than 3, concerning any one carbon atom, within the remaining corresponding carbon atom more than 2, select the minimum carbon atom of atom number between corresponding carbon atom, and this atom number is used as atom number between corresponding carbon atom.

For ease of explanation, lift an object lesson.Being located at the carbon atom between this carbon atom and/or the number of oxygen atom is 1; then can enumerate trimethylolpropane tris (methacrylate) and dipentaerythritol acrylate; it as this number 13 example; can enumerate three [acryloyl group two (oxygen ethyl)] trimethylolpropane; as this number is 0 example, can enumerate in the glycerine three olefin(e) acid esters etc.

As the acryloyl group or the methacryl that in a molecule, have more than 3; and; between the carbon atom of this acryloyl group or the combination of methacryl institute, be combined with the carbon atom below 15 and/or the co-polymerized monomer of oxygen atom; can enumerate following object lesson: trimethylolpropane triacrylate or trimethyl acrylic ester; triacryl or trimethyl acryloyl group ethyl trimethylolpropane; divinyl oxide base trimethylolpropane triacrylate or trimethyl acrylic ester (di (ethyleneoxy) trimethylolpropane triacrylate or methacrylate) pentaerythritol triacrylate or methacrylate; tetramethylol methane tetraacrylate or methacrylate; dipentaerythritol four/five/six acrylate or methacrylate; glycerol tri-acrylate or methacrylate or have at the ortho position of the ester group of the acrylate of contiguous these compounds or methacrylate and inserted single or many (ethoxy) isostructural compound make the compound with the hydroxyl more than 3 carry out polyalcohols that condensation obtains and to the compound that has imported acryloyl group or methacryl more than 3 in the hydroxyl below 10 of the alkyl polyols class of vinyl alcohol oligomer etc. etc.These co-polymerized monomers both can use separately, also can make more than 2 kinds the composition use that combines.When the content of these co-polymerized monomers was very few, the resin strength of figure was low, can not bring into play effect of the present invention, and too much the time, then had to produce the shortcoming in crack etc. on the resin figure.In the present invention, the desirable amount of these co-polymerized monomers is for 100 weight portion prepolymers, contains 1～30 weight portion, and even more ideal is to use in the scope of 3～15 weight portions.

For the photosensitive polymer combination among the present invention,,, can also add various one-tenth as required and assign to use perhaps for the ease of handling in order to obtain better figure.For example, in order to adjust the viscosity of photosensitive polymer combination, also can contain the monomer that in a molecule, has the polymerism functional group below 2, for improve and conductive board between closing force, contain co-polymerized monomer, forbid agent or the like for the keeping quality that improves photosensitive polymer combination contains thermal polymerization with phosphate.In addition,, or improve sensitivity, resolution, can also add luminous sensitivity dose etc. for reaction time, the firm time that shortens photosensitive polymer combination.

Though the wavelength photoreceptor of the Photoepolymerizationinitiater initiater that uses among the present invention does not have special provision, but, the Photoepolymerizationinitiater initiater that uses wavelength to have light absorption maximum in the scope of 300～420nm is suitable, and molar absorption coefficient 5～1000l/molcm is desirable.In other words, the light source of 300～420nm can use common high-pressure mercury-vapor lamp bulb, industrial can the manufacturing extremely cheaply.Under the situation of using molar absorption coefficient above the Photoepolymerizationinitiater initiater of 1000l/molcm, light does not reach the inside of photosensitive polymer combination, can not harden fully.In addition, if increase exposure time, the part that does not then allow to harden is also hardened, and can not form conductor with electroplating.On the other hand, if with the Photoepolymerizationinitiater initiater of molar absorption coefficient less than 5l/molcm, then the sensitivity of photosensitive polymer combination is low excessively, impracticable.

In addition, the mensuration of molar absorption coefficient and light transmission can be with common spectrophotometric determination.

Example as such Photoepolymerizationinitiater initiater, can enumerate following example: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin propyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dihydroxy-2-phenyl acetophenone, 2,2-dimethoxy-2-phenyl acetophenone and 2-diethoxy-2-phenyl acetophenone.

Light absorber among the present invention if having absorption in using wavelength region may, and can dissolve or be distributed to the light absorber of liquid light-sensitive resin composition equably, then is not particularly limited to be pigment, ultraviolet absorber etc.This light absorber can absorb the scattering and the circuitous incident that produced of reflection of exposure system with good efficiency, can not remove the liquid light-sensitive resin composition that does not allow the part of hardening originally with developer solution, prevents that the effect of hardening is just good more.

In the present invention, adopt that to make the light transmission of the way sense of control photosensitive resin composition that Photoepolymerizationinitiater initiater and light absorber combine be very important.For this reason, the light absorption that it is desirable to contain 0.1～10 weight % is the Photoepolymerizationinitiater initiater of 5～1000 liters/molcm of molar absorption coefficient at place greatly, and it is 15～75% that the light absorber that contains 0.01～1 weight % makes light transmission become.When using such Photoepolymerizationinitiater initiater and light absorber with above-mentioned ratio, owing to can prevent the not sclerosis of the photosensitive polymer combination of exposure part, for example, even if thickness is 100 microns such thickness, also can bring into play image dissection pitch such high image dissection definition below 50 microns, but also can improve the not development of exposure part, wait when forming conductor so on conductive board, use to electroplate, the possibility that generation broken string or conductor attenuate is minimum, can form the high low-resistance thick film conductor of reliability.Then can not adjust to light absorber 75% below to the light transmission of photosensitive polymer combination if absorbance is little and do not contain the amount that surpasses 1 weight % because be easy to produce dissolving, dispersion is defective and ooze out (outflow), is unfavorable.If enumerate desirable scope, then the scope of the Photoepolymerizationinitiater initiater of photosensitive polymer combination is 0.5～5 weight %, and the scope of light transmission is 20～60%.In other words, from the viewpoint of the easiness of exposure time and processing, photosensitive polymer combination will become ultraviolet sensitivity and be scope better in practicality.

If employing the present invention uses above-mentioned photosensitive polymer combination can form various thick film circuit conductors.

The schematic diagram of Fig. 2 has illustrated the different pitch connecting wiring parts that the different parts of cloth string pitch are coupled together, but as shown in the figure, can constitute with conductor 6 cloth string pitch big parts 5a and the little parts 5b of cloth string pitch are coupled together.In so different pitch connecting wiring parts, the conductor fig that forms parts 5b one side is difficult especially, if but use photosensitive polymer combination of the present invention, then can form the conductor fig of thick film with high dimensional accuracy and shape stability.

The top view of Fig. 3 shows planar coil, but as shown in the figure, constituting in insulating properties substrate 11 tops of planar coil forms.The photosensitive polymer combination of the application of the invention, as shown in Figure 4, it is high and have a coil-conductor 12 of section configuration of the rectangle of fillet R two marginal portions to obtain aspect ratio.

Also have, in Fig. 3 and Fig. 4, label 13 is terminal parts, and label 14 is the wirings of detouring, and label 15 is hardening things of photosensitive polymer combination, and label 16 is interlayer bonding agents, and label 17 is solder resists.

Below explain the present invention with embodiment.In addition, the present invention is not limited by embodiment.

(embodiment 1)

In 2 times of dilutions of the zincate treatment fluid (SUB-STAR NZ2) that the wild drugmaker of Austria produces, be thickness that 100 microns aluminium base soaked 60 seconds 40 ℃ of temperature, use again after the flowing water cleaning base plate surface, aqueous solution of nitric acid with 5 weight % dissolves the zinc layer on surface, handles with above-mentioned zincate treatment fluid once more.By means of this processing, form thickness in the aluminium base top and be 0.3 micron zinc film.

Secondly, under the state that is adding voltage on this aluminium base of having handled, be dipped in the cupric pyrophosphate electroplate liquid, at 55 ℃, 3A/dm ²Current density under carry out 18 minutes metallide, obtain the copper film of about 20 micron thickness.Then, at 35 ℃, 2A/dm ²Current density under implement 90 minutes metallide.

Silk screen printing bonding agent on the surface of the substrate of making like this (Cemedine EP008, EP007), copy to glass epoxy resin substrate top and carry out bonding after, remove aluminium base with 10% hcl corrosion.

As mentioned above, the result who the amount of the electrolytic copper plating film surface zinc nearby that forms in glass epoxy resin substrate top is carried out quantitative analysis with auger electrons light-dividing device (Hitachi's production), begin to have observed zinc till 3 microns the degree of depth from substrate surface, the average containing ratio of the zinc that exists in this zone is 10 atom %.

When 35 ℃ of humidity of temperature are placed oxygen that resulting electrolytic copper plating substrate begins depth direction with the analysis of auger electrons light-dividing device from the copper facing film surface after 10 days for 90% time and had the zone, learn that oxygen only exists only in the zone till the about 0.4 micron degree of depth in copper surface.

(comparative example 1)

On untreated aluminium base surface, making the copper facing film under the plating condition similarly to Example 1, duplicate again bond on the glass epoxy resin substrate after, remove aluminium base with 10% hcl corrosion.

When 35 ℃ of humidity of temperature are placed oxygen that resulting electrolytic copper plating substrate begins depth direction with the analysis of auger electrons light-dividing device from the copper facing film surface after 10 days for 90% time and had the zone, learn that oxygen is present in the zone till the about 0.9 micron degree of depth in copper surface.

Employing is to the way of conductive surface importing oxygenous layer, and the oxidative resistance on copper surface improves tremendously as can be known.

Secondly, use the method identical with embodiment 1, the aluminium base after handling is dipped in the cupric pyrophosphate plating bath, except that beginning after 1 minute the making alive, other use the condition identical with embodiment 1 to electroplate, and make the electrolytic copper plating substrate.

Measure the table 1 that the results are shown in of the zinc amount that begins depth direction from the surface of resulting electrolytic copper plating substrate with the auger electrons light-dividing device.By this table as can be known, under adding the state of voltage, be dipped under the situation in the electroplate liquid (the present invention), the degree of depth that zinc atom is present in conductor is in 5 microns the top layer part, to this, under making alive not is dipped into situation in the electroplate liquid, because the zinc atom stripping is in electroplate liquid, so do not have zinc atom in the part of conductor top layer.

Table 1

The degree of depth apart from conductive surface is added with not making alive of voltage
	0 (surface) 12.1 do not detect
0.2 micron 10.8 does not detect
	0.6 micron 8.7 does not detect
0.8 micron 6.9 does not detect
	1.0 micron 6.0 does not detect
2.5 micron 1.1 does not detect
	5.0 micron does not detect

(embodiment 2)

Is diethylene glycol, propylene glycol, adipic acid, fumaric acid, itaconic acid that the ratio of 0.38/0.12/0.24/0.14/0.12 makes it to become for 1kg and puts in the reactor with the mol ratio, forbid agent as thermal polymerization, add the 4-metoxyphenol of 0.25g and the triethanolamine phosphate of 2.5g again, in blanket of nitrogen, in reaction temperature is that 200 ℃, reaction time are 4 hours, under reduced pressure carry out polycondensation, makes number-average molecular weight and be 1500 unsaturated polyester (UP) prepolymer composite.In this prepolymer of 100 weight portions, add 12 parts of TEG dimethylacrylates, 5 parts of diethylene glycol dimethylacrylates, 8 parts of 2-hydroxyethyl methacrylates, 15 parts of pentaerythritol acrylate trimethyls, 5 parts of mono phosphoric acid esters (methacryl 2-ethoxyethyl acetate), 2 part 2,2-dimethoxy-2-phenyl acetophenone, 0.05 part of uncle 4--challis butyl catechol and 0.1 part of Kayaset Red A-BR (Japanese chemical drug (strain) production), mix fully, obtain photosensitive polymer combination.

Secondly, the SRB device with Asahi Chemical Industry's industry (strain) is produced is coated to photosensitive polymer combination the aluminium base top of having carried out processing similarly to Example 1.At this moment, regulate with liner and make the thickness of photoresist layer become 100 microns.By with the ultraviolet ray of the corresponding glass mask irradiation of the wiring figure of the density of 20/mm mercury short arc lamp, the Boratex aqueous solution with 1% makes not exposure partly develop, and carries out after-hardening in 10 minutes with 85 ℃ hot water injections, formation resin figure.

Being dipped in the pyrrolin acid copper plating bath (going up village industry society produces) at following resulting resin image substrate of the state that adds voltage, is 3A/dm in cathode-current density ²Condition under, separate out 90 microns copper facing film, form the figure conductor.(Cemedine EP008, EP170) is screen-printed on the surface of resulting substrate bonding agent, duplicate bond on the glass epoxy resin substrate after, peel off with mechanical means and to remove aluminium base, make thick-film conductor circuit.

It is square that resulting substrate is cut into 2cm, and with epoxy resin make it the sclerosis after, with grinder section is carried out mirror ultrafinish, and the result who carries out the shape observation of thick film conductor, the thickness that repeats 50 microns of pitches, conductor upper end is 90 microns, and the thickness at both ends, conductor upper end is 92 microns and presents mild radius of curvature.In addition, the section configuration of conductor integral body is a rectangular shape, and the ratio of the width of conductor width and photosensitive polymer combination is 1: 5.

Resulting circuitous pattern is carried out the result that electrology characteristic is measured, and the resistance between conductor is 2 * 10 ⁵M Ω is above, insulation breakdown voltage more than 1kV, show that the result is good.In addition, at the rate of descent very little (below ± 2%) of the resistance under the environment of 85 ℃ of temperature, humidity 90%, after 1000 hours.Even if in 85 ℃ of temperature, humidity 90%, add 24VDC, under 100 hours, also do not see the surface deterioration of separating out copper etc. from conductive surface, proved the high reliability of the thick-film conductor circuit that obtains with the present invention.

(embodiment 3)

Is diethylene glycol, propylene glycol, adipic acid, fumaric acid, itaconic acid, isophthalic acid the ratio of 0.375/0.125/0.17/0.15/0.15/0.03 with the mol ratio, make it to become 1kg, in the threading reactor, forbid agent as thermal polymerization, add the 4-metoxyphenol of 0.25g and the triethanolamine phosphate of 2.5g again, in blanket of nitrogen, in reaction temperature is that 200 ℃, reaction time are 4 hours, under reduced pressure carry out polycondensation that making acid value is the unsaturated polyester (UP) prepolymer composite of 32mg KOH/g (the number-average molecular weight scaled value is 1750).

In these prepolymer 100 weight portions, add 12 parts of TEG dimethylacrylates, 5 parts of diethylene glycol dimethylacrylates, 8 parts of 2-hydroxyethyl methacrylates, 12 parts of pentaerythritol acrylate trimethyls, 3 parts of pentaerythrite tetramethyl acrylate, 5 parts of mono phosphoric acid esters (methacryl 2-ethoxyethyl acetate), 2 part 2,2-dimethoxy-2-phenyl acetophenone, 0.05 part of uncle 4--challis butyl-4-methylphenol and 0.15 part of Kayaset Red A-2G (Japanese chemical drug (strain) production), mix fully, obtain photosensitive polymer combination.

Secondly, in 2 times of dilutions of the zincate treatment fluid (SUB-STAR NZ2) that the wild drugmaker of Austria produces, be thickness that 100 microns aluminium base soaked 80 seconds 30 ℃ of temperature, use again after the flowing water cleaning base plate surface, aqueous solution of nitric acid with 15 weight % dissolves the zinc on surface, handles with above-mentioned zincate treatment fluid once more.By means of this processing, form thickness in the aluminium base top and be 0.24 micron zinc film.

The above-mentioned liquid light-sensitive resin composition that has modulated is coated to the aluminium base top of having carried out above-mentioned processing, by with the wiring figure of the density of 20/mm (50 microns of cloth string pitch) right-ultraviolet ray of corresponding mask irradiation mercury short arc lamp, the Boratex aqueous solution with 1% makes not exposure partly develop, carry out after-hardening in 10 minutes with 85 ℃ hot water injections, form the resin figure.

Then, (this aluminium base) is dipped in the cupric pyrophosphate electroplate liquid under the state that the aluminium base that has formed the resin figure is added voltage, at 55 ℃, 3A/dm ²Current density under carry out 18 minutes metallide, obtain the copper film of about 20 micron thickness.Afterwards, at 35 ℃, 2A/dm ²Current density under, implement 90 minutes copper sulphate metallide.

Silk screen printing bonding agent on the surface of the substrate of making like this (Cemedine EP008, EP007), copy to glass epoxy resin substrate top and carry out bonding after, hcl corrosion with 10% is removed aluminium base, and obtaining wiring density is that 20/mm, conductor thickness are 100 microns thick-film conductor circuit.

As mentioned above, the result who the amount of the electrolytic copper plating film surface zinc nearby that forms in glass epoxy resin substrate top is carried out quantitative analysis with auger electrons light-dividing device (Hitachi's production), observed zinc till the degree of depth of 2.2 microns of substrate surfaces, the average containing ratio of the zinc that exists in this zone is 8 atom %.

When 35 ℃ of humidity of temperature are placed oxygen that resulting electrolytic copper plating substrate begins depth direction with the analysis of auger electrons light-dividing device from the copper facing film surface after 10 days for 90% time and had the zone, learn that oxygen only exists only in the zone till the about 0.4 micron degree of depth in copper surface.

In the high density thick-film conductor circuit, also has good non-oxidizability as can be known.

(comparative example 2)

Except to make diethylene glycol, propylene glycol, adipic acid, fumaric acid, itaconic acid, isophthalic acid be the ratio of 0.375/0.125/0.30/0.125/0.025/0.05 with the mol ratio than being decided to be packing into, through the processing identical, make the unsaturated polyester (UP) prepolymer composite with embodiment 3.Said composition with the composition of chemical formula (1) expression than not belonging within the scope of the present invention.

Form the resin figure with handling similarly to Example 3, resin visuals crustal inclination is put off till with adjacent figure, just can not form the plating conductor on this part.In addition, the result of liquid chromatogram measuring shows, the infiltration of resinous principle in electroplate liquid taken place, and the stain that produces the copper film reduces the life-span of electroplate liquid.Even if at every 1m ³Electroplate liquid electroplate 100000m ²Substrate after crust test in also lackluster zone.

(embodiment 4)

Make diethylene glycol, fumaric acid, isophthalic acid, itaconic acid, be the ratio of 0.5/0.13/0.24/0.13 with the mol ratio, polycondensation under the condition identical with embodiment 3, making acid value is the unsaturated polyester (UP) prepolymer of 33mg KOH/g (the number-average molecular weight scaled value is 1700).

In these prepolymer 100 weight portions, add 15 parts of TEG dimethylacrylates, 5 parts of diethylene glycol dimethylacrylates, 5 parts of 2-hydroxyethyl methacrylates, 3 parts of diacetone acrylamides, 12 parts of trimethoxy propane trimethyl acrylic esters, 5 parts of mono phosphoric acid esters (methacryl 2-ethoxyethyl acetate), 4 parts of benzoin isobutyl ethers, 0.05 part of uncle 4--challis butyl-4-methylphenol and 0.12 part of Oil Yellow 3G (Orient chemistry (strain) production), mix fully, obtain photosensitive polymer combination A.

In addition, except need not above-mentioned isophthalic acid, obtain photosensitive polymer combination B through same processing and replace adipic acid is used as outside the have chemical formula compound of composition of (3).

Secondly, this photosensitive polymer combination A, B are coated onto the aluminium base top of having carried out processing similarly to Example 1 respectively, thickness is 90 microns, and using with pitch is that the corresponding mask of wiring figure of 45 microns density uses the method identical with embodiment 3 to form the resin figure.Then, use with the same condition of embodiment and carry out electrolytic copper plating, removing aluminium sheet with 10% hcl corrosion, to obtain conductor thickness be 90 microns thick-film conductor circuit parts.

Use photosensitive polymer combination B, can obtain good thick-film conductor circuit parts and do not have broken string.In addition, application photosensitive polymer combination A's, after developing, photosensitive polymer combination finds the development remnants of bridge shape, though found broken string in the parts about 25%, remaining parts can be used as thick-film conductor circuit.

(comparative example 3)

Except replacing without the trimethoxy propane trimethyl acrylic ester of the photosensitive polymer combination B among the embodiment 4, use the method identical to make photosensitive polymer combination with embodiment 4 with the propylene glycol dimethylacrylate.The resin figure of this resin figure and embodiment 4 is than soft or topple over or collide with adjacent figure, and the conductor after the plating is also intermittent, can not be used as thick-film conductor circuit fully.

In addition, in order to strengthen the intensity of resin figure, make ultraviolet irradiation time double to form the resin figure, the result not resin of exposure part is also hardened, and can not form conductor with electroplating.

(embodiment 5)

The thickness of Japan Aluminum (strain) being produced at the SUB STAR-ZN2 treatment fluid of producing with wild pharmaceuticals industry difficult to understand (strain) is that 100 microns aluminium base carries out 30 ℃, 60 seconds surface treatment, after nitric acid with 15% carries out handling and corroding in 30 ℃, 60 seconds, carry out 30 ℃, 60 seconds surface treatment again with SUBSTAR-ZN2, form zincate layer.

Secondly, make diethylene glycol to 100 parts, propylene glycol, adipic acid, itaconic acid, fumaric acid is respectively with the ratio of mol ratio 0.45/0.05/0.20/0.15/0.15, in blanket of nitrogen, reaction temperature is 195 ℃, 5 hours reaction time, polycondensation under reduced pressure, resulting number-average molecular weight scaled value is in 1700 the unsaturated polyester resin, add 15 parts of pentaerythritol acrylate trimethyls, 3 parts of diethylene glycol dimethylacrylates, 7.5 part TEG dimethylacrylate, 4 parts of 2-hydroxyethyl methacrylates, 3.6 part mono phosphoric acid ester (methacryl 2-ethoxyethyl acetate), 2 part 2,2-dimethoxy-2-phenyl acetophenone, 0.04 part 2, uncle 6-di-challis-butyl-4-methylphenol and 0.2 part of Oil Yellow 3G (Orient chemistry (strain) production), and mix fully, obtain photosensitive polymer combination.With the SR-B device that Asahi Chemical Industry's industry (strain) is produced, the photosensitive polymer combination of being modulated is coated onto the aluminium base top of the above-mentioned processing of process with 37 microns thickness.The directional light mode light source of producing with Oak company, by with the corresponding glass mask of wiring figure of the figure that contains 26 microns of minimum wiring pitches, carry out exposure, development (Boratex 1% solution, 40 ℃, discharge pressure 0.1kg/cm ²), make wide 5～10 microns, high 32 microns resin figure in aluminium base top through above-mentioned processing.

Cupric pyrophosphate electroplate liquid with (strain) Murata society produces is adding under the state of voltage, drops in the electroplate liquid, and close at cathode current is 3A/dm ²Condition under, on the aluminium base that has formed above-mentioned resin figure, separate out the electroplated copper film of 30 microns of thickness, form the figure conductor.After having removed the resin figure with the concentrated sulfuric acid, be hot-pressed onto with bonding thin plate on the pi thin plate of 25 micron thickness that company of Du Pont (Dupont) produces, hcl corrosion with 10% is removed aluminium base, obtains containing the thick-film conductor circuit that the minimum wiring pitch is 26 microns a part.No matter this thick-film conductor circuit which can carry out the minimum wiring pitch less than 50 microns high-density wiring, measure the attenuation rate of thick-film conductor circuit with pulse generator (TM502A of Techtronics company) by the signal of front and back, because the resistance of wiring is low, so the attenuation rate of signal is minimum, this conductor circuit can be used as different pitch links and uses.

(embodiment 6)

Make diethylene glycol, propylene glycol, adipic acid, fumaric acid, itaconic acid, isophthalic acid ratio with mol ratio 0.4/0.1/0.22/0.12/0.12/0.04, in blanket of nitrogen, reaction temperature is 200 ℃, 4 hours reaction time, polycondensation under reduced pressure, makes number-average molecular weight and be 1500 unsaturated polyester (UP) prepolymer.

In these prepolymer 100 weight portions, add 12 parts of TEG dimethylacrylates, 5 parts of diethylene glycol dimethylacrylates, 8 parts of 2-hydroxyethyl methacrylates, 12 parts of pentaerythritol acrylate trimethyls, 3 parts of pentaerythrite tetramethyl acrylate, 5 parts of mono phosphoric acid esters (methacryl 2-ethoxyethyl acetate), 2 part 2,2-dimethoxy-2-phenyl acetophenone, 0.05 part uncle 4--challis-butyl catechol is as the light absorber of Photoepolymerizationinitiater initiater and 0.15 part of Kayaset Red A-20 (Orient chemistry (strain) production), mix fully, obtain photosensitive polymer combination.

2, the molar absorption coefficient in the ethanol of 2-dimethoxy-2-phenyl acetophenone is 181l/molcm (336nm).Molar absorption coefficient in mercury vapor lamp emission wavelength zone, do not having glass etc. optical system absorption and to the scope of the effective 300～420nm of initiation reaction in measure with the wavelength of the absorption maximum that provides Photoepolymerizationinitiater initiater.In addition, the light transmission at above-mentioned wavelength place in 100 of this photosensitive polymer combination microns thickness is 24%.

Secondly, this photosensitive polymer combination is coated onto the aluminium base top of having carried out processing similarly to Example 1, thickness is 100 microns, uses the corresponding photomask of wiring density with 25/mm (the cloth string pitch encloses 40 microns), forms the resin figure with similarly to Example 3 method.Then, with similarly to Example 3 method the substrate that has formed the resin figure is implemented metallide, removing aluminium sheet with 10% hcl corrosion, to obtain wiring density be 25/mm, and conductor thickness is 100 microns a thick film conductor wiring plate.

(comparative example 4)

Remove without 2 part 2 among the embodiment 6,2-dimethoxy-2-phenyl acetophenone and replacing with outside 1 part of 2-methylanthraquinone is made photosensitive polymer combination through processing similarly to Example 6.The absorptivity of 2-methylanthraquinone is 3800 l/molcm (326nm), and the light transmission of this photosensitive polymer combination under 100 microns thickness is 1.8%.

Secondly, with method similarly to Example 6 this photosensitive polymer combination is carried out figure and form, but light do not reach on the aluminium base, on aluminium base, do not remain the resin figure.Make ultraviolet irradiation time become 5 times and make light can arrive on the aluminium base, regrettably the resin of exposure part does not harden yet, and can not form and electroplate conductor.

(embodiment 7)

SUB STAR-ZN2 treatment fluid with the wild pharmaceuticals industry of Austria (strain) production, at 40 ℃ of thickness that Japan Alnminum (strain) is produced is that 100 microns aluminium base carries out 60 seconds surface treatment, nitric acid with 15% is after 30 ℃ of processing were corroded in 60 seconds, again with SUB STAR-ZN2 treatment fluid 30 ℃ of surface treatments of carrying out 60 seconds, form zincate.

Secondly, the diethylene glycol that makes to 100 parts, propylene glycol, adipic acid, itaconic acid, the number-average molecular weight that fumaric acid obtains with the ratio polycondensation of mol ratio 0.45/0.05/0.20/0.15/0.15 respectively is in 1700 the unsaturated polyester resin, add 15 parts of trimethylol-propane trimethacrylates, 4 parts of bisphenol-A-two-(ethoxyl methyl acrylate), 7.5 part TEG dimethylacrylate, 4 parts of 2-hydroxyethyl methacrylates, 3.6 part mono phosphoric acid ester (methacryl 2-ethoxyethyl acetate), 1 part of benzoin isobutyl ether, 0.04 part 2,6-two uncles-challis-butyl-4-methylphenol and as 0.014 part of OPLAS Yellow 130 (Orient chemistry (strain) production) of light absorber, fully mix, obtain photosensitive polymer combination C.

In addition, remove without 1 part the benzene idol of photosensitive polymer combination C and draw isobutyl ether, and replace with 2 parts 2,2-dimethoxy-2-phenyl acetophenone, replace outside the Oil Yellow-3G that produces with the Orient chemistry (strain) of 0.05 five equilibrium without the OPLASYellow-130 of Orient chemistry (strain) production, modulation through same with photosensitive polymer combination C obtains photosensitive polymer combination D.

The light transmission of the 365nm of the U3210 type spectrophotometric determination photosensitive polymer combination C that produces with the Hitachi learns when thickness is 350 microns to be 30%, is 71% when thickness is 100 microns.Equally, the light transmission of photosensitive polymer combination D is 26% when thickness is 50 microns, is 59% when thickness is 20 microns.

The photosensitive polymer combination that the SR-B device handle of producing with Asahi Chemical Industry's industry (strain) prepares is coated onto the aluminium base top after the above-mentioned processing.At this moment, regulate with liner and make photoresist layer become the thickness shown in the table 2 respectively.The light source of the directional light mode of producing with the glass mask and the Oak company of regulation according to the way of embodiment 3, is made the resin figure of wide 6～40 microns specified altitudes in the aluminium base top.

The cupric pyrophosphate electroplate liquid of producing with (strain) Murata society add drop into substrate under the state of voltage after, at the slight 3A/dm of cathode current ²Condition under, on resulting resin figure, separate out the copper facing film of the thickness shown in the table 2, form the figure conductor.(Cemedine EP008, EP170) is screen-printed on the surface of resulting substrate bonding agent, and duplicates and bond to after the glass epoxy resin insulated substrate top, removes aluminium base with 10% hcl corrosion, obtains thick film figure conductor.

It is square that resulting substrate is cut into 2cm, behind epoxy cure, with grinder section carried out mirror ultrafinish, observes graphics shape, measures the resistance value of per unit length again, the results are shown in table 2.

Table 2

Sample number	Composition	Minimum wiring pitch (micron)	Numerical value thickness (micron)	Conductor width (micron)	Conductor height (micron)	Conductor resistance (Ω/cm)
							????1 ????2 ????3 ????4	????C ????C ????D ????D	????95 ????50 ????28 ????14	????350 ????100 ????50 ????20	????55 ????30 ????15 ????8	????335 ????95 ????50 ????18	?0.01 ?0.06 ?0.24 ?1.3

As can be known from the results of Table 2, the thick film figure conductor that obtains with the present invention can be the cloth string pitch less than 100 microns, particularly can be high-density wiring figure less than 50 microns, in addition, the resistance value of each cm is also minimum.

(embodiment 8)

Remove outside the light absorber of the various kinds shown in the use table 3, concentration, use the method modulation photosensitive polymer combination same with the photosensitive polymer combination C of embodiment 7, measuring thickness is the light transmission of the 365nm under 80 microns.

Table 3

Sample number	The kind of light absorber	Concentration (weight %)	Transmissivity (365nm) under 80 microns of the thickness
				????5 ????6 ????7 ????8	No Orient chemical production, the chemical drug production of Oil Yellow 3G Japan, Kayaset Red A-2G Orient chemical production, OPLAS Yellow 130	?0％ ?0.15％ ?0.1％ ?0.05％	????83％ ????12％ ????31％ ????33％

Secondly, with method similarly to Example 6, use the above-mentioned photosensitive polymer combination that has prepared, make the photoresist figure of 40 microns pitches (25/mm wiring), 80 microns height, cupric pyrophosphate electroplate liquid with the production of (strain) Murata society, add under the state of voltage drop into substrate after, at cathode-current density 3A/dm ²Condition under separate out 80 microns copper facing film, form thick-film conductor circuit.

(Cemedine EP008, EP170) is screen-printed on the surface of resulting substrate bonding agent, and duplicates and bond to after the glass epoxy resin insulated substrate top, removes aluminium base with 10% hcl corrosion, obtains thick film figure conductor.Shape, the resistance value of resulting conductor are shown in table 4.

Table 4

Sample number	Actual measurement conductor height (micron)	Conductor resistance (Ω/cm)
			????5 ????6 ????7 ????8	????77 ????81 ????80 ????82	Broken string short circuit 0.07 0.07

In table 4, sample number 5,6 does not belong to scope of the present invention, is comparative example.As can be known the light transmission of photosensitive polymer combination greater than 75% situation under, be extremely difficult less than 50 microns high-density wiring perhaps less than cloth string pitch under 15% the situation.Transmissivity greater than 75% situation under, photographic fog phenomenon when developing because of exposure is electroplated conductor part ground and is not separated out, and is easy to break.In addition, transmissivity less than 15% situation under because the sclerosis of photoresist is insufficient, when developing or the photoresist figure peel off, or copper facing is slipped between photoresist and the substrate when electroplating, and is easy to produce short circuit between conductor.

To this, under the situation of sample number 7,8, the cloth string pitch is possible less than 50 microns high-density wiring, and the resistance value of per unit length also is extremely low low resistance for O.1 below the Ω.

(embodiment 9)

The aluminium base of using thickness that AZ401 zincate treatment fluid that village's industry (strain) produces produces Japan Aluminum (strain) and be 100 microns carries out 30 ℃ of surface treatments of 80 seconds.The result of the diffusion reflection surface rate the during 365nm of the resulting aluminium base of producing with Shimadzu Seisakusho Ltd.'s (strain) of MPS-2000 spectrophotometric determination is 18%.Secondly, make diethylene glycol to 100 weight portions, propylene glycol, adipic acid, isophthalic acid, fumaric acid, the number-average molecular weight that itaconic acid obtains with the ratio polycondensation of mol ratio 0.38/0.12/0.2/0.05/0.14/0.11 respectively is in 1830 the unsaturated polyester (UP) prepolymer, add 14 parts of pentaerythritol acrylate trimethyls, 4.5 part diethylene glycol dimethylacrylate, 10.5 part TEG dimethylacrylate, 2 part 2,2-dimethoxy-2-phenyl acetophenone, 0.04 part 2,6-two-uncle-challis-butyl-4-methylphenol and 0.2 part of OPLAS Yellow 140 (Orient chemistry (strain) production), after fully mixing, obtain photosensitive polymer combination.The photosensitive polymer combination of the SR-B device of producing with Asahi Chemical Industry's industry (strain) after modulation is coated onto the aluminium base top after the above-mentioned processing.At this moment, with liner to each sample regulate make the photoresist thickness become for the regulation thickness.The directional light mode light source of the mercury short arc lamp of producing with the glass mask and the Oak company of regulation carries out mask exposure develop (Boratex 1% solution, 40 ℃, discharge pressure 0.1kg/cm ²), make wide 4～35 microns height in the aluminium base top and be the resin figure more than 10 microns.

Use AZ401 zincate treatment fluid that village's industry (strain) produces add drop into substrate under the state of voltage after, be 3A/dm in cathode-current density ²Condition under on resulting photoresist figure, separate out conductor height as shown in table 4 the copper facing film.Bonding agent (Cemedine EP008, EP170) is being screen-printed on the surface of resulting substrate, and duplicate bond to glass epoxy resin insulation board top after, remove aluminium base with 10% hcl corrosion, obtain thick-film conductor circuit.

It is square that resulting substrate is cut into 2cm, and with after the epoxy resin embedding sclerosis, with polishing section is carried out mirror ultrafinish, observes graphics shape, and the resistance value of analytical unit length the results are shown in table 5 again.

Table 5

Sample number	Minimum wiring pitch (micron)	Conductor width (micron)	Conductor height (micron)	Conductor resistance (Ω/cm)
					????9 ????10 ????11 ????12	????20 ????30 ????45 ????10	????10 ????10 ????10 ????6	????15 ????30 ????50 ????8	????1.2 ????0.59 ????0.35 ????3.7

As shown in Table 5, no matter which can carry out the minimum wiring pitch less than 50 microns high-density wiring to the thick-film conductor circuit that obtains with the present invention, in addition, the resistance value of every 1cm is also very little.In addition, the sample with 10, (Tecktronics company, the attenuation rate of the signal after TM502A) generation signal measuring sample passes through because the resistance of wiring is low, so the decay of signal is also low, can transmit signal with pulse generator.

(embodiment 10)

The thickness that Japan Aluminum (strain) is produced is that 100 microns aluminium base carries out the various surface treatments shown in the table 6,7, measures the substrate surface diffuse reflectance with method similarly to Example 8.

Table 6

Processing method	Treatment conditions
		Polishing is rolled and is ground	BUFF3M produces HDFLAPS-SF#600 wheel revolution 220rmp vibration number 480 times/minute
Abrasive blasting	Frosted ScradomR#220 (Aluminum system) water spray pressure 2kgcm 2
		Warm water is handled	85 ℃ of ion exchange waters 10 minutes
The MBV method	90 ℃ of sodium carbonate/chromic acid (10/3w/w) 65g/l 20 minutes
		Permanganimetric method	80 ℃ of potassium permanganate 5g/l copper nitrate 20g/l 5 minutes
Zincate method 1	Last village industry (strain) was produced 30 ℃ of AZ-401 treatment fluids 80 seconds
		Zincate method 2	Wild pharmaceuticals industry difficult to understand (strain) was produced ZN-230 ℃ of SUBSTAR-ZN-2 treatment fluid 60 seconds, 30 ℃ in 15% nitric acid 60 seconds, ZN-230 ℃ 60 seconds

Table 7

Sample number	Processing method	Diffuse reflectance (365nm)
			13	Polishing is rolled and is ground	35％
14	Abrasive blasting	72％
			15	Polishing rolling+zincate is handled	13％
16	Polishing rolling+warm water is handled	16％
			17	MBV handles	17％
18	Permanganimetric method	4％

Secondly, the photosensitive polymer combination made from method similarly to Example 9, make 25 microns pitches, 10 microns wide, 30 microns high resin figure with the exposure developing apparatus, the cupric pyrophosphate electroplate liquid of producing with (strain) Murata society drops into substrate adding under the state of voltage, is 3A/dm in cathode-current density ²Condition under separate out the copper facing film of 30 microns of thickness, form the figure conductor.

(Cemedine EP008, EP170) is screen-printed on the surface of resulting substrate with bonding agent, duplicate bond to the glass substrate top after, remove aluminium base with 10% hcl corrosion, obtain thick-film conductor circuit.The measured value and the resistance value of the height of resulting conductor are shown in table 8.

Table 8

Sample number	Actual measurement conductor height (micron)	Conductor resistance (Ω/cm)
			????13	????28	Broken string
????14	????30	Broken string
			????15	????31	????0.38
????16	????30	????0.39
			????17	????26	????0.45
????18	????28	????0.42

In table 8, sample number 13,14 does not belong to scope of the present invention.Under the diffusion reflection surface rate of aluminium base was situation more than 20%, the high-density wiring of minimum wiring pitch below 50 microns was extremely difficult as can be known.Because the photographic fog phenomenon when exposure is developed is electroplated conductor part ground and is not separated out, and is easy to produce broken string.

In contrast, in sample number 15,16,17 and 18, can carry out the high-density wiring of minimum wiring pitch below 50 microns with that a kind of substrate no matter be.

(embodiment 11)

With the cupric pyrophosphate electroplate liquid of (strain) Murata society production, at cathode-current density 3A/dm ²Condition under the thickness produced at Japan Aluminum (strain) be that 100 microns aluminium base top forms about 6 microns copper facing film.With the condition of the sample number 1 of embodiment 10 this substrate is polished to roll and grind, produce Electrobrite#499 that society produces with (strain) weak former electricity and carry out 85 ℃ of surperficial melanism of 1 minute and handle.The diffusion reflection surface rate of resulting copper base is 3%.

With similarly to Example 10 method photosensitive polymer combination is coated onto on this substrate, carries out exposure and develop and electroplate, obtain conductor circuit substrate.After the pi substrate of the band bonding agent of resulting substrate and E.I.Du Pont Company implemented caking and remove aluminium base with 10% hcl corrosion, corrode with 25% ferric chloride solution and to remove the Copper Foil part.

The section configuration of figure conductor, the result that resistance is measured are shown, can make the thick-film conductor circuit that the different pitch connecting wiring parts that can be used as 22 microns of 15 microns of minimum wiring pitches, 7 microns of conductor widths and conductor height use.

(embodiment 12)

With the aluminium base that has carried out processing similarly to Example 1 with defer to embodiment 3 and carried out the photosensitive polymer combination adjusted and the glass mask of regulation, the coat photoresist layer thickness in the aluminium base top is that 100 microns, cloth string pitch are that 65 microns, photoresist width are that 15 microns, photoresist height are that 100 microns, the number of turn are the coiled type photoresist figure of 24 circles.

This coiled type graphical form 15 φ, 2 kinds at surface, the back side is arranged, by around separately internal diameter with the nest whirlpool shape coil of the spaced a plurality of same kind substantially of equal angles, be used for and the outside terminal that is connected, and these coils each other or the wiring of detouring that is connected between coil and terminal, also is useful on the through hole area formations such as (land) that the surperficial back side is connected.

The pyrrolin acid copper plating bath of producing with (strain) Murata society, add drop into substrate under the condition of voltage after, close at cathode current is 3A/dm ²Condition under in this photoresist figure, separate out 100 microns copper facing film, form conductor.

(Cemedine EP008, EP170) is screen-printed on the surface of resulting substrate bonding agent, the glass fabric (106/AS307) that rising sun シ ュ-ベ Le is produced is clipped in the middle, carry out the position alignment at surface, the back side, and duplicate bonding after, remove aluminium base with 10% hcl corrosion.Then, grind about about 4 microns with the polishing grinder and make the flattening surface that pastes substrate together, the solder resist USR-11G that grinds production with Tamuraization carries out the coating of 30 micron thickness with silk screen print method, implements UV cured.Secondly, form the hole of beating 0.45mm φ on the part with drill bit, after filling out solder(ing) paste, in reflow ovens, make the through hole conducting at through hole.

It is square that resulting planar coil is cut into 2cm, make it sclerosis with epoxy resin after, with grinder section is carried out mirror ultrafinish.Result with observation by light microscope coil-conductor part, learn that conductor width is that 50 microns, conductor height are 100 microns, the mean value of uneven thickness one property of Width for ± 3% being 15 microns and rectangular with interior, distance between conductors, conductor and insulating layer of conductor (liquid light-sensitive resin hardening thing) are in the same plane.

Insulation resistance between the terminal between the out-phase of resulting planar coil is no matter which all is 4 * 10 ⁵More than the M Ω, insulation breakdown voltage is good more than 1kV.In addition, under the environment of 85 ℃ of temperature, humidity 90%, all below ± 2%, rate of change is minimum for the inductance after 1000 hours, changes in resistance rate.In addition, in 85 ℃ of temperature, humidity 90%, add under 24VDC, 100 hours the situation, do not find to separate out and corrode from the copper of conductive surface yet.In addition, do not change yet, do not have short circuit yet even if the steel ball that makes 100g as shock test under the fallen situation of the height of 1m, has been confirmed inductance, resistance value.

(comparative example 5)

It at thickness 100 microns aluminium base top, ' it is 5 microns that Microresist 747-110cst ' makes dried thickness become to coat the negative photoresist that Kodak company produces, behind the prebake film, carry out exposure, development and back roasting film by the coil pattern mask.In the photoresist figure that the aluminium base top forms, the cupric pyrophosphate electroplate liquid of using the production of village industry society is at cathode-current density 4A/dm ²Condition under, separate out 50 microns copper facing film, form conductor.With duplicating with the same method of embodiment, after having finished the conducting of aluminium burn into through hole, use the pyrrolin acid copper plating bath that village industry society produces once more, be 5A/dm in cathode-current density ²Condition under, form 50 microns copper facing film.Then, form protective layer similarly to Example 12, make planar coil.

Learn that by resulting planar coil being carried out the section observation conductor shape is the spherical form that hemispheric two halves up and down connect together, about 50 microns of conductor radius, the conductor spacing is 15 microns.

Insulation resistance between the terminal between the out-phase of resulting planar coil is 2 * 10 ⁵More than the M Ω, more than the insulation breakdown voltage 0.9kV, be reasonable, but confirm, in 85 ℃ of temperature, humidity 90%, add 24VDC, after 100 hours, inductance and resistance have about 20% and 12% the tendency of descending respectively, and short circuit has taken place between conductor in test.In addition, carry out the result with the same shock test of embodiment 12, the coil that inductance, resistance value reduce by 20% or more has 28 in 100, has also observed short circuit or broken string between the conductor that impact caused.

The possibility of industrial utilization

The non-oxidizability of thick-film conductor circuit of the present invention, corrosion resistance are good, even if under hot and humid environment, the reduction of insulating properties, the underproof generations such as short circuit that migration produced of conductor element are few.In addition, owing to having the wiring density height, can freely setting the feature of resistance,, simultaneously, can also cheaply and more stably make so be the thick-film conductor circuit that is suitable for super-high density, low resistance wiring.

Claims (14)

1. thick-film conductor circuit is characterized in that: be in 5 microns the zone apart from the surface of conductors degree of depth that constitutes by copper, exist thickness and be 0.1～5 micron contain the zinc layer, zinc atom is 3～20 atom % to the ratio of copper atom.

2. the described thick-film conductor circuit of claim 1, it is characterized in that: the cross sectional shape on the Width of conductor is rectangular, and two marginal portions have fillet R in the lower end.

3. thick-film conductor circuit, it is characterized in that: the cross sectional shape on the Width of conductor is rectangular, and two marginal portions have fillet R in the lower end.

4. any one described thick-film conductor circuit in the claim 1～3, it is characterized in that: the minimum wiring pitch of conductor contains the part below 100 microns, and the aspect ratio of conductor is greater than 1.2, and the height of conductor is greater than 20 microns.

5. the manufacture method of a thick-film conductor circuit, it is characterized in that: use when containing the aluminium sheet that the zinc alkaline solution handled as conductive board, the photosensitive polymer combination of liquid is coated onto on this conductive board, with high-energy ray the part that should form the resin figure is implemented exposure, then, with the not exposure part of developing and removing this photosensitive polymer combination with liquid dissolving or dispersion, on conductive board, form after the desirable resin figure, the limit powers up flanging conductive board is dipped in the electroplate liquid, formed after the conductor with electrolytic plating method, removed conductive board.

6. the manufacture method of a thick-film conductor circuit, comprise: the photosensitive polymer combination of liquid is coated onto on this conductive board, with high-energy ray the part that should form the resin figure is implemented exposure, then, with the not exposure part of developing and removing this photosensitive polymer combination with liquid dissolving or dispersion, on conductive board, form after the desirable resin figure, the limit powers up flanging conductive board is dipped in the electroplate liquid, formed after the conductor with electrolytic plating method, remove the operation of conductive board, it is characterized in that:

This liquid light-sensitive resin composition contains prepolymer, co-polymerized monomer, photopolymerizer and light absorber with ethene unsaturated group, and,

Prepolymer is that number-average molecular weight that the condensation with dicarboxylic acids composition and diol component obtains is 500～5000 unsaturated polyester resin, the dicarboxylic acids composition, full mol ratio with this dicarboxylic acids composition is 1, calculate with mol ratio, compound (a) with composition of representing with following chemical formula (1) is 0.1～0.4, calculate with mol ratio, the compound (b) with composition of representing with following chemical formula (2) is 0.1～0.4

Chemical formula (1)

Chemical formula (2)

(R ₁, R ₂Expression-COOH or-CH ₂COOH, R ₂, R ₄Expression-H or-CH ₃)

The co-polymerized monomer composition has 3 acryloyl groups or methacryl at least in a molecule; and at least a compound that has carbon atom and/or the oxygen atom below 15 and make institute's combination between the carbon atom of this acryloyl group or the combination of methacryl institute contains 1～30 weight portion for 100 weight portions of this prepolymer.

In addition, the molar absorption coefficient that contains 0.1～10 weight % at light absorption maximum place is the Photoepolymerizationinitiater initiater of 5～1000l/molcm, when containing the light absorber of 0.01～1 weight %,

Light transmission is 15～75%.

7. the manufacture method of the described thick-film conductor circuit of claim 6 is characterized in that: conductive board is with containing the aluminium sheet that the zinc alkaline solution was handled.

8. the manufacture method of the described thick-film conductor circuit of claim 6 is characterized in that: in the composition beyond the composition of representing with the chemical formula (1) and the chemical formula (2) of dicarboxylic acids composition, be the dicarboxylic acids composition with following chemical formula (3) expression more than 75% mole

Chemical formula (3)

HOOC-(CH ₂) _n-COOH???(n=3～8)

9. the manufacture method of the described thick-film conductor circuit of claim 7 is characterized in that: in the composition beyond the composition of representing with the chemical formula (1) and the chemical formula (2) of dicarboxylic acids composition, be the dicarboxylic acids composition with following chemical formula (3) expression more than 75% mole

Chemical formula (3)

HOOC-(CH ₂) _n-COOH????(n=3～8)

10. any one described thick-film conductor circuit in the claim 2 to 4, it is characterized in that: insulating barrier is the hardening thing of the described photosensitive polymer combination of claim 6 between conductor.

11. the manufacture method of the described thick-film conductor circuit of claim 6 is characterized in that: the diffusion reflection surface rate of the conductive board in the wavelength photoreceptor zone of liquid light-sensitive resin is less than 20%.

12. the manufacture method of the described thick-film conductor circuit of claim 7 is characterized in that: the diffusion reflection surface rate of the conductive board in the wavelength photoreceptor zone of liquid light-sensitive resin is less than 20%.

13. planar coil, it is characterized in that: the cross sectional shape of conductor be rectangle coil pattern toward each other, and make the top and bottom conducting and in the planar coil that constitutes, coil-conductor is the described thick film conductor of any any one claim in the claim 1 to 4 by through hole.

14. different pitch connecting wiring parts is characterized in that: in the wired circuit of the different parts of connecting wiring pitch, the employed conductor that connects up is the described thick film conductor of any one claim in the claim 1 to 4.

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