CN101120621A

CN101120621A - Method of forming metallic pattern, metallic pattern and printed wiring board using it and tft wiring circuit

Info

Publication number: CN101120621A
Application number: CN200680004329.9A
Authority: CN
Inventors: 松本和彦; 川村浩一; 加纳丈嘉
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2005-02-08
Filing date: 2006-02-08
Publication date: 2008-02-06
Anticipated expiration: 2026-02-08
Also published as: CN101120621B; JP4606894B2; JP2006222163A

Abstract

The invention provides a method of forming a metallic pattern including: (a) forming, in a pattern form on a substrate, a polymer layer which contains a polymer that has a functional group that interacts with an electroless plating catalyst or a precursor thereof; (b) imparting the electroless plating catalyst or precursor thereof onto the polymer layer; and (c) forming a metallic film in the pattern form by subjecting the substrate having the polymer layer to electroless plating using an electroless plating solution, wherein the substrate is treated using a solution comprising a surface charge modifier or 1xL10-10 to 1xL10-4 mmol/l of a plating catalyst poison before or during the (c) forming of the metallic film. The invention further provides a metallic pattern obtained thereby. Furthermore, the invention provides a printed wiring board and a TFT wiring board, each of which uses the metallic pattern as a conductive layer.

Description

Metallic pattern formation method, metallic pattern, printed leads plate and TFT lead plate

Technical field

The present invention relates to a kind of method and thus obtained metallic pattern that forms metallic pattern.Especially, the present invention relates to method and the thus obtained metallic pattern of a kind of formation as the metallic pattern of printed leads plate and TFT (thin-film transistor) lead plate conductive layer.

Background technology

In the art, main common metal pattern forming method is subtractive method, false add method and full additivity method.

Subtractive method comprises the steps: to form above the metal level that forms on the substrate to the light activated photoresist layer of the activation that shines, the photoresist layer is exposed to form image, form the resist figure by developing, form metallic pattern, finally remove resist by etching metal.The substrate interface of the metal substrate that this method is used is roughened usually, to improve bonding effect, improves the adhesion between substrate and the metal level.As a result, the substrate interface roughening of formed metallic pattern can cause the bad problem of high frequency characteristics change when product is used for electric wiring usually.In addition, owing to needed to carry out the substrate surface roughening before forming metal substrate, this has also brought the problem that needs with complex steps such as treatment substrate such as strong acid such as chromic acid.

For example, in order to overcome these problems, " advanced material (Advanced Materials) " the 20th volume of publishing Japanese Patent Application Laid-Open (JP-A) No.58-196238 and 2000 has proposed in the 1481st～1494 page a kind of by the substrate surface grafting being handled certain adhesion grade to be provided and to simplify the method for processing substrate step thus and change substrate surface, make the substrate inhomogeneities minimize and simplify thus the method for processing substrate step thus by grafting polymerisable compound group thereon.Yet expensive device is necessary as gamma-rays generation device and electron beam generating device.And, can estimate to cause the initial group of polymerization of glycerol polymerization not to be introduced in the substrate, thereby cause having formed a spot of graft polymers.

Therefore, though the metal substrate by the preparation of this method by subtractive method by graphical, but this product still contain following subtractive method intrinsic problem.In order to form the metallic pattern with thin live width by subtractive method, it is effective that the live width of resist figure what is called of attenuation after etching is crossed engraving method.Yet, when meticulous metallic pattern passed through engraving method and directly formed, practical point of view according to forming favourable fine metal figure is difficult to form the metallic pattern with 30 μ m or littler live width, this be since institute form the defective that goes between as ooze out, attenuate, disconnection connection etc.In addition, also can bring the problem with cost and environmental correclation, this is because in order to remove the metal film that exists in the zone outside patterned area, also needs quite to become the original metallic wastewater that is caused by etch processes of handling.

In order to overcome these problems, new metallic pattern formation method has been proposed, i.e. the false add method.The false add method is the method that may further comprise the steps.That is, comprising the thin metal lower layer of Cr etc. and on metal lower layer, forming the resist figure thus by formation such as plating on the substrate.Wiring figure is by form the metal level that comprises Cu etc. and removal resist figure step subsequently produces by electroplating on the metal lower layer zone except the resist patterned area.By etching metal lower floor while mask wiring figure, on the zone except the resist graphics field, form metallic pattern subsequently.Because it is less etch process, so this method can more easily form the thin line graph with 30 μ m or littler live width; And owing to metal only is deposited on the desired zone, so it is also favourable aspect cost.Yet metal needs is wanted the roughening substrate surface, is used to improve the adhesiveness between substrate and the metallic pattern.Consequently, the substrate surface roughening of formed metallic pattern causes the bad problem of high frequency characteristics change when using it for electrical wiring.

The metallic pattern formation method of so-called full additivity method replacedly, has also been proposed.Full additivity method is a kind of like this method, by on the zone except the resist figure by the electroplating deposition metal, remove the resist figure afterwards, on substrate, form the resist figure.Because it is the less technology of etching, the thin line graph that the therefore complete easier formation of additivity method has 30 μ m or littler live width.It also makes that in the mode similar to the false add method substrate interface is coarse, causes the bad problem of high frequency characteristics change when it is used for electrical wiring.

As mentioned above, can form thin line graph, have less substrate interface degree of irregularity, and the metallic pattern formation method that produces more a spot of etching waste water remain to be proposed, and need a kind of new metallic pattern formation method.

Above-mentioned metallic pattern is used for the printed circuit board (PCB) of semiconductor device as wiring (conducting film).In recent years, for electronic installation, be starved of with the high processing rate processing and stored data in batches.The internal clocking frequency or the 1 year year of external clock frequency that are used for handling the semiconductor device of image or control and treatment increase, and the number that connects pin is also increasing.In order to implement high-speed transfer, importantly reduce delay and signal amplitude.In order to reduce the propagation delay of signal, effectively reduce dielectric constant.In order to reduce dielectric absorption, effectively reduce dielectric constant and dielectric loss angle tangent respectively.Yet because the dielectric constant in the dielectric absorption is the root of dielectric constant, therefore, in the reality, dielectric loss angle tangent is very relevant therewith.For this reason, according to the viewpoint of material behavior, the insulating material of usefully taking to have low-dielectric loss angle tangent characteristic is used to implement the high-speed data processing.

And the surface smoothing of electric conducting material is handled to help to form has highdensity material.In the printed circuit board (PCB) that conventional method makes up, roughened has been used to obtain peel strength.Yet present situation is, several microns irregularly shaped also can influence fine wiring.

Therefore, according to the viewpoint of the printed circuit board (PCB) that is formed for semiconductor device, will on smooth insulated substrate, form very fine metallic pattern with high-adhesiveness.

Now disclose a kind of formation conductive metal pattern on substrate and do not had erose method, comprise by using photosensitive silicones to carry out graphically, give catalyst and forming metallic pattern (for example, seeing Japanese Patent Application Laid-Open (JP-A) No.2000-349417) by electroplating.Yet, silicones can not provide and normally used insulating resin as being used for adhesiveness enough between printed leads plate such as polyimide resin and the epoxy resin, needing to provide higher adhering method.

In view of the foregoing, the applicant has proposed a kind of method that forms metallic pattern, and it is included in plated metal particle (for example, seeing JP-A No.2003-114525) on the fine pattern that is formed by graft polymers that is bonded directly to substrate.According to this method, can form required fine pattern according to the exposure accuracy.Yet for the metallic pattern that forms by the plated metal fine granular, there is restriction in its conductivity.In order to be applied to printed leads material etc., need under current environment, further improve conductivity, for example, realize by the technology that increases the accuracy of metallic pattern on metal layer thickness and the while retention wire cross direction.

Summary of the invention

Consider and use the existing the problems referred to above of routine techniques, the invention provides a kind of method that forms metallic pattern, it can produce the metal fine pattern and not need etch process, and can form have with substrate good adhesion, enough conductivity and with substrate interface on have little scrambling metallic pattern.The present invention also provide a kind of have satisfactory electrical conductivity, excellent high frequency characteristics and with the metallic pattern of substrate good adhesion, and use printed leads plate and the TFT lead wire circuit of this metallic pattern as conductive layer.

The initial metal fine pattern that has good adhesion with substrate of finding of the inventor can form by carrying out electroless plating on the zone that is bonded directly to substrate at the polymer with electroless plating catalyst or its precursor with certain figure.According to the present invention, though kept required live width, metal film is selective growth on thickness direction, to realize the further raising of accuracy, keeps certain conductivity simultaneously, and can form conductive metal pattern.

Promptly, the invention provides a kind of metallic pattern formation method, comprise: (a) form polymeric layer with the figure that is formed on the substrate, this polymeric layer contains and has with the functional group of electroless plating catalyst or its precursors reaction and can direct chemical be bonded to the polymer of substrate; (b) electroless plating catalyst or its precursor are applied on the polymeric layer; (c), form metal film with graphic form by using electroless plating solution that the substrate with polymeric layer is carried out electroless plating, wherein before forming metal film or during (c), use to comprise surface charge improver or 1 * 10 ^-10To 1 * 10 ^-4Mmol/l electroplates the solution of catalytic inhibitor and handles the substrate with the polymeric layer that is applied with electroless plating catalyst or its precursor.

In the one side of the inventive method, wherein utilized the surface charge improver, the technology (c) that forms metal film can comprise by use and contains the electroless plating (c-1) that the electroless plating solution of surface charge improver carries out.Replacedly, in aspect this, the technology (c) that forms metal film comprises with the groove that contains the surface charge improver handles the substrate (c-2) with polymeric layer; With the substrate with polymeric layer is carried out electroless plating so that form the metal film (c-3) of graphic form.

The surface charge improver can be an organic compound, has in its molecule: (i) substrate is had the group of affinity and (ii) ion leaving group.

The inventive method on the other hand in, wherein utilized the plating catalytic inhibitor, the technology (c) that forms metal film can comprise by use and contains 1 * 10 ^-10To 1 * 10 ^-4The electroless plating that the electroless plating solution of mmol/l plating catalytic inhibitor carries out (c-1 ').Replacedly, in this aspect, the technology (c) that forms metal film comprises that the substrate with polymeric layer is carried out electroless plating (c-2 ') to be added in the electroless plating solution and remain on 1 * 10 so that electroplate the concentration of catalytic inhibitor in the electroless plating solution electroplating catalytic inhibitor simultaneously ^-10To 1 * 10 ^-4In the scope of mmol/l, so that form metal film with graphic form.

Electroplating catalytic inhibitor can be inorganic anion, and it is selected from the group that is made of iodine anion, bromine anions and sulphur anion.Electroplating catalytic inhibitor can be organic compound, has the group that affinity is arranged with plated metal in its molecule.Organic compound can further have the ion leaving group in its molecule.

In aspect two of the inventive method, the group that the optional free plating solution for electroless copper plating of the electroless plating solution that uses in electroless plating, electroless deposition of silver solution and electroless gold plating solution constitute.And under two kinds of situations of the present invention, method of the present invention is implemented to electroplate after further being included in electroless plating.

And, aspect two of the inventive method in, substrate can have 500nm or littler surperficial unevenness; Adhesiveness between substrate and metal film is 0.2kN/m or bigger; And in meet the following conditions (1) to (3) at least one: (1) thickness of metal film is 3 μ m or bigger; With satisfy relation (q-p)＜r, the figure live width of p presentation graphic form wherein, q represents that the live width of the metal film that forms by electroless plating and r represent the thickness of the metal film that forms by electroless plating; (2) polymeric layer has the zone of wherein scattering fine granular, this fine granular comprises electroless plating catalyst particle and at least a by in the metallic particles of electroless deposition, volume content is 25% or more, and 0.05 μ m or more is being extended at this zone autohemagglutination compound layer and metal film interface on the direction of substrate; With the ratio of metal film and metal film live width be 1 or more; (3) thickness of metal film is 4 μ m or more; Polymeric layer has the zone of wherein scattering fine granular, this fine granular comprises electroless plating catalyst particle and at least a by in the metallic particles of electroless deposition, volume content is 25% or more, and this zone is extended 0.05 μ m or more from the interface of polymeric layer and metal film in the direction towards substrate; With the ratio of thickness of metal film and metal film live width be 1 or bigger.

And, aspect two of the inventive method in, substrate can have 100nm or surperficial unevenness still less.

And, the invention provides a kind of metallic pattern that forms by above-mentioned metallic pattern formation method.

And, the invention provides a kind of printed leads plate and TF T lead plate, its each all have metallic pattern as its conductive layer.

About the present invention, " substrate " refer to have that polymer is located immediately on it and chemical bonding to its surfacing.Directly providing polymer to be arranged under the situation that is formed at the figure on the resin molding, substrate refers to resin molding itself.Providing polymer to be positioned at graphic form under the intermediate layer such as the lip-deep situation of polymerization initiation layer that is formed on basic material such as the surface resin film, substrate refers to intermediate layer carrier film basic material.

In the first aspect of metallic pattern formation method of the present invention, allow to exist jointly in the some cycles of surface charge improver in carrying out electroless plating, so that the surface charge improver absorbs, thereby suppress the deposition of plated metal ion on substrate surface.Thus, electroplating on the grafting patterned surface zone have the high density plating catalyst thereon selectivity carries out.Formed metal film is not grown on the graphic width direction, and has adequate thickness thus.As a result, obtain according to very fine grafting figure and metallic pattern very meticulous and that have high conductivity.

The first aspect advantage of metallic pattern formation method of the present invention is: the metallic pattern with any desired thickness all can form by further electroplating after electroless plating.The adhesion of metal film further increases by carry out dry etching after electroless plating or plating.

In the second aspect of metallic pattern formation method of the present invention, in carrying out electroless technology, add in the electroplating bath specifically measuring the plating catalytic inhibitor, so that a certain amount of plating catalytic inhibitor is bonded to the plated metal ion in the electroless plating groove, and the absorption of plated metal ion pair substrate or plating catalyst is suppressed to a certain degree.Thus, electroless plating is carried out having on the grafting patterned surface zone of the concrete surf zone that has the high density plating catalyst on it selectivity.Thus, electroless development the grafting figure in per unit area with electroplate contacting on the side that takes place more continually of catalytic inhibitor and suppressed effectively, perhaps be not have on the substrate surface of certain reception plated metal ion function and suppressed effectively.Thus, formed metal film is not grown on the graphic width direction, and has adequate thickness thus, and has obtained according to very fine grafting figure and very meticulous and metallic pattern that have high conductivity.

The second aspect advantage of metallic pattern formation method of the present invention is that the metallic pattern with desired thickness can form by further electroplating after electroless plating.The adhesion energy of metal film further increases by carry out dry etching after electroless plating or plating.

In a preferred embodiment of the invention, use substrate with 500nm or littler surface evenness.When satisfying the substrate condition, can have the polymeric layer of 500nm or littler surface evenness, form polymeric layer with graphic form simultaneously.Add electroless plating catalyst or its precursor and caused plating catalyst and plated metal to be contained in (combined state) in the figure cutting electrodeposition of metals further and optionally be formed at state above the figure on the thickness direction, so that adequate thickness and good conductivity are provided to figure with having the surface charge improver jointly or electroplate electroless plating under the catalytic inhibitor situation.Thus interface between metallic pattern of Xing Chenging and the substrate, be that the inhomogeneities at interface becomes and is a bit larger tham the polymer patterned surface between metal and the polymeric layer (organic principle), this is because plating catalyst and plated metal have penetrated in the polymer figure, but degree is very little the product high frequency characteristics is not obviously influenced.Therefore, these metallic patterns have the high frequency characteristics of raising when being used for electrical lead.The transmission loss that high frequency characteristics relates between the high-frequency electrical transmission period refers more particularly to conductor losses.

As mentioned above, in the detailed study that is inserted into the polymeric layer (organic principle) between metal film (metallic pattern) and the substrate, polymeric layer between substrate and metal film has the zone that wherein disperses fine granular, this fine granular comprises electroless plating catalyst particle and at least a by in the metallic particles of electroless deposition, volume content 25% or more, and should zone autohemagglutination compound layer and the metal film interface on the direction of substrate, extending 0.05 μ m or more.Think and exist the fine granular wherein contain metal etc. can be formed for strengthening the adhering state of metal film.

Use have 100nm or still less the substrate of surface evenness be preferred because the less substrate surface uniformity can cause the less unevenness of substrate interface of metallic pattern, it can cause the improvement of the metallic pattern high frequency characteristics that obtains conversely.

Method of the present invention provides accuracy to be higher than those metallic patterns that obtain by the conventional etched pattern forming method that uses the resist figure, this is because it comprises electroless plating catalyst or its precursor optionally to be applied to not zone with electroless plating or its precursors reaction, and this electroless plating and its precursor are by embodiment as described above (1) or (2) and have the surface charge improver jointly or electroplating under the situation of catalytic inhibitor and carry out electroless method formation subsequently.Method of the present invention is also advantageous in that does not discharge etching waste water.

In the present invention, the substrate surface of metallic pattern forms so that minimize the scrambling of substrate interface by substrate being carried out the surface grafting processing.And substrate interface is in the admixture that forms by metal ingredient that makes up metal film and the graft polymers that is bonded directly to substrate.Therefore, think thus the metal film that forms and the adhesiveness height between the substrate.

Among the present invention, the Rz of the parameter that the die mould method of the conventional known relevant with surface texture of serving as reasons limits, promptly " be up to the mean value of the 5th peak value Z data on the particular surface and be low to moderate difference between the mean value of the 5th dark bottom Z data most " the coarse sign that is used as surperficial unevenness.

When being used as conventional material by the metallic pattern that obtains according to the inventive method, the metal in the lead-in wire zone and the scrambling at the interface between the organic material are more little, and the electrical loss (loss) in the high-frequency electrical transmission is just more little.

Therefore, have printed leads plate by using the metallic pattern of the present invention that metallic pattern obtains as its conductive layer (lead-in wire) and TFT lead plate and have flatness, and adhesiveness, fineness, all good lead-in wire of conductivity and high frequency characteristics aspect of substrate.

Description of drawings

Fig. 1 is the SEM cross-section photograph of the metallic pattern of acquisition in embodiment 1～3; With

Fig. 2 is the image that obtains by the section S EM photo among image processing Fig. 1, and wherein white fine granular part and the black represented of formation is represented two kinds of color gradients of polymer moieties.

Embodiment

Below, will describe the present invention in detail.At first, will the method that form metallic pattern of the present invention be described.

Form the method for metallic pattern

Metallic pattern formation method according to the present invention is a kind of method that forms metallic pattern, and it comprises:

(a) form polymeric layer with graphic form on substrate, this polymeric layer comprises and has with the functional group of electroless plating catalyst or its precursors reaction and can direct chemical be bonded to polymer on the substrate;

(b) electroless plating catalyst or its precursor are applied on the polymeric layer; With

(c) form metal film by using electroless plating solution that the substrate with polymeric layer is carried out electroless plating with graphic form,

Wherein, before (c) forms metal film or during, use surface charge improver or 1 * 10 ^-10To 1 * 10 ^-4The plating catalytic inhibitor of mmol/1 is handled the substrate with the polymeric layer that is applied with electroless plating catalyst or its precursor.

Promptly, metallic pattern formation method according to the present invention comprises: on substrate the zone of formation and electroless plating catalyst or its precursors reaction and not with the zone of its reaction, add electroless plating catalyst or its precursor to conversion zone, and afterwards substrate is carried out electroless plating.Among the present invention, the zone (being polymeric layer) that has with the polymer of electroless plating catalyst or its precursors reaction will be called " grafting figure ".

Below, will technology (a) be described in proper order to (c) with this.

(a) on substrate, form the grafting figure

In following method (1) and (2) any all is used as a kind of like this technology, and it is used for (a) has with the polymer of the functional group of electroless plating catalyst or its precursors reaction and can direct chemical be bonded to polymeric layer on the substrate forming to comprise with graphics mode on the substrate.

(1) a kind of method, comprise: directly and the chemical bonding polymer compound to the whole surface of substrate, wherein polymer compound has by heating, the functional group of another kind of functional group is changed in acid or radiation, this another kind functional group can with electroless plating catalyst or its precursors reaction, perhaps have by heat, the functional group of the function of acid or radiation loss and electroless plating catalyst or its precursors reaction (below, this functional group is called " polar switching group " as required), and afterwards based on image apply heat or radiation with form can with the patterned area of electroless plating catalyst or its precursors reaction.

(2) a kind of method comprises: make substrate surface with have polymerizable groups and can contact with the compound of the functional group of electroless plating catalyst or its precursors reaction; With apply based on image radiation with form can with the patterned area of electroless plating catalyst or its precursors reaction.

The surface grafting polymerization thing

By means of the polymeric layer among the so-called surface grafting polymerization thing preparation method (1).Graft polymers is a kind of by reactive specy being added to the polymer compound chain and making it and another kind of monomer polymerization prepares the method for graft polymers with the beginning polymerization, and especially, when the polymer compound that reactive specy is provided is present in solid state surface, it is called surface grafting polymerization.

Be used to realize that the method that changes the surface grafting polymerization of embodiment comprises any process of describing in the literature.Embodiment is included in " the new test method of polymer (New Experimental Methods of polymer) " the 10th volume (Soc.PolymerScience Japan Ed.1994, Kyoritsu Shuppan Co., Ltd, the 135th page) and Japanese Patent Application Laid-Open JP-A No.63-92658,10-296895 and 11-119413 in photo-grafting polymerization and the plasma irradiating graft polymerization procedure described.In addition, embodiment also is included in the use gamma-rays described in " Absorption Technology " (NTS., AkiraTakeuchi Ed., in February, 1999, the 203rd and 695 page) etc. or the radiation grafting polymerization of electron beam.

The specific embodiment of photo-grafting polymerization is included in JP-A No.63-82658, the method for describing among 10-296895 and the 11-119413.

Except above-mentioned those methods, the method that the terminal direct chemical that forms the polymer compound chain is bonded to its surface media comprises the method that reactive functional group group such as trialkoxysilyl group, isocyanates group, amino, hydroxyl or carboxyl is incorporated into the terminal of polymer compound chain and causes coupled reaction between the functional group that exists on its functional group and the substrate surface.

According to the substrate surface of this embodiment be will have the polar switching group from the teeth outwards the polymer compound terminal directly or via the surface of trunk polymer chemical bonding to it, have so this surface characteristic now with raw material, the intermediate layer that perhaps is formed on discretely on the raw material has this specific character.This substrate preferably has 500nm or surperficial unevenness still less.

Have the polar switching group the polymer compound chain terminal via trunk polymer chemical bonding to the formation method on its surface comprise with in coupled reaction can and substrate surface on the functional group of functional group reactions join on the side chain of trunk polymer, preparation comprises polymer compound chain with polar switching group as the polymer compound of grafted chain with allow the method for the coupled reaction between the functional group on polymer and the lower layer surface thus.

Below, will the polar switching group that use in this embodiment be described.Polar switching group according to this embodiment comprises by heat or the sour types of radicals (B) that changes the types of radicals (A) of its polarity and change its polarity by radiation (light).

In the present invention, if group is the functional group that electroless plating catalyst described below or its preceding physical efficiency are bonded, then restriction " with the functional group of electroless plating catalyst or its precursors reaction " especially, but its hydrophilic radical normally.

Change the functional group (A) of its polarity by heat or acid

At first, will the functional group (A) that change its polarity by heat or acid be described.

(A) be classified into two kinds of groups by heat or the sour functional group's type (A) that changes its polarity, change the functional group of polarity and pass through heat or the sour functional group that changes polarity from hydrophily to hydrophobicity to hydrophily from hydrophobicity by hot or acid.

Change the functional group (A-1) of its polarity to hydrophily from hydrophobicity by heat or acid

Comprise in the literature disclosed arbitrary known functional group from hydrophobicity to the functional group (A-1) that hydrophily changes its polarity by heat or acid.

Below, will describe by heat or acid from hydrophobicity to the functional group (A-1) of hydrophily change polarity with have the embodiment of the compound of functional group.

The embodiment of functional group comprises alkyl sulfate, two sulfones and the sulfanilamide (SN) of describing among the JP-A No.10-282672; The alkyl alkoxy of describing among European patent No.0652483 and the W.O.No.92/9934; The t-butyl that people's such as H.Ito " Macromolecules " the 21st describes in rolling up the 1477th page; The group that decomposes by the theobromine described in the document such as the carboxylate of protections such as silyl ester, vinyl esters; Or the like.

This embodiment also is included in the imino group sulfonate groups that Masahiro Tsunooka describes in " Surface " the 133rd rolls up (1995) the 374th pages; β-ketone sulfonated ester that the MasahiroKadooka of Japan describes in " Polymer preprints " the 46th rolls up (1997) the 2045th pages; The nitrobenzyl sulfonate of in the JP-A of Tuguo Yamaoka No.63-257750, describing, but the invention is not restricted to these functional groups.

The functional group of describing in JP-A No.2001-117223 is also suitable.In the functional group of in JP-ANo.2001-117223, describing, the alkoxyalkyl ester group that more preferably passes through the secondary alkylsurfuric acid ester group of general formula (1) expression, three carboxylic acid ester groups and represent by general formula (2), and therein, secondary alkylsurfuric acid ester group by general formula (1) expression is preferred especially, although the invention is not restricted to this.Below listed the specific embodiment of certain preferred functional group.

Change the functional group (A-2) of its polarity to hydrophobicity from hydrophily by heat or acid

Among the present invention, comprise the functional group that any is known from hydrophily to the functional group (A-2) that hydrophobicity changes its polarity by heat or acid.

Below, change the functional group (A-2) of its polarity and have the embodiment of the compound of this functional group to hydrophobicity from hydrophily describing by heat or acid.

The embodiment of functional group is included in the polymer of the salt group of describing in JP-A No.10-296895 and the U.S. Patent No. 6,190,830 that contains complex cation, and especially contains the polymer of ammonium salt group.Its specific embodiment comprises (methyl) acryloyloxyalkyl trimethyl ammonium etc.

The functional group of describing in JP-A No.2001-117223 is also suitable.In the middle of the functional group of in above-mentioned patent disclosure, describing, especially preferably, still the invention is not restricted to these embodiment by the carboxylic acid group and the carboxylic acid ester groups salt group of general formula (3) expression.Below, listed the specific embodiment of preferred especially functional group.

According to the graft polymers with polar switching group of the present invention can be the homopolymers that is made of the single monomer with above-mentioned functional group or the copolymer of two or more this monomers.In addition, other monomers can add in the copolymer with the quantity that does not weaken advantageous effects of the present invention.

The specific embodiment of monomer that changes the functional group (A-1) of its polarity by heat or acid from the hydrophobicity to the hydrophily below is shown.

Below illustrate and have the specific embodiment of monomer that from the hydrophily to the hydrophobicity, changes the functional group (A-2) of its polarity by heat or acid.

Optical-thermal conversion material

If be applied to the polymeric layer that on substrate, forms, be used for realizing that by above-mentioned surface grafting polymerization the energy of polar switching is a for example IR laser of light energy, then preferably realize that with being used for transform light energy becomes the optical-thermal conversion material of heat energy to add in any of polymeric layer, substrate and intermediate layer.Replacedly, it can be added in the optical-thermal conversion material layer that between polymerization initiation layer and raw material, separates formation.

Can be with any compound as optical-thermal conversion material, as long as it is absorbing light as ultraviolet ray, visible light, infrared ray or white light and converts thereof into hot material, and embodiment comprises carbon black, carbon, dyestuff, pigment, phthalocyanine, phthalocyanine pigment, metal fine granular such as iron powder, powdered graphite croci, lead oxide, silver oxide, chromium oxide, iron sulfide and chromic sulfide etc.Particularly preferably be dyestuff, phthalocyanine and metal fine granular, it has maximum absorption wavelength in the infrared laser power exposure wavelength zone (760 to 1200nm) that is used for applying energy.

The embodiment of dyestuff comprise obtainable dyestuff and document on the market (for example, by Society of Synthetic Organic Chemistry edit in " the Dye Handbook " at Japanese publication in 1970) in the known dyestuff of the public described.More specifically, the embodiment of dyestuff comprises dyestuff such as azo group dyestuff, bimetallic salt complex azo group dyestuff, pyrazolone azo group dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dyestuff, quinoneimine dye, methine dyes, cyanine dye or metal mercaptide salt composite.The dyestuff preferred embodiment for example comprises: the cyanine dye of describing among JP-A 58-125246,59-202829, the 60-78787; The naphthoquinone dyestuff of Japanese Patent Application Laid-Open (JP-A) No.58-273696, the open middle methine dyes of describing such as 58-181690,58-194595, description in JP-ANo.58-112793,58-224793,59-48187,59-73996,60-52940No.60-63744 etc.; The squarylium dyestuff of in JP-ANo.58-112792 etc., describing; With GB patent No.434, the cyanine dye of describing in 875 grades.

Also preferably use U.S. Patent No. 5,156, the near infrared absorption emulsion of describing in 938, and, the preferred embodiment of INFRARED ABSORPTION emulsion is included in U.S. Patent No. 3,881, aryl benzo (sulphur) the pyrans ocean salt of describing in 924, Japanese Patent Application Laid-Open (JP-A) No.57-142645 (U.S. Patent No. 4,327,169) the cyclonite sulphur pyrans ocean salt of describing in, JP-A No.58-181051,58-220143,59-41363,59-84248,59-84249,59～146063 and 59-146061 in the pyrans described foreignize compound, the cyanine dye of describing among the JP-A No.59-216146, in U.S. Patent No. 4, the pentamethine cyanine sulphur pyrans ocean salt of describing in 283,475, the pyrans of describing among JP-B No.5-13514 and the 5-19702 foreignizes compound etc.As another preferred embodiment of dyestuff, also mentioned in U.S. Patent No. 4,756, describe in 993 the specification by molecular formula (I) or (II) expression hear-infrared absorption dye.Its particularly preferred embodiment comprises dyestuff, cyanine dye, squarylium dyestuff, pyrans ocean dyestuff and mercaptan nickel composite.

Can use the embodiment of pigment to comprise obtainable pigment on the market and the pigment of in following document, describing: " Color Index (C.I.) handbook, " Latest PigmentsHandbook ", published in 1997, and published Japan by Society of Pigment Technology; " Latest Applied Technology of Pigment " published in 1986, and be open by CMC; And/or " Printing Ink Technology ", published in 1984, open by CMC.The embodiment of this type pigment comprises melanin, uranidin, the plain brown pigment of orange, haematochrome, purpurin, cyanine, marennin, fluorchrome, metal dust pigment and polymer-bound dyestuff.Can use the specific embodiment of pigment to comprise insoluble azo group pigment, azo group color lake pigment, concentrate the azo group pigment, chelating azo group pigment, phthalocyanine composition pigment, the anthraquinone compounds pigment, perylene compound pigment, perinone compound pigment, thioindigo compound pigment, quinoline a word used for translation ketonic compound pigment, dioxazines compound pigment, isoindolinone compound pigment, quinophthalone compound pigment, dyeing color lake pigment, inorganic pigment, carbon black etc.In the middle of above-mentioned pigment, preferably use carbon black.

When using optical-thermal conversion material in the present invention, consider that optical-thermal conversion material comprises the photonasty and the intensity of layer, the optical-thermal conversion material amount is with respect to the ratio of the total solids content of the layer that comprises optical-thermal conversion material 0.01 to 50 quality % and be more preferably 0.1 to 10 quality % preferably.When dyestuff was used as optical-thermal conversion material, amount of dye was 0.5 to 10 quality % with respect to the ratio of the total solid two of the layer that comprises dyestuff.When pigment was used as optical-thermal conversion material, amount of pigment was 3.1 to 10 quality % with respect to the preferred ratio of the total solids content of the layer that comprises pigment.

Acid produces material

To apply the acid that is used for polar switching in order being formed at when the figure that uses the polymer with polar switching group forms on the material surface, preferably acid to be produced material and add in any structure that figure forms material when the grafting figure.Acid is produced the constructed embodiment that material is added into it comprise figure cambium layer, intermediate layer and raw material.

It is by heat or the acidic compound of light that acid produces material, light trigger, the light trigger of light atomic group polymerization, dyestuff light decolorizer, phototropic agent, the optics that embodiment generally includes the light cationic polymerization be created in the acid of using in the application as little resist conventional known compound, and composition thereof or the like.The material that is suitable for being selected from these materials can be used for the present invention.

Its specific embodiment comprises people's such as T.S.Bal S.I.Schulesinger, " Photogr.Sci.Eng. ", the diamino salt of describing in 18,387 (1974), polymer, 21,423 (1980) etc.; The amine salt of describing among the JP-A No.3-140140 etc.; United States Patent (USP) Mo4, the microcosmic salt of describing in 069,055 grade; Among the JP-A No.2-150848 and 2～296514 etc. salt compounded of iodine is described; People's such as J.V.Crivello " PolymerJ. " 17,73 (1985), US Patent No 3,902,114, European patent No.233,567,297,443 and 297,442, U.S. Patent No. 4,933,377,4,491,377,4,491,628,5,041,358,4,760,013,4,734,444 and 2,8827, Deutsche Bundespatent No.2,904,626,3, the mercapto salt of describing in 604,580 and 3,604,581 grades.

People's such as J.V.Crivello " Macromolecules ", the people's such as selenium salt C.S.When that describe in 10 (6), 1307 (1977) etc. Teh,, Proc, Conf, Rad, the salt of describing among the 478th page of CuringASIA, Tokyo October (1988) etc. that comprises arsenic salt; The organohalogen compound of describing among the JP-A No.63-298339 etc.; Organic metal/the people such as organohalogen compounds S.Hayase that describe among the JP-ANo.2-161445 etc. are at " J.Polymer Sci. ", 25,753 (1987), describe among JP-A No.60-198538 and the 53-133022 etc. have an o-nitrobenzyl blocking group; The photolysis of describing in JP-ANo.64-18143,2-245756 and 3-140109 etc. by expressions such as imino group sulfonate produces the compound of sulfuric acid; With the disulfo compound of in JP-A No.6-166544 etc., describing.

According to the sensitiveness of the layer that contains acid generation material and the viewpoint of intensity, with respect to the total solid material in the layer that comprises acid generation material, these sour amounts of materials that produce are in the scope of 0.01 to 50 quality %, preferably in the scope of 0.1 to 30 quality %.

Change the functional group (B) of its polarity by light

In the middle of a lot of embodiment of the functional group that changes its polarity, exist by have 700nm or still less the radiation of the light of wavelength change some groups of polarity.This functional group (B) (polar switching group: to 700nm or the light activated polar switching group of wavelength still less) that changes its polarity by light is characterised in that, the radiation by causing decomposition, annular opening or obstructed overheated or longer wavelength light such as infrared-ray but carry out dimerization reaction by the irradiation of certain wavelength light and change the polarity with hypersensitivity.Below, with describe by 700nm or more the irradiation of small wavelength light change the functional group of polarity.

The functional group (B) that changes its polarity by light also is divided into two groups, changes the functional group (B-1) of its polarity and change the functional group (B-2) of its polarity from the hydrophobicity to the hydrophily from the hydrophily to the hydrophobicity.

From the hydrophobicity to the hydrophily, change the functional group (B-1) of its polarity

The embodiment that changes the functional group (B-1) of its polarity from the hydrophobicity to the hydrophily is included in the functional group of describing among the JP-A No.2003-222972 that passes through general formula (1) to (4) and (7) to (9) expression.

From the hydrophily to the hydrophobicity, change the functional group (B-2) of its polarity

The embodiment that changes the functional group (B-2) of its polarity from the hydrophily to the hydrophobicity comprises the bispyridinioethylene group.

Substrate

The substrate that is used among the embodiment (1) has surface grafting layer and substrate surface, above-mentioned polymer compound terminal with polar switching group directly or by the trunk polymer compound chemistry is bonded to this surface grafting layer, and the terminal of polymer compound directly or by the trunk polymer compound chemistry is bonded to this substrate surface.As mentioned above, the materials statement mask has this specific character, and perhaps replacedly, the intermediate layer with this specific character is formed on the raw material surface.

Substrate surface

Substrate surface can be inorganic or organic layer, as long as this surface has the synthetic characteristic that forms aforesaid surface grafting layer of the grafting of being adapted to pass through.In this embodiment, the polarity of substrate surface is unimportant, and can be hydrophily or hydrophobic, and this is because the conversion between hydrophily and the hydrophobicity state is managed by the thin figure cambium layer with polymer compound.

In the intermediate layer, especially when the thin polymeric layers of present embodiment prepares by photo-grafting polymerization, plasma irradiating graft polymerization procedure or radiation grafting polymerization, this department preferably has the layer on organic surface, and especially preferably has the layer of organic polymer layers.The embodiment of organic polymer comprises synthetic resin such as epoxy resin, acrylic resin, urethane resin, phenolic resins, styrene resin, vinylite, mylar, polyamide, melmac or forms resin; With natural resin such as gel, casein, cellulose or starch.Because in methods such as photo-grafting polymerization, plasma irradiating graft polymerization procedure, radiation grafting polymerization, glycerol polymerization is to extract hydrogen from organic polymer, therefore according to the viewpoint of output, preferred especially the use extracted very easy polymer such as acrylic resin, urethane resin, styrene resin, vinylite, mylar, polyamide or the epoxy resin that damages to hydrogen.

The intermediate layer can be further to play the layer of raw material effect described below or the layer that forms on raw material as required.

In this embodiment, for when substrate is formed by resin molding etc., make that the substrate surface unevenness is 500nm or littler, the surperficial unevenness of preferably adjusting raw material (being substrate) is 500nm or littler.In order to make that the substrate surface unevenness is 500nm or littler by the intermediate layer is provided when substrate when the source material surface forms, preferably adjusting interlayer surfaces is 500nm or littler.In order to make that the substrate surface unevenness is 500nm or littler, preferentially be chosen in the good resinogen material in surface smoothness aspect and when forming the intermediate layer, form the good intermediate layer of the thickness uniformity.

Layer with polymerization initial characteristic

In embodiment (1), according to effective generation activity site and the purpose of improving figure formation susceptibility, be preferably formed can demonstrate the polymerization initial characteristic layer as the intermediate layer, or by adding as forming substrate surface by applying polymerizable compound or polymerization initiator to the raw material surface that energy can demonstrate the compound of polymerization initial characteristic.

The layer (below, suitably be called " polymerizable layer ") that demonstrates the polymerization initial characteristic can be dissolved into by the composition with necessity in the solvent that can dissolve these compositions, on the raw material surface by cambium layer such as coating with by heating or rayed this layer that hardens and form.

Be used in the not restriction especially of polymerizable compound in the polymerizable layer, as long as it adheres to substrate securely and is attached to the hydrophilic compounds that has polymerizable groups on terminal and/or its side chain and by applying energy such as active rayed is included in the upper layer, and in the middle of a lot of this compositions, the hydrophobic polymer that has polymerizable groups in its molecule is preferred.

The homopolymers that the specific embodiment of hydrophobic polymer comprises diene homopolymers such as polybutadiene, polyisoprene or polyprene and contains the allyl monomer group is as poly-propyl group (methyl) acrylate or 2-pi-allyl ethoxyl methyl acrylates; The copolymer of two or more components in styrene, (methyl) acrylate, (methyl) acrylonitrile etc., and contain diene monomer such as butadiene, isoprene or pentadiene or contain the formation unit of allylic monomer; The polymer that has the linear polymer of carbon-carbon double bond or three kinds of compositions in its molecule closes as not saturated polyester, insatiable hunger that polyepoxides, insatiable hunger close polyamide, polypropylene or high density polyethylene (HDPE) are closed in insatiable hunger; Or the like.

In specification, the group of expression " propylene and 2 methacryls " group the two or one of them is known as " (methyl) propylene " group.

About solid matter in the polymerizable layer, the polymerizable compound amount is preferably in the scope of 0 to 100 quality %, more preferably in 10 to 80 quality % scopes.

(b) polymerization initiator

Polymerizable layer among the embodiment (1) preferably contains by applying the polymerization initiator that energy has the polymerization initial characteristic.Being used in terminal polymerization initiator of the present invention can suitably select by applying according to purpose thermal polymerization that certain energy such as active rayed, heating, irradiating electron beam etc. demonstrate the polymerization initial characteristic, the Photoepolymerizationinitiater initiater etc. from routine is known.In the middle of these polymerization initiators, owing to photopolymerization height than thermal polymerization aspect reaction speed (polymerization speed), therefore consider output, it is preferred using Photoepolymerizationinitiater initiater.

Available Photoepolymerizationinitiater initiater in this embodiment is restriction especially not, as long as it can be by shining active photoactivation and can aggregate packet being contained in the polymerizable compound in the polymerizable layer and having the hydrophilic compounds of polymerizable groups and be included in the upper layer on terminal or its side chain, embodiment comprises atomic group polymerization initiator, anionic polymerization initiator, cationic polymerization initiators etc.

The specific embodiment of Photoepolymerizationinitiater initiater comprises acetophenone such as p-trihydroxy alcohol～butyl trichloroacetophenone, 2,2 '～two close acetyl or 2～hydroxyl～2～methyl～1-ketone; Ketone such as benzoyl ketone, 4,4 '～secondary dimethyl amine benzoyl ketone, 2～diuril ton copper, 2～methyl thioxanthones, 2～ethyl group thioxanthones or 2～isopropyl thioxanthone; Benzoin esters such as benzoin, benzoin methyl ester, benzoin isopropyl esters or benzoin isobutyl; Benzyl ketone ketal such as benzyl dimethyl ketone ketal or hydroxy-cyclohexyl phenyl ketone; Or the like.

About solid matter in the polymer layer, in the scope of preferred 0.1 to the 70 quality % of the amount of polymerization initiator, more preferably in the scope of 1 to 40 quality %.

Be used to apply the not restriction especially of solvent of (coating) polymerizable compound and polymerization initiator, as long as it dissolves these compositions.According to being convenient to dry and exercisable viewpoint, solvent does not preferably have too high boiling point, and especially, the preferred solvent of boiling point in about 40 to 150 ℃ of scopes.

Its specific embodiment comprises acetone, methyl ethane base ketone, thiacyclohexane, ethane acetate, oxolane, toluene, the ethylene glycol monomethyl ether, ethylene glycol list ethane ether, ethene diethanol dimethyl ether, the propyleneglycoles monomethyl ether, propyleneglycoles list ethane ether, acetylacetone,2,4-pentanedione, cyclohexanone, methyl alcohol, ethanol, 1～methoxyl group～2～propyl alcohol, 3～methoxypropanol, divinyl glycol monomethyl methyl ether, divinyl glycol monomethyl ethane ether, the divinyl ethylene glycol dimethyl ether, the divinyl ethylene glycol diethyl ether, propyleneglycoles n-formyl sarcolysine base ether acetate, propyleneglycoles list ethyl ether acetate salt, 3～methoxy-propyl acetate etc.

These solvents can be used alone or in combination.With respect to the gross mass of coating solution, the solid matter of appropriate amount is in the scope of 2 to 50 quality % in coating solution.

When polymerizable layer is formed on the raw material when forming substrate, consider to demonstrate enough polymerization initial characteristics and prevent that layer from peeling off so that keeps a layer characteristic, the amount of polymerizable layer coating amount as dry mass preferably 0.1 to 20g/m ²Scope in, and as dry mass more preferably 1 to 15g/m ²Scope in.

As mentioned above, it is easy so that polymerizable layer is formed form membrane to apply the composition formation polymerizable layer and the removal that are used for polymerizable layer by use coating etc. on substrate surface.Preferred heating and/or rayed this layer that is used to harden that adopts.Especially, preferably by heating with come dry this layer by rayed pre-hardening this layer subsequently, this permission is hardened polymerizable compound extremely to a certain degree, is used for effectively preventing as finishing the hydrophilic compounds grafting problem peeled off of whole polymerizable layer afterwards.The reason that the use rayed is used for hardening is similar to the description of Photoepolymerizationinitiater initiater part.

Suitably select temperature conditions and heating cycle to be preferably 100 ℃ or lower and be preferably 30 minutes drying time or still less so that it is enough to remove the solvent of coating and temperature.More preferably, according to the viewpoint of output, select heating condition so that its baking temperature in 40 to 80 ℃ scope, its drying time is in 10 minutes or shorter scope.

The light source of figure in forming that be used in described below also is used in the rayed that heating is carried out after raising as required.Consider and prevent forming the grafting figure subsequently and by applying energy forms bonding between activity site on the polymerizable layer and grafted chain inhibition, preferably carry out the degree of rayed to the atomic group polymerization that can carry out the polymerizable compound that exists in the polymerizable layer, this is not complete polymerization but partially polymerized.Light-struck time span can change according to the employed intensity of light source, and is preferably 30 minutes usually or still less.Being used for prevulcanized roughly standard and being wherein in the amount with rest layers after the solvent washing is 10% or still less and to remain amount of initiator after pre-hardening be 1% or still less condition.

Raw material

" substrate " that uses among the present invention means that polymer can be bonded directly to its lip-deep material.When intermediate layer such as polymerization initiation layer are formed on the surface of material such as resin molding and polymer when being provided with graphic form, material such as resin molding are called " raw material " at this.

Being used in the metallic pattern of the present invention and constituting the optimal seeking of raw and processed materials that provides the substrate with above-mentioned characteristic surface is board-like material, and it has surperficial unevenness is 500nm or smooth surface still less and high spatial stability.Embodiment comprises that paper, lamination have paper, the metallic plate (as aluminium, zinc, copper etc.) of plastics such as polyethylene, polypropylene, polystyrene etc.; Plastic film (as cellulose diacetate, primary cellulose acetate, cellulose propionate, cellulose butyrate, cellulosic acetate, cellulose nitrite, polyethylene to titanate, polyethylene, polystyrene, all propylene, poly-carbonic acid, polyvinyl acetal, polyimides, epoxy resin etc.); Lamination or vapour deposition are the paper of the plastic film of above-mentioned metal on it; Or the like.Polyester or polyimide film are used among this embodiment of the present invention preferably as substrate.

And, when the metallic pattern of printed leads plate the application of the invention forms as conductive layer, preferably use insulating resin as substrate.

The embodiment of insulating resin comprises the resin that is formed by compound such as polyphenylene oxide, unsaturation polyphenylene oxide, cyanate ester compounds or epoxy resin compound.Preferably use by containing the substrate that compositions of thermosetting resin at least a in these resins forms.When at least two kinds of combinations in these resins were used to form resin combination, the preferred embodiment of resin combination comprised: a kind of composition in cyanate esterification and thing and polyphenylene oxide and the unsaturation polyphenylene oxide; A kind of composition in epoxy resin compound and polyphenylene oxide and the unsaturation polyphenylene oxide; With a kind of composition in cyanate ester compounds, epoxy resin compound and polyphenylene oxide and the unsaturation polyphenylene oxide.When multi-sheet printed lead plate formed by using the thermosetting resin compound, preferred use did not contain the thermosetting resin compound of inorganic filler, and this inorganic filler is selected from the group that is made of silica, mica, aluminium hydroxide and magnesium hydroxide.In addition, preferred use further contains the thermosetting resin compound of bromine compounds or phosphorus compound.

The preferred embodiment of insulating resin that is used to form the substrate of printed leads plate comprises 1,2-2 (thiazolinyl penylene) ethane resin and by polyphenylene oxide resin and 1, the nonsaturated resin that 2-2 (thiazolinyl penylene) ethane resin forms.The further details of this resin will be described in " the Journal of Applied Polymer Science " that edited by people such as SatoruAmaba, the 92nd rolls up the the 1252nd to 1258 (2004) page.

The preferred embodiment of other insulating barrier comprises liquid crystal polymer, and it can obtain to be " VECSTER " (trade (brand) name is made by Kuraray limited liability company system) and fluororesin such as polytrifluorochloroethylene on market.

In the middle of these resins (polymeric material), polytrifluorochloroethylene (PTFE) is a unsurpassed material aspect high frequency characteristics.Yet PTFE is a kind of thermoplastic resin with low stress (Tg), and has poor spatial stability for heat.PTFE is poorer than the thermosetting resin material on mechanical strength.And, but PTFE has the problem of formation property poor operability.Thermoplastic resin such as polyhenylene ether (PPE) can be by getting up to use with fusion such as thermosetting resin.The embodiment of fusion comprises: the fluxing resin of PPE and epoxy resin; The fluxing resin of PPE and triallylisocyanate; Fluxing resin with the PPE resin with the polymerizable functional group that is incorporated into wherein and other thermosetting resins.

Not improved epoxy resin demonstrates not enough dielectric property.Yet, by introducing the improvement of expection epoxy resin characteristics such as big framework.By this way, the resin of characteristic and structure are introduced separately, the resin that is used to compensate its defective such as unsaturated is preferred wherein to use it to a great extent.

For example, although in the middle of thermosetting resin, the cyanate ester is to have the material of dielectric property par excellence, and it uses separately hardly, but is used as the nonsaturated resin of epoxy resin, maleimide or thermoplastic resin.For further details, see " Electronic technology " the 35th page of No.9 (2002), can be open to select insulating resin as described above with reference to it.

As mentioned above, when metallic pattern is used as the wiring (conductive layer) of printed leads plate, to handle the viewpoint of storing data in batches according to telling, to postpone and suppress signal in order reducing, each is effective in reduction dielectric constant and the dielectric loss tangent.Use low-dielectric loss tangent material just as the 397th page of (2004) middle description of " Electronics Packaging Institutional Journal " the 7th volume No.5.According to the data processing viewpoint of telling, use insulating material preferred especially with low-dielectric loss tangent characteristic.More specifically, preferable substrate by dielectric constant, be relative dielectric constant under 1GHz be 3.0 or littler insulating resin form, more preferably substrate is that 0.0l or littler insulating resin form under 1GHz by dielectric constant.The dielectric constant of insulating resin and node loss tangent are determined by conventional method, this method for example is the method for describing in the 189th page of the 18th JIEPAnnual conference summary in 2004, has wherein used the cavity oscillator perturbation motion method that utilizes measurement mechanism and the ε r of system and tan δ to be used for the superthin section made by the wired company of Keycon.Thus, this is useful for select insulating resin in the light of dielectric constant and dielectric loss tangent.Have 3.5 or still less dielectric constant and 0.01 or still less the embodiment of the insulating resin of dielectric loss tangent comprise liquid crystalline resin, polyimide resin, poly-different close numerical value and cyanate ester resin, two (two penylenes) ethane resin etc., and further comprise its improved resin.

Form figure (image)

In embodiment (1), form figure by illumination radiation line such as light.When carrying out rayed under the situation that has optical-thermal conversion material, figure can heat by the scan exposure via the laser beam of the wavelength with infrared-ray zone etc. and form.

The method embodiment that is used to form figure comprises such method, and it comprises the exposure that comprises light that writes by heating or irradiation with radiation.Its specific embodiment comprises the rayed of using infrared laser, uviol lamp, visible light etc., and electron beam irradiation as radiation gamma, the heat by heat write etc.The light source embodiment that is used for it comprises mercury vapor lamp, metal halide lamp, xenon lamp, chemical lamp, carbon arc lamp etc.The embodiment of radiation comprises electron beam, X-ray, ion beam, far infrared etc.In addition, can use g-ray, i-ray, dark UV ray and high density energy bundle (laser beam).

The specific embodiment of normally used embodiment comprises by first-class the writing direct of heat record; Scan exposure by infrared laser; High brightness quickflashing exposure by xenon discharge lamp etc.; Infrared lamp exposure or the like.

Replacedly, under the situation that polymeric layer obtains by the polar switching group that uses the photothermographic dry under wavelength 700nm or the littler wavelength, any light illuminating method can both use, as long as it causes polar switching in the figure cambium layer, that is, it can be by decomposing, open or replace the hydrophilic/hydrophobic that the polar switching group changes the polar switching group.For example, can obtain rayed by uviol lamp or visible light etc.The embodiment of these light sources comprises mercury vapor lamp, metal halide lamp, xenon lamp, chemical lamp, carbon arc lamp etc.

The preferred method of introducing polar switching of using is used for by laser explosure directly graphical based on computer digital data.The embodiment of laser comprises gas laser such as carbonic acid gas laser, Ar laser, He/Cd laser or Kr laser; Solid state laser such as liquid (dyestuff) laser, ruby laser or Nd/YAG laser; Semiconductor laser such as GaAs/GaAlAs or InGaAs laser; Excimer laser such as KrF laser, XeCl laser, XeF laser or Ar ²Laser; Or the like.

Embodiment (2)

In embodiment (2), the grafting figure by make have polymerizable groups and with the compound of the functional group of electroless plating catalyst or its precursors reaction with substrate contacts and form with graphics mode illumination radiation ray afterwards.In the following description, " with the functional group of electroless plating catalyst or its precursors reaction " can be called " group that reacts to each other " and have polymerizable groups and the compound of group of reacting to each other is known as " group that reacts to each other that contains polymerisable compound ".

Form the grafting figure by surface grafting

In embodiment (2), by making the polymerizable compound contain the group that reacts to each other and substrate contacts and apply energy with graphic form, can between the polymerizable thing group of the polymerizable compound that contains the group that reacts to each other and substrate, form chemical bond, with formation and electroless plating catalyst or its precursors reaction hard district good aspect the durability (below, the words that need can be called it " district reacts to each other " simply).The formation of this type bonding is called " surface grafting ".Surface grafting according to embodiment (2) is almost similar to the surface grafting polymerization of description among the top embodiment (1).Though will be had polar switching group among the embodiment (1) by the polymers grafted compound, but the synthetic Zhi Jie Hey that contains the polymerizable compound with the group that reacts to each other among this embodiment contacts with substrate surface, so that this synthetic is bonded to the reactive specy that produces on substrate surface.

Synthetic can be implemented by substrate is immersed in the liquid composition that contains the polymerizable compound with the group that reacts to each other with contacting of reactive specy.Replacedly, consider and be convenient to the validity handling and make, preferably provide the layer that contains synthetic to substrate surface by coating method as described below, this synthetic contain have the group that reacts to each other polymerizable compound as main component.

The surface grafting relevant with embodiment (2) can form in the mode identical with the surface grafting of explanation in embodiment (1).

The polymerizable compound that contains the group that reacts to each other

The polymerizable compound that contains the group that reacts to each other of Shi Yonging is a kind of like this polymer in this embodiment, wherein can add polyene unsaturation group (polymerizable groups) is introduced in monomer with the group that reacts to each other described below or at least one group that is selected from this monomer by use as polymerizable groups as vinyl groups, allyl group or (methyl) propylene group homopolymers or copolymer.But polymer at least one of terminal or its side chain, have the dimerization group and more preferably polymer on terminal and its side chain, have polymerizable groups.

But the polyacetylene compound that contains the group that reacts to each other can be following synthetic.

The synthetic embodiment that contains the polymerizable compound of the group that reacts to each other comprises:

The embodiment of synthetic method comprises i) wherein have the monomer of the group that reacts to each other and have the monomer of polymerizable groups by the method for copolymerization, ii) wherein have the monomer of the group that reacts to each other and have two key precursors monomer copolymerization and after react to each other with the method for introducing pair keys (polymerizable groups) thus with the method for introducing two keys and the monomer that iii) wherein has the monomer of the group that reacts to each other and have a polymerizable groups with processing such as raw material.In the middle of these methods, aspect synthesis capability, preferably use the monomer that wherein has the group that reacts to each other and have two key precursors monomer copolymerization and after react to each other iii) with cloud material processed monomer that ii) and wherein has the group that reacts to each other with the method for introducing pair keys and monomer with the method for introducing polymerizable groups thus with polymerizable groups.

The specific embodiment that is used for the monomer of the synthetic polymerizable compound that comprises the group that reacts to each other comprise () acrylic acid, alkaline metal salt and its ammonium salt, methylene succinic acid, alkaline metal salt and its ammonium salt, the 2-ethoxy () acrylate, () acrylamide, the N-monomethylol () acrylamide, the N-dihydroxymethyl () acrylamide, arylamine or its hydrogen halides hydrochlorate, 3-vinyl propionic acid, alkaline metal salt and its ammonium salt, vinyl sulfuric acid, alkaline metal salt and ammonium salt thereof, 2-sulphur ethyl () acrylate, polyoxyethyleneglycol mono (meta) acrylate, 2-acrylamide-2-methylpropane sulfuric acid, acidphosphooxypolyoxyethyleneglycol mono (meta) acrylate, with N-vinyl pyrrolidone (having following structure).In a word, the monomer (perhaps being its salt when forming the salt structure thus) that has as the functional group of carboxylic group, sulfate group, phosphate group, ammonium group, hydrogen-oxygen group, acid amides group, hydrogen phosphide group, pyridine group or ether group is known as embodiment

The monomer embodiment that contains the allyl group of the group copolymerization that can and react to each other comprise pi-allyl () acrylate, 2-pi-allyl ethoxyl methyl acrylate etc.

Monomer embodiment with two key precursors comprises 2-(3-chloro-1-oxopropoxy) ethylmethacrylate and 2-(3-bromo-1-oxopropoxy) ethylmethacrylate.

Monomer embodiment with polymerizable groups, it is used for utilizing with the reaction of the functional group of polymer with the group that reacts to each other such as carboxyl or amino or its salt, oh group, epoxy resin group etc. introduces the unsaturation group, and it comprises () acrylic acid, glycidyl () acrylate, allyl glycidyl, 2-isocyanatether (meta) acrylate etc.

The embodiment that contains the polymerizable compound of the group that reacts to each other further comprises little monomer.Produce little monomer methods of using in this embodiment and for example comprise Publishing﹠amp by Industrial; Consulting, Inc on September 20th, 1989 the disclosed the whole bag of tricks of (Ed.YuyaYamashita) describing among " the Synthesisi of Macromonomers " of second portion at " Chemistry and Industry of Macromonomers ".The particularly preferred embodiment of little monomer of Shi Yonging comprises from containing carboxyl group as the derivative little monomer of acrylic or methacrylic acid in this embodiment; From monomer such as 2-acrylamide-2-methylpropanesulfonic acid, the acid of sulfonate vinyl styrene or the little monomer of the derivative sulfate of its salt; From the nitrogen body as (methyl) acrylamide, N-ethene acetamide, N-vinyl formamide, the big monomer of the derivative amide groups of N-vinylcarboxylic acid acid amides, monomer such as the derivative big monomer of hydroxyethyl meth acrylate, hydroxy ethyl methacrylate or glycerol monomethacrylates from containing hydroxyl; From monomer such as the derivative big monomer of methoxy ethyl acrylate, methoxyl group polyethylene glycol acrylate or polyethylene glycol acrylate that contains alkoxyl or ethylene oxide,1,2-epoxyethane base; Or the like.In addition, the big monomer with polyethylene glycol chain or glycol polypropylene chain also can be effectively as the big monomer that uses in this embodiment.

This slightly the molecular weight of monomer preferably in 250 to 100000 scope and particularly preferably in 400 to 30000 the scope.

Be used to contain the not restriction especially of solvent of the synthetic of polymerizable compound with the group that reacts to each other, as long as it can dissolve its main component, that is, and little monomer, monomer etc.The preferred embodiment of this solvent comprises water-based solvent such as water, water-soluble solvent, its mixture or further contains those of surfactant.

" water-soluble solvent " is that the solvent that can mix with arbitrary ratio with water and embodiment comprise alcohol solvent such as methyl alcohol, ethanol, propyl alcohol, ethylene glycol, glycerol etc.; Acid is as acetic acid; Ketone solvent such as acetone; Ammonium solvent such as formamide; Or the like.

Can be added to the not restriction especially of surfactant in the solvent as required, as long as it dissolves in solvent, embodiment comprises anion surfactant such as sodium n-pelopon A; Cationic surfactant such as n-dodecyltrimethylammonium chloride; The surfactant of nonionic formula such as polyethylene glycol oxide nonyl phenolic ester (product embodiments on the market comprises EMYL GEN 910 (trade name is made by KAO. Corp. SA)), polyethylene glycol oxide sorbitan mono laurate (product embodiments on its market comprises " TWEEN  20 "); With the polyethylene glycol oxide lauroyl; Or the like.

When synthetic is liquid state, the direct in any way and substrate contacts of synthetic.Based on the solids content of layer, the coating amount that contains the layer that the synthetic of the group that reacts to each other forms by coating preferably 0.1 to 10g/m ²Scope in, more preferably 0.5 to 5g/m ²Scope in, obtaining even coated film, and be enough to react to each other with plating catalyst or its precursor.

Substrate

Be used in substrate among the embodiment (2) and be terminal with the above-mentioned polymerizable compound that contains the group that reacts to each other or side chain directly or by the substrate of main chain polymerizable compound chemical bonding to its surface.Raw material can have its primary characteristic, and replacedly, the intermediate layer with this characteristic can be formed on the source material to form substrate.

And the other layer with initial polymerization characteristic can form in the mode similar to embodiment (1).

In embodiment (2), use that to have unevenness also be preferred as 500nm or substrate still less.

Form figure (image)

The method of using in the figure of embodiment (2) forms of giving energy is restriction especially not, with can use any method, as long as it can produce activity site on substrate surface, and the polymer-based group that will be enough to contain the polymerizable compound of the group that reacts to each other is attached on the substrate surface and gets final product.Preferentially select the method for the active light of irradiation according to the viewpoint of cost and simplification device.

If take active rayed, then can use based on the scan exposure of numerical data or by using the graph exposure of photoetching film.

In the various wiring methods of describing among the embodiment 1 any also can be preferably used as the method that figure writes among this embodiment in the above.

Apply by aforesaid energy, the polymerization with the polymerizable compound that the grafting figure of the higher grafted chain of mobility can be by having the group that reacts to each other and the activity site that produces on substrate surface forms.In a preferred embodiment, use can additionally be attached to grafted chain polymerizable groups on the grafted chain side chain that is being bonded on the substrate having containing of polymerizable groups the react to each other polymerizable compound of group on terminal or the side chain, branch grafted chain structure is provided, and therefore cause the rapid improvement of the density and the mobility of the grafting that forms, and cause and electroless plating catalyst or higher the reacting to each other of its precursor.

(b) electroless plating catalyst or its precursor are applied to the grafting figure

Electroless plating catalyst

The electroless plating catalyst that uses in this technology mainly is a zero-valent metal, and embodiment comprises Pb, Ag, Cu, Ni, Al, Fe, Co etc.Among the present invention, management and catalytic capability are good being convenient to, preferred P b and Ag.Be used for fixing zero-valent metal and wherein adjust the metallic colloid of electric charge to the common use of method on the grafting figure (zone reacts to each other).The metal-to-metal adhesive physical efficiency is made by reducing the solution metal ion, has charged surfactant or charged protective agent in this solution.The charge energy of metallic colloid reaches by employed surface activity or protective agent is adjusted.The group phase reaction that reacts to each other on feasible wherein controlled thus metallic colloid of electric charge and grafting figure, the metal-to-metal adhesive physical efficiency is optionally absorbed on the grafting figure.

The precursor of electroless plating catalyst

As the precursor of the electroless plating catalyst that in this technology, uses, can restrictedly not use any material, as long as can be used as electroless plating catalyst by this material of chemical reaction, the main zero-valent metal ion that in electroless plating catalyst, uses that uses.The zero-valent metal that causes being used as electroless plating catalyst for the metal ion of electroless plating catalyst precursor by reduction reaction.This metal ion can be changed by another kind of reduction reaction and be zero-valent metal, and perhaps because the electroless plating catalyst precursor is changed into metal by the reducing agent in the electroless plating groove thus, it is dipped in the electroless plating groove.

In fact be applied to the grafting figure of slaine state for the metal ion of electroless plating catalyst precursor.As employed slaine, can adopt any material and do not limit, as long as this material can be dissolved in the appropriate solvent, perhaps be broken down in metal ion and the raw material (anion).The slaine specific embodiment comprises M (NO ₃) _n, MCl _n, M _N/2(SO ₄), M _3/n(PO ₄) (wherein M represents n valency metallic atom) etc.The embodiment of suitably used metal ion comprises the metal ion that forms by decomposing metal salt.The specific embodiment of metal ion comprises silver ion, copper ion, aluminium ion, nickel ion, cobalt ions, iron ion, palladium ion etc.Aspect catalytic capability, preferentially use silver ion and palladium ion.

Be used to apply metallic colloid as electroless plating catalyst or apply slaine and comprise a kind of like this method to the method embodiment on the grafting figure as the electroless plating precursor, it comprises metallic colloid is distributed in the suitable decentralized medium, or slaine is dissolved in the appropriate solvent, comprise the decomposing metal ion solution with preparation, there is this solution of diffusion on the raw material surface of grafting figure thereon, also be a kind of like this method, it comprises dipping in and is taken at the raw material that have the grafting figure in the solution.When making when comprising that metal ion solution contacts with raw material, metal ion can be by utilizing inner ion to react to each other or dipole ion reacts to each other be absorbed into the group that reacts to each other on the graphics field.In order to be enough to absorb and flood, the concentration of metal ion or the solution metal salinity that makes its contact are preferably in the scope of 1 to 50 quality %, more preferably in the scope of 1 to 30 quality %.Contact required time span preferably near one minute to 24 hours with more preferably near five minutes to one hour.

(c) form metal film by electroless plating

In method provided by the present invention, form graphical metal film by the electroless plating on the substrate that obtains by technology (c).In this technology, electroplate in the catalytic inhibitor electroless plating groove (second aspect) and carry out electroless plating carrying out under the situation that has surface charge improver (first aspect) or containing specified amount, have the high fine pattern metal film of adequate thickness with formation.

About electroless treatment, for example, J.W.M.Jacobs and J.M.G.Rikken, " J.Electrochem.Soc. ", 135,2822 (1988) and A.M.T.van derPutten, people's such as G.de.Bakker " J.Electrochem.S oc. ", 140,2229 (1993) disclose the technology that is used to form thin anisotropy electroplating film, and it comprises only electroplating film on required direction.These document suggestions can be controlled the metal film shape in electroless plating.Yet, to compare with the present invention, these documents to form fine pattern or lead-in wire etc., perhaps disclose or advise its usability less than open its applicability of also not advising.

The surfactant that a large amount of open source literatures that comprise JP-A No.2003-49280 disclose the structure with the surface charge improver that uses among the present invention of being analogous to is added in the electroless plating solution, so that the stable electrical coating bath.Yet, the inventor finds that at first anisotropic growth can be used to form graphical metal film, with identical among the present invention, only can realize advantageous effects of the present invention when the anisotropic growth technology is used in following technical combinations, this technology comprises provides with graphical form that have can with electroless plating catalyst or its precursor reacts to each other and directly or chemically be bonded to the polymer of the functional group of substrate.

Be well known that also electroplating bath can be stablized by adding the plating catalytic inhibitor to electroless plating solution, and is similar to the present invention, for example as described in JP-A No.09-287078.Yet, the inventor at first finds to electroplate catalytic inhibitor can be used to form graphical metal film, as disclosed in this, only can realize advantageous effects of the present invention when electroplating when catalytic inhibitor is used in the combination with following technology, this technology provides with graphical form to be had and can and directly and chemically be bonded to the polymer of the functional group of substrate with electroless plating catalyst or its precursors reaction.

Allow to work in the arbitrary steps of surface charge improver in electroless plating.The surface charge improver can be added in the solution of electroless plating groove, is used for electroless treatment, and perhaps substrate surface prepared by the surface charge improver before electroless plating.

Particularly, before a kind of mode corresponding to using electroless plating solution to form the technology (c-1) of metal film by the substrate with polymeric layer being carried out electroless plating with graphics mode, back one mode is carried out electroless plating so that form the technology (c-3) of metal film with graphics mode corresponding to the technology (c-2) of handling the substrate with polymeric layer with the grass that contains the surface charge improver with to the substrate with polymeric layer.

The surface charge improver preferably has the organic compound of following group in its molecule: (i) substrate is had the group of affinity and (ii) ion leaving group.If carry out electroless plating existing under the situation of this surface improver, have then that high density conforms to adequate thickness and with the grafting figure that obtains by above-mentioned technology and metal membrane-coating be formed on the figure.As a result, formed metallic pattern has high conductivity and high-adhesiveness.

In electroless plating, any method all can be used for the plating catalytic inhibitor is added in the electroplating bath.Before beginning plating or after beginning to electroplate, can add electroless plating solution to specifically measuring catalytic inhibitor.Replacedly, electroplating catalytic inhibitor can add at interval with certain hour, remain in the concrete scope so that electroplate catalytic inhibitor concentration in the solution of electroless plating groove, perhaps add so that its concentration remains in the concrete scope as required, measure this concentration simultaneously.

Usually, technology (c-1 ') can comprise using and contains 1 * 10 ^-10To 1 * 10 ^-4The electroless plating solution that nmol/l electroplates catalytic inhibitor carries out electroless plating to the polymer layer bearing substrate, to form graphical metal film, and technology (c-2 ') comprise the polymeric layer bearing substrate is carried out electroless plating to form graphical metal film, add the plating catalytic inhibitor to electroless plating solution simultaneously, remain on 1 * 10 so that electroplate the concentration of catalytic inhibitor ^-10To 1 * 10 ^-4In the scope of nmol/l.

Below, will describe each technology in detail.Use contains (c-1) surface charge improver or (c-2) 1 * 10 ^-10To 1 * 10 ^-4The electroless plating solution that nmol/l electroplates catalytic inhibitor forms metal film with graphic form by the substrate with polymeric layer being carried out electroless plating

Electroless plating

Electroless plating is by using the metal ion solution that contains that will be deposited to come the technology of plated metal and the increase that metal deposition causes conductivity in chemical reaction.For example by remove have the graphic form electroless plating catalyst via the water flushing and it is immersed in excess metal on the substrate of acquisition in technology (b) in the electroless plating groove that contains the surface charge improver or electroplate catalytic inhibitor and slaine carries out electroless plating in this technology.General known any electroless plating groove can be used as the electroless plating channel parts except surface improver and plating catalytic inhibitor in this area.Be used for being positioned at the electroless plating solution (groove) that electroless plating catalyst precursor on the grafting figure that is absorbed or is dipped into forms metal film and also can adopt the generally well-known electroless plating groove in any this area by use.

Generally, the electroless plating groove has and contains the synthetic that (1) plated metal ion, (2) reducing agent and (3) are used for the additive (stabilizer) of stable metal ion as main component.Among this embodiment, the electroless plating groove further contains (4) above-mentioned surface charge improver or electroplates catalytic inhibitor.Except these, electroplating bath can further contain the stabilizer of known additive of arbitrary routine such as electroplating solution etc.

The metal that is used in the electroless plating groove comprises copper, tin, lead, nickel, gold, palladium and rhodium, and in the middle of these, according to special preferably copper of the viewpoint of conductivity and gold.

The embodiment that is used for the metallic compound that can be used on electroless plating solution of electroless plating groove comprises sulfate, sodium salt, carbonate, oxide, hydroxide etc.The metallic compound amount that contains in electroless plating solution is considered amount of metal in 0.1 to 5g/L scope, it is preferably near 0.8 to 1.2g/L scope.When the amount of metallic compound is lower than 0.1g/L and since form metal film become not enough and thus in following technology deposition electroplate and become not enough, therefore this is not preferred for the present invention.On the other hand, when the amount of metallic compound exceeded 5g/L, owing to there is not the additional effect that obtains by rising concentration, therefore this was not preferred for the present invention.According to economic point of view, increase is disadvantageous with the proportional aequum complexing agent of concentration, and is except these, poor for the applicability of solution waste water treatment.

Best reducing agent and additive can be selected according to metal.For example, copper electroless plating groove contains Cu (SO ₄) ₂As mantoquita, HCOH as reducing agent and additive such as EDTA (is stabilizer for copper ion), Rochelle salt (chelating agent) etc.The electroplating solution that is used for electroless plating CoNiP contain cobaltous sulfate and nickelous sulfate as slaine, sodium hypophosphite as reducing agent and sodium malonate, natrium malicum, sodium succinate as complexing agent.And palladium electroless plating groove contains (Pd (NH ₃) ₄) Cl ₂As metal ion, NH ₃And H ₂NNH ₂As reducing agent and EDTA as stabilizer.These electroplating solutions also contain the composition except mentioned component.

The specific embodiment that has reduction characteristic and be added to the sugar in the electroless plating solution comprises glucose, dextrose, D-sorbite, cellulose, sucrose, sweet mellow wine and glucose lactone.Sugar content can be from about 3 to about 50g/L, preferably from about 10 to about 20g/L.Sugared content less than about 3g/L is not preferred, and this is because by this content, it is not enough forming the electroless plating film, thereby makes that the deposition properties of electroplating in next technology is poor.Sugared content more than 50g/L is not preferred, and this is because by this content, the stability of electroless plating solution reduces, and can form the electroless plating film with poor profile easily.

The embodiment that adds the complexing agent in the electroless plating solution to is comprised hydantoins, organic carboxyl acid class and organic amino yl carboxylic acid class.The specific embodiment of hydantoins comprises hydantoins, 1～methyl hydantoins, 1,3～dimethyl hydantoin, 5,5～dimethyl hydantoin and allantoin.The specific embodiment of organic carboxyl acid class comprises that the specific embodiment of citric acid, tartaric acid, butanedioic acid and malonic acid, organic amino yl carboxylic acid class comprises ethene diaminourea four acetic acid, 1,3-propane diaminourea four acetic acid, NTA, ethene diaminourea disuccinic acid, imino-diacetic acetic acid and any salt thereof.Separately or its two or more be used in combination complexing agent.

Be mixed into compound dosage in the electroless plating solution in about scope of 2 to about 50g/L, preferably in about scope of 10 to about 40g/L.Be less than 2g/L mix complexing agent amount be not preferred because this amount can provide not enough load and energy and not enough thus copper solubility.More than 50g/L mix complexing agent amount be not preferred, although this is because this amount can improve copper solubility, is disadvantageous economically, and can makes waste water treatment complicated.

Reducing agent embodiment comprises organic acetaldehyde such as formalin or glyoxalic acid, sugar, reduction phenol such as hydroquinones, hypophosphorous acid, borohydrides and diamines borine.Consider electroplating velocity, formalin and borohydrides are preferred, and this is because its high reducing power.When the sugar with relative lower reducing power was used as reducing agent, the hydantoins with low relatively compound ability can be used as complexing agent.

Must further contain alkali metal hydroxide for electroless plating solution.Consider easy acquisition and cost, alkali metal hydroxide is NaOH, potassium hydroxide or lithium hydroxide preferably.Alkali metal hydroxide can use separately or can multiplely as required be used in combination.With the amount that is mixed into the alkali metal hydroxide in the solution in about scope of 10 to about 80g/L, preferably in about scope of 30 to about 50g/L.The alkali metal hydroxide amount that is lower than 10g/L is not preferred, and this is that the formation of electroplating metal film is not enough, thereby makes the electroplating deposition poor performance in the next step in the low current density scope owing to have this amount.The alkali metal hydroxide amount that is higher than 802g/L is not preferred, and this is that copper solubility can increase and reduce along with concentration owing to have this amount, and this can cause the electroplating solution poor stability.

When the preparation electroless plating solution, the combination of above-mentioned each composition and blending ratio are preferably suitably adjusted in above-mentioned scope, so that the pH of electroplating bath is in 10.0 to 14.0 scope, preferably in 11.5 to 13.5 scope.

If necessary, electroless plating solution can further contain stabilizer such as potassium ferrocyanide, cyanogen salt, pyridine compounds, tannic acid or if tannin.Only any in these compounds of interpolation a small amount of (a few ml/l) can keep good stability.

In having the treatment process of electroless plating solution, solution temperature is in about 20 to about 70 ℃ scope, preferably about 35 to about 50 ℃ scope and this material can be entered into electroplating solution and reached about 30 seconds to about 120 minutes, preferably reach about 10 to about 60 minutes.The electroplating solution temperature that is lower than 20 ℃ is not preferred, and this is because under this temperature, it is not enough that the electroless plating film forms.The electroplating solution temperature that is higher than 70 ℃ is not preferred, and this is because the stability of electroplating solution can reduce under this temperature.The immersion time less than 30 seconds in the electroplating solution is not preferred, and this is because under this time, it is not enough forming the electroless plating film.More than 120 minutes immersion times was not preferred, and this is owing under this time, can not find to exceed the effect of optimum range and can reduce output.

The surface charge improver

The surface charge improver of Shi Yonging can be any compound in the present invention, as long as it can be absorbed into source material surface and can suppress the absorption of metal ion to the raw material.The preferred use has (i) and substrate had the organic compound that has ion leaving group (decomposition group) in the group of affinity and its molecule.

At this, (i) group that has an affinity with substrate comprises hydrophobicity or hydrophilic functional group.Its preferred embodiment comprises alkyl with four or more carbon atoms, have the aryl of 6 or more carbon atoms and have the fluorinated alkyl of 3 or more a plurality of carbon atoms.(ii) the preferred embodiment of ion leaving group comprises hydroxyl, amino, amido and synergist group.The organic compound that has these functional groups in its molecule is preferably as the compound of surface charge improver.

For example, when use has the organic compound of amido, optionally it is absorbed on the substrate surface, so that should the surface positively charged.In this case, the surface potential of substrate preferably at+0.1mV to the scope of+500mV, more preferably at-1.0mV to the scope of+100mV.Zone with this positively charged surface can prevent that metal ion is (as Cu in the electroplating bath ²⁺) deposition, and metal ion only optionally is deposited on the zone with the plating catalyst (perhaps precursor) that attaches to graphical graft polymers thus.

Consider and to form fine pattern, this optimal process need not the electroless plating groove at thin metal film to be undertaken by after using surface charge to improve to be formed on the grafting figure, be used for preventing that undesirable surface charge improver from absorbing a part of hydrophilic radical such as hydroxyl, it does not react and stays in the grafted chain.

Preferably low molecule of surface charge improver used in this invention or high molecular organic amine compound.

The preferred embodiment of low molecule organic amine compound comprises the compound by following molecular formula (C-1) expression.

Molecular formula (C-1)

In molecular formula (C-1), R ¹To R ⁴Each all represents the unit price organic group separately, and preferably represents alkyl, and it can have substituting group or have substituent aryl.Embodiment comprises alkyl such as methyl, ethyl group or butyl and aryl such as alkyl such as phenyl, the naphthyl with 1 to 20 carbon atom or has phenyl as substituent benzyl.

X ^-Expression counting anion and its specific embodiment comprise CH ₃SO ₄ ^-, C ₂H ₅SO ₄ ^-, Cl ^-, Br ^-, H ₂PO ₄ ^-, CH ₃COO ^-, CH ₃SO ₃ ^-And NO ₃ ^-

The preferred embodiment of scintilla organic amine compound comprise by copolymerization have four ammonium salt groups monomer, have the monomer of glycol chain and have the copolymer that the monomer of the hydrocarbon that comprises four or more a plurality of carbon atoms is made; And have amino monomer by copolymerization, have the monomer of glycol chain and have the hydrocarbon that contains four or more carbon atoms and occupy the copolymer that the monomer that obtains copolymer 1/4th is made.

Any dimerization monomer of ammonium group all can be used as the monomer with four ammonium salt groups in four according to the present invention but have, and is used to form copolymer (for the molecule organic amine compound).Embodiment comprises (methyl) acrylate, acrylamide, allyl ether, vinethene, vinyl acetate and styrene and replaced styrene (R in its substituting group and the following molecular formula (C-2) ⁴Those are similar).Especially, preferred (methyl) acrylate or have the acrylamide of four ammonium salt groups, the embodiment with (methyl) acrylate of four ammonium salt groups comprises the compound by following molecular formula (C-2) expression.The embodiment of monomer comprises that also the betaine type compound is as using bromine ethene or monochloroacetic acid sodium by occupying the monomer that dimethyl amine vinyl acetate acid esters 1/4th is made.

Molecular formula (C-2)

In molecular formula (C-2), R ¹The expression hydrogen atom or-CH ₃R ²And R ³In each hydroxyalkyl R that all represents hydrogen atom separately, has the alkyl of 1 to 4 carbon atom or have 1 to 4 carbon atom ⁴The alkyl of 1 to 20 carbon atom of expression, have the hydroxyalkyl of 1 to 10 carbon atom or have the aralkyl of 1 to 10 carbon atom; A represents to have the alkylene or the oxygen alkano groups of 1 to 10 carbon atom or has the polyoxy alkano groups of 1 to 10 carbon atom; And X ^-Expression counting anion.

At this, by X ^-The technology anion of expression have with molecular formula (C-1) in identical implication, and its preferred embodiment also is identical.

But any copolymerization that has glycol chain in its molecule all can be used as the monomer with glycol chain, is used for organic amine compound formed according to the present invention.Embodiment comprises (methyl) acrylate, acrylamide, allyl ether, vinethene, vinyl acetate and styrene and replaced styrene (R in its substituting group and the molecular formula (C-2) ⁴Those are similar), its each in its molecule, all have glycol chain.Especially, preferred embodiment comprises (methyl) acrylate, and it has glycol chain.Embodiment with (methyl) acrylate of glycol chain comprises (gathering) glycol monomethyl (methyl) acrylate of being represented by molecular formula (C-3).

Molecular formula (C-3)

CH ₂＝C(R ⁵)COO(C ₂H ₄O) _nR ⁶

In molecular formula (C-3), n represents from 1 to 50 integer, is preferably 4 to 20; R ⁵The expression hydrogen atom or-CH ₃And R ⁶The expression hydrogen atom ,-CH ₃Or-C ₂H ₅

The embodiment that contains the monomer of diethanol strand comprises that obtainable product is as passing through Nippon Oil﹠amp on the market; The AE-350 (trade (brand) name n:6 to 8) that Fats Co., Ltd makes.

Any copolymerisable monomer with the hydrocarbon structure that contains four or more carbon atoms in its molecule all can be used for having the monomer of the hydrocarbon that contains four or more a plurality of carbon atoms, is used to form organic amine compound.Embodiment comprises (methyl) acrylate, acrylamide, allyl ether, vinethene, vinyl acetate and styrene and replaced styrene (R in its substituting group and the molecular formula (C-2) ⁴Those are similar), its each all have hydrocarbon.Especially, preferred embodiment comprises (methyl) acrylate with hydrocarbon.

Hydrocarbon can have any structure, as saturated, undersaturated linearity, branch or annular structure.Hydrocarbon preferably have 4 or more a plurality of carbon atom, preferably have 4 to 30 carbon atoms, more preferably have a linear hydrocarbons of 6 to 22 carbon atoms.Among the present invention, have and contain 4 or the preferred embodiment of the monomer of the hydrocarbon of the more a plurality of carbon atoms alkyl ether that comprises by (methyl) acrylic acid and have 4 or more a plurality of carbon atom, have the linear aliphatic alcohol that has 4 to 30 carbon atoms and more preferably have 6 to 22 carbon atoms to form.

Can use to have amino any copolymerisable monomer, as long as it has amino and can be by copolymerization.Embodiment comprises (methyl) acrylate, acrylamide, allyl ether, vinethene, vinyl acetate and styrene and replaced styrene (R in its substituting group and the molecular formula (C-2) ⁴Those are similar), its each all have amino.Its particularly preferred embodiment comprises (methyl) acrylate and acrylamide, its each all have amino.Embodiment further comprises the compound with loop configuration, and its specific embodiment comprises the propylene morpholine.Specific embodiment with amino monomer comprises dimethyl amine acetate (methyl) acrylate, dimethyl amine propyl group acrylate, DMAA, propylene morpholine, N-isopropylacrylamide and diethyl acrylamide.

According to the present invention, the monomer that uses in the organic amine compound in preparation, promptly have four ammonium salt groups monomer, have glycol chain monomer, have the monomer of the hydrocarbon that contains four or more a plurality of carbon atoms and have amino monomer and can use separately or can two or morely be used in combination, be used to form copolymer.

The surface charge that is added in the electroless plating solution used in this invention is improved dosage and preferably is adjusted, so that the concentration of the surface charge improver in the electroless plating groove is set at 1 * 10 ^-6To 1 * 10 ^-1In the scope of mol/l, more preferably be arranged on 5 * 10 ^-4To 2 * 10 ^-2In the scope of mol/l.

The concentration of surface charge improver should be adjusted as follows in solution, if this is because this concentration is low excessively, then can not be enough to obtain to control the function of electroplating film growth, thereby making on the thickness direction metal membrane to grow suppress effect tends to be lowered, if and because this excessive concentration, the absorption of agent in plating catalyst that then can improve so that the deposition of electroplating velocity or plated metal tends to reduce, and either way is not preferred thus.

Among the present invention, it further comprises the surface charge improver is added in the electroplating bath simultaneously can to carry out generally well-known electroless plating.

Though waiting by the temperature of the concentration of slaine in the electroplating bath or metal ion, the time span that enters into electroplating bath, electroplating bath, the thickness of the metal film that obtains controls, but, consider conductivity, it is preferably 0.5 μ m or more, is more preferably 3 μ m or more.

The immersion time span that enters into electroplating bath preferably about 1 minute to about 3 hours scope, more preferably at about 1 minute to about 1 hour scope.In conventional method, the immersion time that exceeds in electroplating bath or the increase of electroplating bath concentration of metal ions have additionally promoted the growth of metal film on the required direction of graphic width, so that it is difficult to form required very fine metallic pattern.Compare, the method according to this invention, metal film is optionally growth on thickness direction, has the metal film of adequate thickness with acquisition, and does not limit relevant technology, and can form the very fine metallic pattern with adequate thickness easily.

Electroplate catalytic inhibitor

The embodiment of the plating catalytic inhibitor that uses in electroless plating according to the present invention comprises metal ion, inorganic anion, in its molecule, have with plated metal have affinity group organic compound and in its molecule, have for plated metal the group of affinity and the organic compound of ion leaving group arranged.

The embodiment as the metal ion of electroplating catalytic inhibitor that uses in the present invention comprises the metal ion of selecting in any ion from Pb, Sn, As, Sb, Bi, Cr, Mo, Cd, In, Ti, W, Nb and Ti.The preferable alloy ion is suitably selected according to the metal species of using in electroless plating.When copper, silver or gold are used as plated metal, preferably use the metal ion of Pb, Sn, Sb or Bi.

Embodiment as the inorganic anion of electroplating catalytic inhibitor comprises iodine anion, bromine anions and sulphur anion and preferred especially iodine anion.

In its molecule, have the embodiment of organic compound that has a group of affinity with plated metal and comprise having the organic compound that with plated metal the functional group of affinity is arranged and be selected from the substituent of alkyl, aryl and cyclic group, go out as listed below.

The embodiment that has the group of affinity with plated metal comprises carboxyl, carbonyl, amino, sulfenyl and three carbonyls.The preferred embodiment of functional group depends on the kind of plated metal.When plated metal is good conductor such as copper, silver or when golden, preferred sulfenyl or three carbonyls.

Have sulfenyl or three carbonyls, be used as compound, disulphide, thioamides and Thiourea that the organic compound embodiment that contains sulphur that electroplates catalytic inhibitor comprises mercaptan compound, is convertible into mercaptan compound owing to enantiotropy.

The embodiment of mercaptan compound comprises thiocyanuric acid, 2-mercaptothiazoline, 2-mercaptopyridine, 2-mercaptobenzothiazole and 2-mercapto-tetrazole.Can comprise 2-thiobarbituricacid, 2-imidazoles alkene thioketones, four times carbazoles of 1-phenyl-2--5-thioketones and 2-deracil by the Kazakhstan that enantiotropy converts mercaptan compound to.

The embodiment of disulphide comprises bisbenzothiazole based bisulfide and tetramethyl thiuram disulphide.

The embodiment of thioamides comprises N-trihydroxy alcohol-butyl-2-[4-morpholinodithio base sulfenamide.The embodiment of Thiourea comprises thiocarbamide, methylthiourea and octyl group thiocarbamide.

Having in its molecule with plated metal has the organic compound as electroplating catalytic inhibitor of affinity further to have the atom substituent in its molecule.At this, the atom substituent comprises carboxyl, amino, amido, synergist group etc.

Have the embodiment that with plated metal the group of affinity is arranged and in its molecule, have the organic compound of ion leaving group and comprise 2-(3-carboxyl-phenyl)-5-mercapto-tetrazole, 2-(3-synergist-phenyl)-5-mercapto-tetrazole, thiosalycilic acid, 2-(3-(2-nitrilo acetic acid)-phenyl)-5-mercapto-tetrazole, sodium-2-mercaptobenzothiazole-5-sulfonate and sodium 2-(2-mercaptobenzothiazole base) ethane sulfonate.

The amount of the plating catalytic inhibitor that is used for the present invention in the electroless plating solution is added in adjustment to, is set at 1 * 10 so that electroplate the concentration of catalytic inhibitor in the electroless plating solution ^-10To 1 * 10 ^-5In the scope of mol/l, more preferably 1 * 10 ^-7To 5 * 10 ^-6In the scope of mol/l.

The concentration of electroplating catalytic inhibitor in solution should be adjusted as described above, if this is because this concentration is low excessively, the function of control electroplating film growth is just not enough, thereby the inhibition effect of metal membrane to grow is tended to reduce on Width, if and because this excessive concentration, then electroless plating itself will be limited, so that the deposition velocity of electroplating velocity or plated metal will be tended to reduce, and thus, not preferred both of these case.

Form with its solution is added the plating catalytic inhibitor in the electroless plating solution to.Electroplating catalytic inhibitor can tentatively be added in the electroless plating solution, so that concrete concentration to be provided, and perhaps disposable interpolation when process some cycles after the beginning electroless plating.

As being well known that, when not adding when electroplating catalytic inhibitor, starting stage electroplating velocity (the perhaps deposition velocity of plated metal) is all low usually and carry out along with plating afterwards and increase electroplating.Thus, comprise with the plating of not adding the valid density catalytic inhibitor begin and afterwards when the compound that adds as catalytic inhibitor during some cycles in the past after the beginning electroless plating be to comprise adding the technology pattern that has the electroless plating solution of the concentration in the above-mentioned scope in the electroless plating groove with formation to the back optimal process that concentration in the above range is provided with electroplating catalytic inhibitor.

Among the present invention, electroplate catalytic inhibitor to electroplating bath, carry out generally well-known electroless plating except it further comprises adding.

Can control by the concentration of slaine in the electroplating bath or metal ion, immersion time in electroplating bath or the temperature of electroplating bath though obtain the thickness of metal film,, consider conductivity, preferred 0.5 μ m or more, preferred 3 μ m or more.

The time span that in containing the electroplating bath of electroplating catalytic inhibitor, immerses preferably about 1 minute to about 3 hours scope, be more preferably at about 1 minute to about 1 hour scope.In conventional method, the immersion time span that prolongs in the electroplating bath or the increase meeting of electroplating bath concentration of metal ions further promote the not growth of metal film on the desired directions of graphic width, so that it is difficult to form required very fine metallic pattern.Yet, the method according to this invention, metal film is optionally growth on thickness direction, has the metal film of adequate thickness with acquisition, and does not limit related process, and can easily form the very fine metallic pattern with adequate thickness.

In the preference pattern of this metal film, satisfy relation (q-p)＜r, the graph layer live width of p presentation graphic form wherein, q represents that the live width of the metal film that forms by electroless plating and r represent the thickness of the metal film that forms by electroless plating.By especially being preferred for lead wire circuit etc., as described below at metal membrane to grow on the thickness direction and downtrod metal membrane to grow causes on Width this graphical metal film.

Below provide detailed description, be used for illustrating the technology that comprises the substrate that uses by use surface charge improver treatment substrate electroless plating first aspect present invention subsequently.

Technology (c-2): handle the polymeric layer bearing substrate with the groove that contains the surface charge improver

In this embodiment, in the solution that contains the surface charge improver, the material with the electroless plating catalyst (or precursor) that is deposited on the graphical graft polymer layer is immersed in back on polymeric layer (b) at deposition electroless plating catalyst or its precursor, it is formed on the substrate surface of acquisition, so that the surface charge improver optionally absorbs on a part of surface of the substrate with polymeric layer.

The surface charge improver and middle use similar of technology (c-1) that are used for this embodiment.Particularly, surface improver is dissolved in the water-miscible organic solvent such as ethanol that distillation crosses, and improves solution so that form surface charge.

In this case, the preferred amount of adding the surface charge improver solution in the groove to of adjusting is so that surface charge improver concentration is set at 1 * 10 in the groove ^-6To 1 * 10 ^-1Mol/l, more preferably 5 * 10 ^-4To 2 * 10 ^-2Mol/l.

During this is handled, the temperature of groove solution preferably about 5 to about 60 ℃ scope and the immersion time preferably in 20 seconds to 10 minutes scope.After immersing, carry out the water flushing or arbitrarily other technologies improve solution with the surface charge of removing unnecessary amount.

Handle (c-3): surface charge is improved treatment substrate carry out electroless plating

The technology (c-2) of handling the polymeric layer bearing substrate with the groove with surface charge improver is electroless plating afterwards.This technology is similar to technology (c-1), and uses similar treatment conditions as immersing the time span of time, except electroplating bath does not as used herein contain the surface charge improver.

And, below provide detailed description, be used for illustrating comprising that carrying out electroless plating adds technology in the electroless plating solution that can be used in second aspect present invention to electroplating catalytic inhibitor simultaneously.

Technology (c-3 '): the polymeric layer bearing substrate is contained 1 * 10 ^-10To 1 * 10 ^-4Mol/l electroplates the electroless plating of catalytic inhibitor

Among this embodiment, deposition electroless plating catalyst or its precursor are such technology after polymeric layer (b) is gone up, it does not add the plating catalytic inhibitor in the electroplating solution to, carries out electroless plating to having the material that electroless plating catalyst (or precursor) is deposited on the graphical graft polymer layer on the substrate surface that is formed at acquisition simultaneously; With carry out electroless plating, the concentration that remains on the plating catalytic inhibitor in the electroplating bath simultaneously is 1 * 10 ^-10To 1 * 10 ^-4In the scope of mol/l.This technology is similar to technology (c-1), and uses similar treatment conditions as immersing the time span of time, except controlling the concentration of electroplating catalytic inhibitor in the electroplating bath.

Similar to technology (c-1) is that the concentration of electroplating catalytic inhibitor in the electroless plating solution should be 1 * 10 ^-10To 1 * 10 ^-5In the scope of mol/l and be more preferably at 1 * 10 ^-7To 5 * 10 ^-6Mol/l.

Adding the plating catalytic inhibitor can be undertaken by catalytic inhibitor solution is added in the electroless plating solution.Catalytic inhibitor solution once adds in the time of can passing by some cycles after electroless plating begins, and perhaps adds with the rectangle time interval of scheduled volume, perhaps uses lasting and interpolations gradually such as pump.

Consider the accuracy that increases concentration control, electroless plating preferably include setting can monitor in real time the detector of electroplating catalytic inhibitor concentration in the electroplating solution, and in the future the signal of self-detector send to the catalytic inhibitor supply pump, with catalytic inhibitor concentration in the control electroplating solution to required grade, carry out electroless plating simultaneously.

Among this embodiment, this method is preferably included in beginning and keeps electroplating catalytic inhibitor concentration during electroless plating and be lower than preset range, perhaps when electroless plating begins, do not add electroplate catalytic inhibitor and after after beginning to electroplate, add the plating catalytic inhibitor so that concentration is controlled in the above-mentioned scope.

After forming metallic pattern by technology (c-1), and technology (c-2) and combination (c-3), technology (c-1 ') or technology (c-2 ') form after the metallic pattern, according to the adhering viewpoint of increase, preferably the metallic pattern that is obtained is carried out drying process.Drying process uses any means such as air dry, heated drying, step-down drying and air drying.In the middle of these, consider to prevent because the polymeric layer that causes of drying process becomes bad, drying process preferably at normal temperatures or near carry out.More specifically, preferred use material with polymeric layer and be kept at the air dry of the metal film under the normal temperature atmosphere, in drying under the normal temperature step-down and the air drying under the normal temperature.In order under situation about not heating, to remove the water that is included in the polymeric layer as much as possible, carry out these technologies and reach one or more hour, preferred 24 hours or more.Drying condition can consider that required adhesiveness suitably selects.Particularly, for example, drying means comprises following like this method, be used under about 25 ℃ temperature preserving that the material with polymeric layer and metal film reaches about 1 to 3 day, the method in about 1 to 3 week or about 1 to 3 months and be used for it is kept at that step-down was assigned about 1 to 3 day or the method in about 1 to 3 week.

Although wherein dried can be improved adhering not sufficiently clear of action,, suppose that sufficient drying can prevent to make the water of adhesiveness variation to gather in the conductive pattern material, and can reduce since the adhesiveness that causes of water along with the change of time is bad.

The SEM of the metal film partial cross section of thus obtained metallic pattern observation demonstrates existence and gently is spread in electroless plating catalyst and a large amount of fine granulars of plated metal and the extra play of deposition relatively large particle thereon in the surface grafting layer.Because the interface is the admixture of graft polymers and fine granular, even therefore when the unevenness at the substrate (organic principle) of preferred embodiment and the interface surface place between the inorganic substances (electroless plating catalyst and plated metal) be 500nm or still less, adhesiveness is also better.

The state of the metal that below will describe fine granular such as electroless plating catalyst in detail and in surface grafting polymerization thing layer, deposit by electroless deposition.Constitute electroless plating catalyst and/or the metallic particle by electroless deposition is dispersed in (graft polymer layer) the polymeric layer with the interface of high density between polymeric layer and metal film towards substrate.Apply the viewpoint of adhesiving effect according to metal film, preferred 25 volume % or more, more preferably 30 volume %, again be preferably 40 volume % or more, be preferably 50 volume % or more fine granulars exist and near interface.Fine granular with high density be present in the polymeric layer the zone preferred 0.05 μ m or more, more preferably 0.1 μ m or more, more preferred 0.2 μ m or more, most preferably extend in direction from the interface of polymeric layer and metal film in 0.3 μ m or the more scope towards substrate.

Electroplate

Metallic pattern formation method according to the present invention can have and is used for after above-mentioned technology by using the additional process of metal film as the plating of electrode.It can be based on easily preparing the new additional metal film with desired thickness with the good metallic pattern of the adhesiveness of substrate.Increase this process spread the thickness of graphical metal film to desirable value, it is beneficial to metallic pattern according to the present invention is applied to and comprises the patterned various application of lead-in wire thus.

Conventional known method can be used as the electroplating technology among the present invention.The metal that is used in this technology in electroplating comprises copper, chromium, lead, nickel, gold, silver, tin, zinc etc., and preferably copper, Jin Heyin, and according to more preferably copper of the viewpoint of conductivity.

The thickness of metal film that obtains after electroplating varies depending on the application, and can wait and control by adjusting the metal concentration, immersion time span, the current density that contain in the electroplating solution.According to the viewpoint of conductivity, the thickness that is used for the common metal film of electrical lead etc. is preferably 0.5 μ m or more, and 3 μ m or more more preferably.

Metallic pattern

Metallic pattern according to the present invention is characterised in that having the part is formed at metal film on the substrate, wherein substrate have 500nm or still less, be preferably 100nm or surperficial unevenness still less, and the adhesiveness between substrate and metal film is 0.2kN/m or more.That is, this metallic pattern is characterised in that and has smooth substrate surface and have good adhesion between substrate and metal film.

More specifically, metallic pattern according to the present invention is the metallic pattern that the part provides metal film, this metal film is by providing having with the polymer of the functional group that can be chemically bonded to the electroless plating catalyst of substrate or its precursors reaction, electroless plating catalyst or its precursor is applied on the figure and electroless plating afterwards obtains figure being formed of graphic form on the substrate with surface, wherein substrate has 500nm or each sold inside the country unevenness, be preferably 100nm or littler, and the adhesiveness between substrate and metal is 0.2kN/m or more.

This metallic pattern can form resemble process ground preparation with metallic pattern, except it comprises that also from have surperficial unevenness for selection in the middle of the described substrate of the metallic pattern method of formationing be that 500nm or substrate still less are as substrate.

The surface unevenness is by cutting substrate on perpendicular to the direction of substrate surface or the metallic pattern that forms thus and the value of observing its cross section determine by SEM.

More specifically, about as the surperficial unevenness (Rz) determined according to conventional known method, the difference between the mean value that is deep to most the 5th dark bottom on the mean value of the Z of peak-peak data and the particular surface should be 500nm or littler.

Adhesion value between substrate and metal film is determined by means, use (the trade (brand) name: ARALDITE of epoxy resin-matrix adhesive, make by Ciba-Geigy Corp.) with copper coin (thickness: 0.1mm) adhere to metallic pattern surface (width: 5mm), reach 4 hours 140 ℃ of following specimen, and carry out 90 degree according to the conventional known method of testing (IEC 60429-1 (1982)) of the graphic boards copper laminated plate that is used to go between afterwards and peel off test, perhaps directly remove metallic pattern periphery and after carry out carrying out 90 degree and peel off test according to the conventional known method of testing that is used for the copper laminated plate.

By common metallic pattern, can be by making the interface unevenness between substrate and the metal be 500nm or still less obtain at metallic pattern good aspect the high frequency characteristics.Yet the reduction of the substrate surface unevenness of common metal figure is accompanied by adhering reduction between substrate and the metal film usually.Therefore, the interface unevenness of common metal figure is generally 1000nm or more.

On the contrary, because substrate interface is in metal ingredient and the admixture that is combined to form that is bonded directly to the graft polymers of substrate by the combination metal film, therefore have little unevenness in the interface of metallic pattern according to the present invention between the plating catalyst (inorganic constituents) of electroplated metal layer and polymeric layer (organic layer), and have remarkable adhesiveness usually.

Metallic pattern according to the present invention is characterised in that the substrate that selection has 500nm or littler surperficial unevenness.The surface unevenness is preferably 300nm or littler, is preferably 100nm or littler again, and especially is preferably 50nm or littler.The lower limit of surface unevenness is restriction especially not; Yet, make and otherwise practical problem according to being convenient to, think that it is about 5nm.If metallic pattern according to the present invention is used for metal lead wire, then less surperficial unevenness preferably causes the metal that is used to go between and the reduction of the interface unevenness between the organic material, and causes electrical power consumed less between the high-frequency electrical transmission period thus.

If be expressed as the average unevenness of measuring by the method after the above-mentioned conventional known method (Rz) of 10 points, then preferred at 500nm or still less, be preferably 300nm or still less, more preferably or still less and select the substrate surface unevenness in particularly preferably in 50nm or scope still less at 100nm.

Can be used as substrate and used the higher substrate of surperficial unevenness even have the substrate such as the resin substrate of smooth surface inherently, also can be by providing intermediate layer control surface unevenness in preferable range.

And, metallic pattern according to the present invention be characterised in that the adhesiveness of tool between substrate and metal film be 0.2kN/m or more, be preferably 0.3kN/m or more.There is not special maximum constraints for adhering value; Yet its general scope of agreeing is about 0.2 to 2.0kN/m.In the common metal figure, in the adhesiveness between substrate and the metal film usually in about scope of 0.2 to 3.0kN/m.Consider the above-mentioned fact, be appreciated that metallic pattern according to the present invention has in fact enough adhesivenesses.

As mentioned above, metallic pattern according to the present invention is reduced to the unevenness of substrate surface in the interface at utmost, has kept the adhesiveness between substrate and the metal film simultaneously.

The very fine metallic pattern with adequate thickness that obtains is by simplifying the cost product manufactured, and it provides the substrate that is formed with the adhering metallic circuit that has improved between metal and the substrate on it.Thus, this substrate provides the lead-in wire substrate of effective conduction, and it can be used for the outer shell of various types of printed leads plates, TF T lead wire circuit, flexible switch, battery electrode, solar cell, transducer, integrated circuit and motor.

The printed leads plate

Printed leads plate of the present invention can be made by the conductive layer (lead-in wire) that forms metallic pattern according to the present invention on substrate.

About restriction especially of substrate, and embodiment comprises the lamination of lamination, glass cloth, glassine paper and epoxy resin of lamination, paper and epoxy resin of lamination, paper and the phenolic resin of known lamination such as glass cloth and epoxy resin.Embodiment further comprises bismaleimides-cyanate resin dipping substrate (BT substrate) and uses polyimide film as raw-material polyimide film substrate.

In order to form circuit layer, the conductive layer (metallic pattern) that is formed with graft polymers according to the present invention on substrate can be used in the combination with required any known method.The embodiment that makes the known method of lead plate comprises subtractive method and additive process, subtractive method comprises use copper-coating lamination (lamination of Copper Foil and insulated substrate) and removes the unnecessary part of Copper Foil by etching, and the necessary part that additive process is included in insulated substrate goes up by electroless plating and forms circuit.Also be used in the both sides of the copper coating lamination that all has Copper Foil on two surface on the both sides of insulated substrate and form circuit layer.

When lead plate (multi-sheet printed lead plate) was formed at circuit substrate on the insulation material layer by construction, insulation material layer was stacked and placed on the circuit substrate.If necessary, the bottom that then is used in the formation of graft polymer layer can be formed on the insulation material layer.

If necessary, then the surface of circuit layer can be by surface treatment, so that have the state that is suitable for adhering to.The aqueous alkali solution by clorox forms the acicular crystal of cupric oxide and reduces formed cupric oxide acicular crystal by the aqueous solution that acicular crystal is immersed in dimethyamine borane the embodiment that is used for the surface-treated technology on the circuit layer surface as being included in including, but not limited to known method.

The lamination of circuit substrate and insulation material layer can be by comprising the circuit substrate that setting and insulation material layer or another circuit substrate that forms are relative and heating and/or pressurize with the method formation with its lamination on insulation material layer.This laminated process can use hydraulic pressurization or any other technology such as vacuum pressed or vacuum stacked.Especially, vacuum pressed and vacuum lamination are preferably used, this be since during lamination its can prevent in lamination entrained air and can provide with internal circuit be embedded into the high-performance in the stacked layer.

Insulation material layer can form by following any method, embodiment comprises such method, this method comprises that the varnish with insualtion resin composition is coated on the supporter, and dry varnish is to form supported dielectric film and it is stacked on the circuit board to form insulation material layer.When being coated to varnish on the circuit board, can use any general coating method, as cross bar coating, spin coating and silk screen printing.When being coated to varnish on the supporter, can suitably use comma coater, cross bar coater, contact coater, circle roller coat glassware etc. according to the thickness of insulation material layer.In all cases, can use coating to wait any applied thickness, any drying condition afterwards, preferably vapor away 80 weight % or more varnish solvent by drying simultaneously.The embodiment that varnish is applied to its supporter comprises plastic film such as PET film and metal forming.Separable and removal supporter after cured varnish.In this case, discharge plastic film etc. and be preferably used as supporter.Be used for the second circuit layer serially and need do not peel off as the metal forming of substrate such as Copper Foil.The insualtion resin composition layer of institute's supports insulative film is relative with the circuit layer of circuit board, and uses overlapping method or device for exerting to be stacked with circuit board.If necessary, then preferably by hot curing insualtion resin composition layer.

Second conductive pattern (second circuit) is formed on the insulation material layer, to make the multilayer lead plate.This optimal process uses the conductive layer that is formed with according to graft polymers of the present invention.In this case, be used for before forming the grafting figure, to carry out in the technology in insulation material layer formation hole.Any method such as laser means or blasting method all can be used for forming through hole.

Can be by making electric conducting material adhere to it or be formed at conductive material layer on the figure simultaneously and be formed in the through hole by electroless plating,

Under the certain situation, the inner surface of through hole preferably this electroplate with the technology of giving conductivity before as required by alligatoring a little.The solution embodiment that is used for alligatoring comprises the fluorine/chromium/sulfuric acid roughening solution or the fluoboric acid roughening solution of the roughening solution of oxidation such as chromium/sulfuric acid roughening solution, alkaline permanganate roughening solution, sodium.For example, surface coarsening is handled and to be comprised substrate immersed in the aqueous solution of diethylidene glycol monomethyl butyl ester and NaOH and reach 1 minute, is heated 70 ℃ and as expansion solutions; Substrate is immersed in the aqueous solution of KMnO and NaOH and reach 2 minutes, be heated 80 ℃ and as roughening solution; At room temperature substrate is immersed in the inferior tin (SnCl of neutral solution such as dichloro subsequently ₂) the water-based hypochlorite solutions in reach 5 minutes with the neutralization.Be deposition plating catalyst (palladium) after the roughening process, it can be undertaken by substrate being immersed in the palladium chloro plating catalytic solution.Afterwards substrate is immersed in the electroless plating solution, being that the electroless plating (conductor layer) of 0.3 to 1.5 μ m is deposited on the grafting figure (if with forming through hole before this technology also on the inner surface of through hole) with thickness.If necessary, further electroplate, to obtain desired thickness.Any conventional known electroless plating solution all can be used in the electroless plating, and not restriction especially.Any known conventional crimen publicum technology also all can be used on not restriction especially in the plating.In these electroplating technologies, it is preferred the use that copper is electroplated.Manufacturing process provides second conductive pattern and according to metallic pattern formation method of the present invention, can form the very fine metallic circuit figure with adequate thickness.Thus, can form by the present invention and have the circuit that high-quality and shape can variation.

Subsequently, can make and have three layers or more multi-layered multilayer lead plate.In this case, another kind of second insulation material layer can be formed on second conductive pattern, and can repeat same process so that the lead plate of the multilayer with three layers of trace layer to be provided, and if necessary afterwards, form lead plate in the same manner with more wires layer.

The method feature that the conductive layer that use forms by metallic pattern formation method of the present invention is made the printed leads plate is to guarantee easily insulation characterisitic when forming circuit.In the false add method of routine, the deposition of the electroless plating catalyst of the electroless plating of copper or copper is carried out on the whole surface of insulated substrate, so that metal can easily keep and cause the reduction of insulation between the lead-in wire on the lead plate of acquisition.On the contrary, according to formation method of the present invention, the deposition of the electroless plating of copper or the electroless plating catalyst of copper does not apply (adhesion) to the whole surface of insulated substrate, and only apply (adhesion) to the necessary figure of lead-in wire, so that wherein the electroless plating of copper or catalyst are retained on the part except figure and the problems referred to above that will become insulated part can not take place.Thus, the method for making according to lead plate of the present invention can form the high-density circuit (lead-in wire) that has good adherence, enough conductivity and good insulation characteristic with substrate.

Thin-film transistor

Thin-film transistor among the present invention (TFT) forms by following technology, and this technology comprises by pattern forming method formation conductive layer of the present invention (as grid) and form gate insulating film, semiconductor film and source-drain electrode afterwards on grid.

The gate electrode of metal level among the TFT (conductive layer) is made of metal film, and it forms on the patterned graft polymers that is formed on the glass substrate by electro-plating method.Conductive layer is preferably formed by the copper metal, and its sheet resistor is preferably about 0.1D/ square.Gate insulation SiN _xFilm is formed on the gate electrode by CVD.As the a-Si film of channel layer, as the n of contact layer ⁺Type a-Si film, Al source electrode, drain electrode, pixel ITO electrode and insulation protection SiN _xFilm is further formed thereon.

TFT device with the grid that forms by method of the present invention can have reverse cross structure (bottom gate configuration), and grid perhaps according to the present invention can be used for forming the TFT with cross structure (top grid structure).This conductive layer that forms with required figure according to the present invention not only can be used for forming TFT, and can be used for forming any other nonlinear device such as both-end diode.

The grid or the metal lead wire that obtain by aforesaid metallic pattern formation method of the present invention can be used to flat-panel monitor such as LCD (LCD), Field Emission Display (FED), electrophoretic display device (EPD) (EPD), plasma scope (PDP), Electrochromic Display (ECD) or electroluminescent display (ELD), so that easily form electrode or the lead-in wire that has good adhesion and required accuracy with substrate, with for all situations, the present invention uses conductive layer to work effectively, to realize the reducing TFT size or to improve the TFT performance or the purpose of reduction LCD lead resistance.

When the wet film that is formed for forming electrode or lead-in wire at needs is handled and replaced dry film process and when needing to amplify display area, TFT lead wire circuit of the present invention is very useful.The active array display unit that combines TFT lead wire circuit of the present invention not only can be used for flat-panel monitor, can also be used for the plate type image sensing device, and is preferred for various types of LCD.

Embodiment

Under w, describe reference example in detail the present invention, still should be appreciated that to the invention is not restricted to these embodiment.

Embodiment relevant and comparative example embodiment 1-1 to 1-4 for preparing for substrate with utilizing the surface charge improver.

Following synthetic with following general formula is applied to as (KAPTON  on the surface of raw-material pi film by the coating cross bar that uses bar No.18, make by DuPont-Toray), and 80 ℃ down dry 2 minutes so that the intermediate layer with 6 μ m thickness is provided.

Obtain thus to have after the raw material in intermediate layer, reach precuring in 10 minutes by high-pressure mercury-vapor lamp (trade (brand) name: UVL-400P is made by the Riko Kagaku Sangyo) rayed of using 400W, so that prepare the substrate A that in embodiment 1-1, uses.

As by being 15nm according to above-mentioned conventional known method surface measurements and the Rz by using the determined raw material of NANOPICS 1000 (trade (brand) name is by Seiko InstrumentsInc. manufacturing), polyimide film 40 μ m * 40 mu m ranges in.Be formed at the surface of the substrate A on the polyimide film when also measured in the same manner when having the intermediate layer, Rz is 10nm, and the surperficial unevenness of the substrate A that expression is used in an embodiment is in preferable range of the present invention.

Intermediate layer coating solution

The copolymer of allyl methyl acrylate/methacrylate (copolymerization volume molar ratio: 80/20, divide equal molecule weight: 100000) 2g

The improved bisphenol a diacrylate 4g of vinyl oxide

1-hydroxy-cyclohexyl phenyl ketone 1.6g

1-methoxyl group-2-propyl alcohol 16g

The preparation figure forms material

Precuring substrate A is immersed in and contains acrylic acid (10 quality) and sodium metaperiodate (NaIO ₄, 0.01 quality) the aqueous solution in, and the light that it is exposed under the argon atmospher is reached 30 minutes by the high-pressure mercury-vapor lamp that uses above-mentioned 400W.After rayed, wash the film that is obtained fully with ion exchange water, but comprise the cambial figure formation of the figure materials A that optics becomes the polymer of bad functional group to provide to have.

The formation of grafting figure

It is by with 20mJ/cm that the figure that obtained forms material ²Energy emission have the blue beam laser (beam diameter: 1 μ m) become image exposure, of 400nm wavelength so that grafting graphic material 1-A is provided.

Rz as the patterned area of the grafting graphic material 1-A that has the grafting layer in the mode similar to the polyimide film raw material on substrate A is 15nm, and the surperficial unevenness of the grafting graphic material 1-A of expression embodiment 1-1 is in preferable range of the present invention.

The formation of metallic pattern

Grafting graphic material 1-A is immersed in reaches 1 hour in 1 quality % palladium nitrate (making) aqueous solution and clean with distilled water afterwards by Wako PureChemical Industries.Subsequently, the electroless plating that grafting iconography 1-A is had following general formula reaches 20 minutes, so that metallic pattern A1-1 to A1-4 is provided.

The composition of electroless plating groove

OPC copper H T1 (by Okuno Chemical Industries CO., Ltd. makes)

6mL

OPC copper H T2 (by Okuno Chemical Industries CO., Ltd. makes)

1.2mL

OPC copper H T3 (by Okuno Chemical Industries CO., Ltd. makes)

10mL

Surface charge changes agent (compound shown in the table 1) amount: describe in the table 1

Water 83mL

	Metallic pattern	The surface charge improver	Addition
	Metallic pattern	The surface charge improver	Addition	Embodiment 1-1	Metallic pattern A 1-1	Trimethyl-cetyl ammonium halide	5ppm
Embodiment 1-2	Metallic pattern A 1-2	Connection-base-methyl-ammonium-triflate	25ppm	Embodiment 1-1	Metallic pattern A 1-1	Trimethyl-cetyl ammonium halide	5ppm
Embodiment 1-2	Metallic pattern A 1-2	Connection-base-methyl-ammonium-triflate	25ppm	Embodiment 1-3	Metallic pattern A 1-3	Compound P 1	5ppm
Embodiment 1-4	Metallic pattern A 1-4	Compound P 1	20ppm	Embodiment 1-3	Metallic pattern A 1-3	Compound P 1	5ppm
Embodiment 1-4	Metallic pattern A 1-4	Compound P 1	20ppm	Comparative example 1-1	Metallic pattern A 1-5	Do not have	Do not have

Table 1

Comparative example 1-1

Metallic pattern A 1-5 prepares in the mode identical with embodiment 1-1, is not added in the electroless plating groove that uses in embodiment 1-1 to 1-4 except the surface charge improver.

Embodiment 1-5 to 1-8

With the cross bar of #6 acrylic acid is applied on the surface of the substrate A for preparing in the mode similar and is coated with surperficial lamination the PET film with 25 μ m thickness is arranged to embodiment 1-1.

And, after the chromium deposition mask graph of the figure of the figure with 5 μ m line lengths and 25 μ m gap widths and 10 μ m line lengths and 20 μ m gap widths is set up thereon, substrate A is exposed to UV light (400W high-pressure mercury-vapor lamp: UVL-400P according to above-mentioned situation, by Piko Kagaku Sangyo Co., make exposure period: 30 seconds).After rayed, remove mask and stacked film and water flushing substrate so that the polyacrylic grafting graphic material 1-B that has with the graphic form grafting is provided.

The Rz of the patterned area of the grafting graphic material 1-B that determines as the mode similar to the polyimide film raw material is 14nm.

Form metallic pattern

Grafting graphic material 1-B is immersed in and reaches 1 hour in 0.1 quality % palladium nitrate (being made by the Wako PureChemical Industries) aqueous solution and clean with distilled water afterwards.Subsequently, further grafting iconography 1-B is immersed in 0.2M NaBH ₄The aqueous solution in reach 20 minutes be immersed in the electroless plating groove with the identical synthetic that uses among the embodiment 1-1 to 1-4 so that be applied to its palladium, so that metallic pattern B1-1 to B1-4 is provided.

Comparative example 2

Metallic pattern B1-5 prepares in the identical mode of embodiment 1-5, is added to the electroless plating groove that is used for embodiment 1-5 to 1-8 except the surface charge improver.

Embodiment 1-9 to 1-12

Preparation grafting figure

The coating solution that will have following synthetic with the cross bar of #18 is applied on the surface of the substrate A for preparing in the mode similar to embodiment 1-1.The thickness of thus obtained film is 0.8 μ m.

The synthetic of coating solution

Hydrophilic polymer (below its preparation method is shown) 0.25g

Water 5g

Acetonitrile 3g

The preparation method who is used for hydrophilic polymer

18g polyacrylic acid (mean molecule quantity: 25000) be dissolved among the 300GDMAc; 0.41g hydroquinones, 19.4g2-methacryloyl base oxethyl isocyanates and 0.25g dibutyrin two laurate are added into it; With make this mixture 65 ℃ down reaction reach 4 hours.Thus obtained polymer has the acidic value of 7.02meq/g.Afterwards, the aqueous solution of carboxyl and 1N NaOH neutralization.This is added to the vinylacetic acid fiber and polymer is precipitating after the flushing fully, and has obtained hydrophilic polymer.

And, after the chromium deposition mask graph of the figure of the figure with 5 μ m line lengths and 25 μ m gap widths and 10 μ m line lengths and 20 μ m gap widths is set up thereon, reach 1 minute by using the 400W high-pressure mercury-vapor lamp that thus obtained film is carried out graph exposure.The film that water flushing is afterwards obtained is so that provide grafting graphic material 1-C, and wherein Bao Guang part becomes hydrophilic.

The Rz of the patterned area of the grafting graphic material 1-C that determines as the mode similar to the polyimide base film raw material is 15nm.

Form metallic pattern

Being immersed in the grafting graphic material 1-C that will be obtained is immersed in and reaches 1 hour in 0.1 quality % silver nitrate (being made by the Wako Pure Chemical Industrie s) aqueous solution and clean with distilled water afterwards.Subsequently, with embodiment 1-1 to 1-4 in it is carried out electroless plating in the identical electroless plating groove and reaches 20 minutes so that metallic pattern C1-1 to C1-4 is provided.

Comparative example 1-3

Prepare metallic pattern C1-5 in the mode identical, be not added in the electroless plating groove that in embodiment 1-9 to 1-12, uses except the surface charge improver with embodiment 1-9.

Embodiment 1-13 to 1-16

In having the electroplating bath of following synthetic, further the metallic pattern for preparing in embodiment 1-9 to 1-12 is electroplated and reached 15 minutes, so that metallic pattern D1-1 to D1-4 is provided.

The composition of electroplating bath

Copper sulphate 38g

Sulfuric acid 95g

Hydrochloric acid 1mL

Brightener (trade (brand) name: COPPER GLEAM PCM, make by Meltex Inc.) 3mL

Water 500g

Embodiment 1-17 to 1-20

The preparation figure forms material

With to embodiment 1-1 in the substrate A for preparing of similar mode be immersed in t-butylacrylic acid salting liquid (30 quality %, solvent, propyleneglycoles monomethyl ester (MFG)) in, and under argon atmospher, reaches 30 minutes by using the 400W high-pressure mercury-vapor lamp that it is exposed to light.

After rayed, the film that is obtained is washed fully with propyleneglycoles monomethyl ester (MFG), so that poly--t-butylacrylate-grafting figure-formation material 1-E is provided.

The preparation of grafting graphic material

Solution with following synthetic is applied to metal (fine granular) film pattern and forms on the material 1-E.Obtained poly--t-butylacrylate film is 0.5 μ m.

triphenylsulfonium triflate 0.05g

Methyl ethyl ketone (MEK) 1g

And, after chromium deposition mask graph with figure of the figure of 5 μ m line lengths and 25 μ m gap widths and 10 μ m line lengths and 20 μ m gap widths is set up thereon, reach 1 minute by using the 400W high-pressure mercury-vapor lamp that thus obtained film is carried out graph exposure, and under 90 ℃, its heating is reached 2 minutes afterwards.Wash the film that is obtained by methyl ethyl ketone (MEK) afterwards, so that grafting graphic material 1-E is provided, wherein functional group is converted into absorbing group in the exposure area.

Rz as the patterned area of the grafting graphic material 1E that determines in the mode identical with the polyimide film raw material is 15nm.

The preparation of metallic pattern

Thus obtained grafting graphic material 1-E is immersed in the dispersion liquid that contains carrying positive charge Ag fine granular for preparing by the following method and reaches 1 hour and use distilled water flushing afterwards.Subsequently, in the electroless plating groove identical, it is carried out electroless plating so that metallic pattern E1-1 to E1-4 is provided with embodiment 1-1 or 1-4.

The preparation method of carrying positive charge Ag fine granular

2 (1 of 3g; 1-trimethyl ammonium capryl ammonium acetate) disulphide is added to 50ml and contains in the ethanolic solution of silver perchlorate (5ml); further dropwise be added into it with the borohydride sodium solution (0.4M) of 30ml; simultaneously effectively stir this solution, thereby the dispersion liquid of the silver-colored fine granular that is coated with quaternary amino is provided so that make ion be lowered.

Comparative example 1-4

Prepare metallic pattern E 1-5 in the mode identical, be not added in the electroless plating groove that in embodiment 1-117 to 1-20, uses except the surface charge improver with embodiment 1-17.

Embodiment 1-21 to 1-24

To all carrying out electroless plating Ni to each of the similar metallic pattern that in embodiment 1-17 to 1-20, forms, and gold-plated to its immersion that approaches afterwards, so that metallic pattern F1-1 to F1-4 is provided.

Electroless nickel plating

Under the situation in mechanical agitation under 85 ℃ metallic pattern is being immersed in (trade (brand) name: ICP NICORON USD in the electroless plating Ni-P electroplating solution, by OKUNOCHEMICAL INDUSTRIES CO., LTD. make) reach 10 minutes, with Ni-P film (P content 6.8%) by electroplating deposition 0.4 μ m.

The thin gold that immerses is electroplated

Also use and immerse golden electroplating solution (trade (brand) name: OKUNO CHEMICALINDUSTRIES CO., LTD. manufacturing), wherein, the immersion metallic pattern reaches 10 minutes and does not stir under 90 ℃, to deposit the gold of about 0.05 μ m.Can further use the autocatalysis type electroless gold plating solution (trade (brand) name: 509RS of no cyano group, by KANTOCHEMICAL CO., INC makes), wherein under 60 ℃ and 7.2pH, under mild stirring situation, immersing to deposit 0.5 μ m gold and to obtain metallic pattern.

Assessment

The measurement of the thin live width of metallic pattern

The thin line width of each metallic pattern that obtains in embodiment 1-1 to 1-24 and comparative example 1-1 to 1-4 is by using optical microscope measuring (trade (brand) name: OPTIPHOTO-2 makes by Nikon Corp.).The result who measures is summarised in the following table 2.

Determine the thickness of metal film

Each metallic pattern that obtains in embodiment 1-1 to 1-24 and comparative example 1-1 to 1-4 all cuts by the use slicing machine on perpendicular to the direction of substrate surface, and the thickness of the metal film that forms is definite by the cross section that SEM obtains by observation.Measurement result is three points of each sample place average thickness value.Measurement result is summarized in the following table 2.

Interface unevenness between assessment electrodeposited coating/plating catalyst layer and the graft polymer layer

Each metallic pattern that in embodiment 1-1 to 1-24 and comparative example 1-1 to 1-4, obtains all on the direction vertical with substrate by using the slicing machine cutting, the surperficial unevenness between electrodeposited coating and plating catalyst layer (inorganic constituents) and graft polymer layer (organic principle) is definite by the cross section that SEM obtains by observation.According to obtaining surperficial unevenness from the peak averaging value of peak value to the five peak values with from the difference of each the sample 1 μ m between the little value mean value of minimum value to the five little values.Measurement result is summarised in the following table 2.

The assessment adherence

Copper coin (thickness: 0.1mm) be adhered to by on each the metallic pattern surface that obtains among embodiment 1-1 to 1-24 and the comparative example 1-1 to 1-4 by epoxy resin-matrix adhesive (trade (brand) name: ARAL DITE, make) by Ciba-Geigy Corp..And under 140 ℃, be dried and reach 4 hours.Afterwards, the copper that is used for down the printed leads plate according to the 90 degree conventional known method of testing of covering lamination is carried out 90 degree and is adhered to test.Measurement result is summarised in the following table 2.

Metal

Expose portion has 5 μ m thickness

It is thick to have 10 μ m

Substrate interface is not

Adhesiveness (kN/

	Belong to figure	Metallic pattern live width (μ m)	Thickness of metal film (μ m)	Aspect ratio	Metallic pattern live width in the exposure area of 10 μ m thickness (μ m)	The unevenness of face	(kN/ m)
	Belong to figure	Metallic pattern live width (μ m)	Thickness of metal film (μ m)	Aspect ratio		The unevenness of face	(kN/ m)	Embodiment 1	A1- 1	6.0	5.8	0.96	11.4	100 μ m or still less	0.32
Embodiment 2	A1- 2	5.8	5.6		12.6	100 μ m or still less	0.30	Embodiment 1	A1- 1	6.0	5.8	0.96	11.4	100 μ m or still less	0.32
Embodiment 2	A1- 2	5.8	5.6		12.6	100 μ m or still less	0.30	Embodiment 3	A1- 3	5.7	5.9	1.04	12.4	100 μ m or still less	0.32
Embodiment 4	A1- 4	5.4	5.6	1.04	12.3	100 μ m or still less	0.31	Embodiment 3	A1- 3	5.7	5.9	1.04	12.4	100 μ m or still less	0.32
Embodiment 4	A1- 4	5.4	5.6	1.04	12.3	100 μ m or still less	0.31	Comparative example 1-1	A1- 5	16.1	5.6	0.35	22.2	100 μ m or still less	0.25
Embodiment 5	B1- 1	5.4	5.5	1.02	12.2	100 μ m or still less	0.28	Comparative example 1-1	A1- 5	16.1	5.6	0.35	22.2	100 μ m or still less	0.25
Embodiment 5	B1- 1	5.4	5.5	1.02	12.2	100 μ m or still less	0.28	Embodiment 6	B1- 2	5.4	5.8	1.08	12.7	100 μ m or still less	0.28
Embodiment 7	B1- 3	5.2	5.9	1.13	11.2	100 μ m or still less	0.29	Embodiment 6	B1- 2	5.4	5.8	1.08	12.7	100 μ m or still less	0.28
Embodiment 7	B1- 3	5.2	5.9	1.13	11.2	100 μ m or still less	0.29	Embodiment 8	B1- 4	5.1	5.9	1.16	12.4	100 μ m or still less	0.32
Comparative example 1-2	B1- 5	10.3	5.8	0.56	17.7	100 μ m or still less	0.28	Embodiment 8	B1- 4	5.1	5.9	1.16	12.4	100 μ m or still less	0.32
Comparative example 1-2	B1- 5	10.3	5.8	0.56	17.7	100 μ m or still less	0.28	Embodiment 9	C1- 1	5.5	5.9	1.08	11.4	100 μ m or still less	0.29
Embodiment 10	C1- 2	5.1	5.9	1.14	12.9	100 μ m or still less	0.28	Embodiment 9	C1- 1	5.5	5.9	1.08	11.4	100 μ m or still less	0.29
Embodiment 10	C1- 2	5.1	5.9	1.14	12.9	100 μ m or still less	0.28	Embodiment 11	C1- 3	5.2	5.8	1.12	12.8	100 μ m or still less	0.31
Embodiment 12	C1- 4	5.1	5.7	1.12	11.3	100 μ m or still less	0.31	Embodiment 11	C1- 3	5.2	5.8	1.12	12.8	100 μ m or still less	0.31
Embodiment 12	C1- 4	5.1	5.7	1.12	11.3	100 μ m or still less	0.31	Comparative example 1-3	C1- 5	11.9	5.7	0.48	22.6	100 μ m or still less	0.29
Embodiment 13	D1- 1	9.5	9.5	1	15.0	100 μ m or still less	0.30	Comparative example 1-3	C1- 5	11.9	5.7	0.48	22.6	100 μ m or still less	0.29

Embodiment 14	D1- 2	8.7	9.6	1.1	16.9	100 μ m or still less	0.31
Embodiment 14	D1- 2	8.7	9.6	1.1	16.9	100 μ m or still less	0.31	Embodiment 15	D1- 3	8.9	9.8	1.1	16.8	100 μ m or still less	0.32
Embodiment 16	D1- 4	9.0	9.5	1.05	15.3	100 μ m or still less	0.31	Embodiment 15	D1- 3	8.9	9.8	1.1	16.8	100 μ m or still less	0.32
Embodiment 16	D1- 4	9.0	9.5	1.05	15.3	100 μ m or still less	0.31	Comparative example 1-4	D1- 5	15.7	10.4	1.66	26.5	100 μ m or still less	0.32
Embodiment 17	E1- 1	5.4	5.6	1.03	11.5	100 μ m or still less	0.30	Comparative example 1-4	D1- 5	15.7	10.4	1.66	26.5	100 μ m or still less	0.32
Embodiment 17	E1- 1	5.4	5.6	1.03	11.5	100 μ m or still less	0.30	Embodiment 18	E1- 2	5.9	5.6	0.96	11.4	100 μ m or still less	0.28
Embodiment 19	E1- 3	5.8	5.7	0.68	13.0	100 μ m or still less	0.30	Embodiment 18	E1- 2	5.9	5.6	0.96	11.4	100 μ m or still less	0.28
Embodiment 19	E1- 3	5.8	5.7	0.68	13.0	100 μ m or still less	0.30	Embodiment 20	E1- 4	5.5	5.7	1.05	12.5	100 μ m or still less	0.32
Comparative example 1-5	E1- 5	11.2	5.8	0.52	20.5	100 μ m or still less	0.31	Embodiment 20	E1- 4	5.5	5.7	1.05	12.5	100 μ m or still less	0.32
Comparative example 1-5	E1- 5	11.2	5.8	0.52	20.5	100 μ m or still less	0.31	Embodiment 21	F1- 1	6.0	6.3	1.03	12.0	100 μ m or still less	0.32
Embodiment 22	F1- 2	6.5	6.2	0.96	12.0	100 μ m or still less	0.30	Embodiment 21	F1- 1	6.0	6.3	1.03	12.0	100 μ m or still less	0.32
Embodiment 22	F1- 2	6.5	6.2	0.96	12.0	100 μ m or still less	0.30	Embodiment 23	F1- 3	6.4	6.4	0.99	12.0	100 μ m or still less	0.32
Embodiment 24	F1- 4	6.1	6.4	1.04	13.1	100 μ m or still less	0.28	Embodiment 23	F1- 3	6.4	6.4	0.99	12.0	100 μ m or still less	0.32
Embodiment 24	F1- 4	6.1	6.4	1.04	13.1	100 μ m or still less	0.28	Comparative example 1-6	F1- 5	11.8	6.4	0.54	21.2	100 μ m or still less	0.29

Table 2

Embodiment 1-25

The preparation of grafting figure

Be applied on the surface of the substrate A for preparing in the mode similar with the cross bar acrylic acid of #6 and coating surface is stacked with the PET film that has behind the 25 μ m to embodiment 1-1.

And, after the chromium deposition mask graph of the figure of the figure with 5 μ m line lengths and 25 μ m gap widths and 10 μ m line lengths and 20 μ m gap widths is set up thereon, substrate A is exposed to UV light (400W high-pressure mercury-vapor lamp according to above-mentioned situation, trade (brand) name: UVL-400P, by Piko Kagaku Sangyo Co., make exposure period: 30 seconds).After rayed, remove mask and stacked film and water flushing substrate so that the polyacrylic grafting graphic material 1-G that has with the graphic form grafting is provided.Thus obtained grafting figure is immersed in the aqueous solution that contains 1% dyestuff, and by light microscope observation (measurement).Found by having the grafting figure that 10 μ m live widths and 10 μ m figure is at interval made again.

The formation of metallic pattern: thin copper is electroplated as main and is electroplated

Grafting graphic material 1-G is immersed in and reaches 1 hour in the palladium nitrate that contains 0.1 quality % (being made by the Wako Pure Chemical Industries) aqueous solution and clean with distilled water afterwards.Further grafting iconography 1-G is immersed in 0.2M NaBH ₄The aqueous solution in reach 20 minutes be lowered to zeroth order so that be applied to its palladium.Therefore, with graphic material be immersed in have with embodiment 1-1 to 1-4 in reach 20 minutes in the electroless plating groove of the identical synthetic that uses so that metallic pattern G is provided 1-1.Has 11 μ m line lengths, 10 μ m interval and 1 μ m thickness by S EM observation (measurement) to the grafting figure.

Surface potential is applied to part except the copper figure

Polymer P 1 synthetic with quaternary amido

(trade (brand) name: AE-350 is by Nippon Oil﹠amp for the lauroyl acrylate of 10 parts of weight, the polyethylene glycol acrylate of 10 parts of weight; Fats Co., Ltd. makes, and the ethylene glycol chain length: 6 to 8), the dimethyl ammino ethylacrylic acid ester of 40 parts of weight and the oxolane of 150 parts of weight are added in the container that is equipped with reflux condenser, thermometer and blender.Atomic group polymerization initiator (trade (brand) name: V-65, by WakoPure Chemical Industries, Ltd. makes) is added into it and carries out polymerization reaction under the backflow of oxolane and reaches 10 hours.Therefore, measure the Dimethylsulfate identical and add in the reaction system, and further backflow reaches 1 hour, is used to carry out quaterisation with dimethyl ammino ethylacrylic acid ester.After finishing this reaction, wash reaction solution with hexane, and it is precipitated so that Compound P 1 to be provided again.Note, also can by with Dimethylsulfate to start with material use monomer that identical Compound P 1 is provided by the manufacturing of quaternary ammoniated dimethyl ammino ethylacrylic acid ester.The Compound P 1 that obtains is dissolved in the mixed solvent of second alcohol and water (weight ratio is 20: 100), and the solution with the Compound P 1 by 5 quality % is assigned therein as solution A 2.

Aforesaid thin copper figure is immersed in and reaches 5 minutes in this solution, and dry afterwards.As the measurement result of using zeta potentiometer (by Otsuka Electronics Co., Ltd makes), the surface potential of copper visuals is+0.0mV, and the surface potential of the part except the copper figure is+30mV.

Form thick copper figure as electroplating for the second time

Substrate is by electroplating identical method and reached 30 minutes by electroless plating with thin, and obtaining the thick figure of 10 μ m, it has 13 live width and the interval of 7 μ m, and finds thus, electroplates on thickness direction selectivity and carries out.

Comparative example 1-5

Except do not carry out ammonium handle with embodiment 1-25 in identical mode carry out electroless plating and reach 35 minutes.Form the thick figure of 10 μ m; Yet, electroplate and also continue to proceed to compartment with the figure of degenerating fully.

Observation has the state of the fine granular that disperses in the polymer of metallic pattern

The zone of metal film with the metallic pattern C that obtains among the comfortable embodiment 1-3 is by being equipped with the diamond cutter (trade (brand) name: SUMIKNIFE of slicing machine (being made by Leica), make by Sumitono Electric Hardmetal Corp.) cut, with the cleaning cross section of preparation plating.Observe the result of thus obtained sample be with SEM, the dispersity of fine granular can be found in the polymer adjacent with metal film.Fig. 1 is the SEM photo in the cross section of the metallic pattern C of acquisition in embodiment 3.Among Fig. 1, the inhomogeneous part of 10 expression electrodeposited coatings (catalyst) and graft polymers bed boundary, 11 expression electrodeposited coatings, 12 expression electroless platings and 13 expression organic/inorganic mixed layers.

Photo according to Fig. 1 can determine, seems that the electroless plating catalyst that is made of the metal by means of at least a type of electroless deposition and fine granular are present in the polymeric layer with metal film near interface place to high-density.Near dark base section (substrate) at polymeric layer locates to observe very small amount of fine granular.

Use software PHOTOSHOP  (making) that the SEM photo is carried out image processing afterwards by Adobe SystemsIncorporated.In image processing, demonstrating a part of image that polymeric layer (the organic/inorganic mixed layer among Fig. 1) in the comfortable 6 μ m wide regions and the interface depth between the metal film (electroless plating) be the zone of 0.1 μ m, 0.2 μ m or 0.3 μ m is cut, and convert thereof into black and white (image processing), wherein the image of fine granular part is converted into whitely, and polymer moieties is converted into black (black and white switch condition: boundary threshold is 100).The image that obtains is shown in Figure 2.

In image histogram, can calculate the white part ratio at each degree of depth place in Fig. 2, and it is defined as the content of the fine granular in the graft polymer layer below being present in the electrodeposited coating bottom.As a result, be that the content of fine granular in the zone of 0.3 μ m, 0.2 μ m and 0.1 μ m is calculated as 53 volume % respectively in the degree of depth, 60 volume % and 60 volume %, and can determine, fine granular with high density be present in the metal film interface near.

The relevant utilization of the plating catalytic inhibitor of embodiment and comparative example

Comparative example 2-1

The formation of metallic pattern

Just Ei is immersed in to graphic material 1-A and reaches 1 hour in 0.1 quality % palladium nitrate (being made by the WakoPure Chemical Industries) aqueous solution and clean with distilled water afterwards.Subsequently, the electroless plating that grafting graphic material 1-A is had following general formula reaches 20 minutes, so that metallic pattern A2-1 is provided.

The composition of electroless plating groove

OPC copper H T1 (by Okuno Chemical Industries CO., Ltd. makes)

6mL

OPC copper H T2 (by Okuno Chemical Industries CO., Ltd. makes)

1.2mL

OPC copper H T3 (by Okuno Chemical Industries CO., Ltd. makes)

10mL

Water 83mL

Embodiment 2-1 to 2-4

With comparative example 2-1 in identical mode prepare metallic pattern A2-2 to A2-4, except further being added as the plating catalytic inhibitor of listing in the following table 3 so that become concentration separately shown in table 3.

	Metallic pattern	Electroplate catalytic inhibitor	Concentration
	Metallic pattern	Electroplate catalytic inhibitor	Concentration	Embodiment 2-1	Metallic pattern A2-2	PbC12	2.5×10 ^-6mol/L
Embodiment 2-2	Metallic pattern A2-3	KI	8×10 ^-5mol/L	Embodiment 2-1	Metallic pattern A2-2	PbC12	2.5×10 ^-6mol/L
Embodiment 2-2	Metallic pattern A2-3	KI	8×10 ^-5mol/L	Embodiment 2-3	Metallic pattern A2-4	5-sulfydryl-2-phenyltetrazole	1×10 ^-6mol/L

Embodiment 2-4

Metallic pattern A2-5

2-(2-mercaptobenzothiazole base) ethane sulfonate

2.5×10 ^-6mol/L

Table 3

Comparative example 2-2 to 2-5

Metallic pattern A2-6 to A2-9 prepares in the mode identical with embodiment 2-1, except the plating catalytic inhibitor of listing in the following table 4 is further added to become the concentration separately shown in the table 4.

	Metallic pattern	Electroplate catalytic inhibitor	Concentration
	Metallic pattern	Electroplate catalytic inhibitor	Concentration	Comparative example 2-2	Metallic pattern A2-6	PbC12	2.5×10 ^-4mol/L
Embodiment 2-3	Metallic pattern A2-7	KI	4×10 ^-3mol/L	Comparative example 2-2	Metallic pattern A2-6	PbC12	2.5×10 ^-4mol/L
Embodiment 2-3	Metallic pattern A2-7	KI	4×10 ^-3mol/L	Embodiment 2-4	Metallic pattern A2-8	5-sulfydryl-2-phenyltetrazole	2×10 ^-4mol/L
Embodiment 2-5	Metallic pattern A2-9	2-(2-mercaptobenzothiazole base) ethane sulfonate	5×10 ^-4mol/L	Embodiment 2-4	Metallic pattern A2-8	5-sulfydryl-2-phenyltetrazole	2×10 ^-4mol/L

Table 4

Comparative example 2-6

Preparation grafting graphic material

With the cross bar of #6 acrylic acid is applied on the surface of the substrate A for preparing in the mode similar and is coated with surperficial lamination the PET film with 25 μ m thickness is arranged to embodiment 2-1.

And, after the chromium deposition mask graph of the figure of the figure with 5 μ m line lengths and 25 μ m gap widths and 10 μ m line lengths and 20 μ m gap widths is set up thereon, substrate A is exposed to UV light (400W high-pressure mercury-vapor lamp: UVL-400P according to above-mentioned situation, by Piko Kagaku Sangyo Co., make exposure period: 30 seconds).After rayed, remove mask and stacked film and water flushing substrate so that the polyacrylic grafting graphic material 2-B that has with the graphic form grafting is provided.

The Rz of the patterned area of the grafting graphic material 2-B that determines as the mode similar to the polyimide film raw material is 14nm.

Form metallic pattern

Grafting graphic material 2-B is immersed in and reaches 1 hour in 0.1 quality % palladium nitrate (being made by the WakoPureChemical Industries) aqueous solution and clean with distilled water afterwards.Subsequently, further grafting iconography 1-B is immersed in 0.2M NaBH ₄The aqueous solution in reach 20 minutes be reduced to zeroth order so that be applied to its palladium.Subsequently, with graphic material be immersed in have with comparative example 2-1 in reach 20 minutes in the electroless plating groove of the identical synthetic that uses so that metallic pattern B2-1 is provided.

Embodiment 2-5 to 2-8

Metallic pattern B 2-2 to B2-5 with comparative example 2-6 in identical mode prepare, except, except in embodiment 2-1 to 2-4, use and in table 3, list further be added into it so that have respectively and the identical concentration shown in the table 3.

Comparative example 2-7

The coating solution similar to the coating solution that contains hydrophilic polymer that uses among the embodiment 1-9 to 1-12 is coated on the substrate A, this substrate A with to embodiment 2-1 in similar mode prepare.Afterwards substrate is carried out graph exposure, and with embodiment 1-9 to 1-12 in identical mode wash so that grafting graphic material 2-C is provided, wherein expose portion becomes hydrophilic.Rz as the patterned area of the grafting graphic material 2-C that determines in the mode similar to polyimide film is 15nm.

Form metallic pattern

The grafting graphic material 2-C that is obtained is immersed in and reaches 1 hour in 0.1 quality % silver nitrate (being made by the Wako Pure Chemical Industries) aqueous solution and clean with distilled water afterwards.Subsequently, in the electroless plating groove identical, it is carried out electroless plating and reach 20 minutes, so that metallic pattern C2-2 to C2-5 is provided with the electroless plating groove that uses among the comparative example 2-1.

Comparative example 2-8

Further to with comparative example 2-7 in the metallic pattern that forms of identical mode electroplate and reach 15 minutes so that metallic pattern D2-1 is provided.Use therein electroplating bath have with embodiment 1-13 to 1-16 in the identical synthetic that uses.

Embodiment 2-13 to 2-16

Further to embodiment 2-9 to 2-12 in the metallic pattern that forms of same way as electroplate and reach 15 minutes so that metallic pattern D2-2 to D2-5 is provided.

Comparative example 2-9

The preparation figure forms material

With to embodiment 2-1 in the substrate A for preparing of similar mode be immersed in t-butylacrylic acid salting liquid (30 quality %, solvent, propyleneglycoles monomethyl ester (MFG)) in, and under argon atmospher, reaches 30 minutes by using the 400W high-pressure mercury-vapor lamp that it is exposed to light.

After rayed, the film that is obtained is washed fully with propyleneglycoles monomethyl ester (MFG), so that poly--t-butylacrylate-grafting figure-formation material 2-E is provided.

The preparation of grafting graphic material

triphenylsulfonium triflate 0.05g

Methyl ethyl ketone (MEK) 1g

And, after chromium deposition mask graph with figure of the figure of 5 μ m line lengths and 25 μ m gap widths and 10 μ m line lengths and 20 μ m gap widths is set up thereon, reach 1 minute by using the 400W high-pressure mercury-vapor lamp that thus obtained film is carried out graph exposure, and under 90 ℃, its heating is reached 2 minutes afterwards.Wash the film that is obtained by methyl ethyl ketone (MEK) afterwards, so that grafting graphic material 2-E is provided, wherein functional group is converted into absorbing group in the exposure area.

Rz as the patterned area of the grafting graphic material 2E that determines in the mode identical with the polyimide film raw material is 15nm.

The preparation of metallic pattern

Thus obtained grafting graphic material 2-E is immersed in the dispersion liquid that contains carrying positive charge Ag fine granular for preparing by the following method and reaches 1 hour and use distilled water flushing afterwards.Subsequently, in the electroless plating groove identical, carry out electroless plating and reach 20 minutes, so that metallic pattern E2-1 is provided with comparative example 2-1.

The preparation method of carrying positive charge Ag fine granular

Comparative example 2-17 to 2-20

Prepare metallic pattern E2-2 to E2-5 in the mode identical, except plating catalytic inhibitor that use and that list in embodiment 2-1 to 2-4 further is added into it so that have the similar concentration shown in the chart 3 respectively in table 3 with comparative example 2-9.

Comparative example 2-10

To further carrying out electroless plating Ni, and afterwards it is approached and immerse gold and electroplate, so that metallic pattern F is provided 2-1 to the similar metallic pattern that in conventional embodiment 2-9, forms.Electroless plating Ni and thin immerse gold electroplate with embodiment 1-21 to 1-24 in carry out under the same terms of using.

Embodiment 2-21 to 2-24

To carrying out electroless plating Ni to each of the similar metallic pattern that in embodiment 2-10, forms, and afterwards with comparative example 2-10 in identical mode it is approached immerse gold and electroplate so that metallic pattern F2-2 to F2-5 is provided.

Assessment

The thin live width of each in the metallic pattern that in embodiment 2-1 to 2-24 and comparative example 2-1 to 2-10, obtains with measure for the identical mode of embodiment 1-1 to 1-24.Measurement result is summarised in following table 5 and 6.

	Metallic pattern	Expose portion with 5 μ m thickness			Has metallic pattern live width (μ m) in the exposure area of 10 μ m thickness	The unevenness of substrate interface	Adhesiveness (kN/ m)
		Expose portion with 5 μ m thickness						Metallic pattern live width (μ m)	Thickness of metal film (μ m)	Aspect ratio
		Comparative example 2-1	A2-1	12.6				Metallic pattern live width (μ m)	Thickness of metal film (μ m)	Aspect ratio	5.6	0.44	21.4	100 μ m or still less	0.25
Embodiment 2-1	A2-2	Comparative example 2-1	A2-1	12.6	5.5	5.7		12.0	100 μ m or still less	0.31	5.6	0.44	21.4	100 μ m or still less	0.25
Embodiment 2-1	A2-2	Embodiment 2-2	A2-3	6.0	5.5	5.7		12.0	100 μ m or still less	0.31	5.8	0.98	12.2	100 μ m or still less	0.29
Embodiment 2-3	A2-4	Embodiment 2-2	A2-3	6.0	5.2	5.6	1.07	11.8	100 μ m or still less	0.32	5.8	0.98	12.2	100 μ m or still less	0.29
Embodiment 2-3	A2-4	Embodiment	A2-5	6.0	5.2	5.6	1.07	11.8	100 μ m or still less	0.32	5.7	0.95	11.6	100μ	0.31

2-4						M or still less
2-4						M or still less		Comparative example 2-2	A2-6	5.8	2.7	0.46	11.0	100 μ m or still less	0.30
Comparative example 2-3	A2-7	5.1	2.1	0.40	11.0	100 μ m or still less	0.31	Comparative example 2-2	A2-6	5.8	2.7	0.46	11.0	100 μ m or still less	0.30
Comparative example 2-3	A2-7	5.1	2.1	0.40	11.0	100 μ m or still less	0.31	Comparative example 2-4	A2-8	6.6	5.9	0.50	11.7	100 μ m or still less	0.28
Comparative example 2-5	A2-9	6.3	5.9	0.42	11.6	100 μ m or still less	0.32	Comparative example 2-4	A2-8	6.6	5.9	0.50	11.7	100 μ m or still less	0.28
Comparative example 2-5	A2-9	6.3	5.9	0.42	11.6	100 μ m or still less	0.32	Comparative example 2-6	B2-1	16.2	5.8	0.34	16.5	100 μ m or still less	0.31
Embodiment 2-5	B2-2	5.9	5.9	0.94	11.5	100 μ m or still less	0.32	Comparative example 2-6	B2-1	16.2	5.8	0.34	16.5	100 μ m or still less	0.31
Embodiment 2-5	B2-2	5.9	5.9	0.94	11.5	100 μ m or still less	0.32	Embodiment 2-6	B2-3	5.8	5.9	1.02	12.6	100 μ m or still less	0.32
Embodiment 2-7	B2-4	5.0	5.8	1.12	11.1	100 μ m or still less	0.31	Embodiment 2-6	B2-3	5.8	5.9	1.02	12.6	100 μ m or still less	0.32
Embodiment 2-7	B2-4	5.0	5.8	1.12	11.1	100 μ m or still less	0.31	Embodiment 2-8	B2-5	5.9	5.7	0.97	12.4	100 μ m or still less	0.31
Comparative example 2-7	C2-1	16.9	5.7	0.33	22.3	100 μ m or still less	0.29	Embodiment 2-8	B2-5	5.9	5.7	0.97	12.4	100 μ m or still less	0.31
Comparative example 2-7	C2-1	16.9	5.7	0.33	22.3	100 μ m or still less	0.29	Embodiment 2-9	C2-2	5.6	9.5	1.04	12.1	100 μ m or still less	0.32
Embodiment 2-10	C2-3	5.4	9.6	1.06	11.5	100 μ m or still less	0.32	Embodiment 2-9	C2-2	5.6	9.5	1.04	12.1	100 μ m or still less	0.32
Embodiment 2-10	C2-3	5.4	9.6	1.06	11.5	100 μ m or still less	0.32	Embodiment	C2-4	5.8	9.8	1.02	12.7	100μ	0.29

2-11						M or still less
2-11						M or still less		Embodiment 2-12	C2-5	5.8	9.5	0.98	12.9	100 μ m or still less	0.28

Table 5

	Metallic pattern	Expose portion with 5 μ m thickness			Has metallic pattern live width (μ m) in the exposure area of 10 μ m thickness	The unevenness of substrate interface	Adhesiveness (kN/ m)
		Expose portion with 5 μ m thickness						Metallic pattern live width (μ m)	Thickness of metal film (μ m)	Aspect ratio
		Comparative example 2-8	D2-1	13.5				Metallic pattern live width (μ m)	Thickness of metal film (μ m)	Aspect ratio	11.0	0.81	19.2	100 μ m or still less	0.31
Embodiment 2-13	D2-2	Comparative example 2-8	D2-1	13.5	9.0	9.4	1.05	16.1	100 μ m or still less	0.28	11.0	0.81	19.2	100 μ m or still less	0.31
Embodiment 2-13	D2-2	Embodiment 2-14	D2-3	9.4	9.0	9.4	1.05	16.1	100 μ m or still less	0.28	9.6	1.02	16.8	100 μ m or still less	0.31
Embodiment 2-15	D2-4	Embodiment 2-14	D2-3	9.4	9.1	9.1	0.99	15.5	100 μ m or still less	0.28	9.6	1.02	16.8	100 μ m or still less	0.31
Embodiment 2-15	D2-4	Embodiment 2-16	D2-5	9.5	9.1	9.1	0.99	15.5	100 μ m or still less	0.28	9.3	0.98	16.6	100 μ m or still less	0.32
Comparative example 2-9	E2-1	Embodiment 2-16	D2-5	9.5	12.6	6.0	0.48	22.1	100 μ m or still less	0.29	9.3	0.98	16.6	100 μ m or still less	0.32
Comparative example 2-9	E2-1	Embodiment 2-17	E2-2	5.8	12.6	6.0	0.48	22.1	100 μ m or still less	0.29	5.8	1.00	11.8	100 μ m or still less	0.29
Embodiment 2-18	E2-3	Embodiment 2-17	E2-2	5.8	5.1	5.9	1.17	12.9	100 μ m or still less	0.32	5.8	1.00	11.8	100 μ m or still less	0.29
Embodiment 2-18	E2-3	Implement	E2-4	5.4	5.1	5.9	1.17	12.9	100 μ m or still less	0.32	5.9	1.09	12.8	100μ	0.29

Example 2-19						M or still less
Example 2-19						M or still less		Embodiment 2-20	E2-5	5.6	5.7	1.02	12.9	100 μ m or still less	0.30
Comparative example 2-10	F2-1	12.7	6.4	0.50	19.8	100 μ m or still less	0.28	Embodiment 2-20	E2-5	5.6	5.7	1.02	12.9	100 μ m or still less	0.30
Comparative example 2-10	F2-1	12.7	6.4	0.50	19.8	100 μ m or still less	0.28	Embodiment 2-21	F2-2	5.6	6.4	1.15	12.3	100 μ m or still less	0.28
Embodiment 2-22	F2-3	6.2	6.2	1.00	12.7	100 μ m or still less	0.30	Embodiment 2-21	F2-2	5.6	6.4	1.15	12.3	100 μ m or still less	0.28
Embodiment 2-22	F2-3	6.2	6.2	1.00	12.7	100 μ m or still less	0.30	Embodiment 2-23	F2-4	6.2	6.2	1.00	12.0	100 μ m or still less	0.30
Embodiment 2-24	F2-5	6.2	6.2	1.02	11.8	100 μ m or still less	0.28	Embodiment 2-23	F2-4	6.2	6.2	1.00	12.0	100 μ m or still less	0.30

Table 6

Table 3,5 result have shown that all metallic patterns that obtain in an embodiment according to the present invention have the fine lines that width is at most 10 μ m respectively, and this is difficult to obtain by routine techniques.This result also confirms and can control this fine linewidth by grafting pattern forming method and conditions of exposure.

Find that also all metallic patterns of Huo Deing all have the copper thickness that is enough to provide conductivity respectively in an embodiment according to the present invention.Can observe fine lines live width that less increases and the metallic pattern that has obtained to have the exposure figure fine linewidth of reproducing easily about the live width that exposes figure.Find that also the ratio that can obtain to have its thickness of metal film and its metal film live width is 1 or more metallic pattern, and this metallic pattern can easily obtain by conventional method.

Also have been found that, if added the plating catalytic inhibitor, then very high catalytic inhibitor concentration (with identical among the comparative example 2-2 to 2-5) has caused can not realizing advantageous effects of the present invention thus to the enough inhibition of plating and the obvious reduction of electroplating velocity in electroplating solution.

Verified in embodiment 1-9 to 1-12 and 2-13 to 2-16, the graphical metal film with desired thickness can obtain by further electroplating.

Also find, all metallic patterns that in according to the embodiment of the invention, obtain each all to have degree of irregularity be 100 μ m or membrane interface still less and this good surface flatness, and between substrate and metal film, also have good adhesion.

And all metal films that obtain in according to the embodiment of the invention and conducting film all are formed at has unevenness (Rz) for 500nm or substrate surface still less, and grafting layer or grafting figure are formed on the substrate.As a result, the unevenness Rz of grafting layer or grafting patterned surface is 500nm or still less; Forming all metal films of figure or metallic pattern by plating has preferably at the interface between electrodeposited coating (metal film) and plating catalyst layer and the graft polymer layer (organic material composition) in 500nm or the unevenness in the scope still less.On this point, mix the surface that plated metal or plating catalyst can be by not only entering into graft polymer layer, the inside that also enters into graft polymer layer.Because this mixing, the interface between electrodeposited coating (metal film) and plating Catalytic Layer (inorganic material composition) and graft polymer layer (organic material composition) has good surface flatness, and also has good adhesiveness between substrate and metal film.

By with reference to its whole content, the disclosure of Japanese patent application No.2005-323221 and 2005-40610 is incorporated this paper into.

At this, all documents, patent application and the technical standard of mentioning in this specification all incorporated this paper to some extent into, is designated as particularly and individually by reference as each independent document, patent application or technical standard and incorporates into.

Claims

1. metallic pattern formation method is characterized in that comprising:

(a) form the polymeric layer that contains polymer with graphic form on substrate, this polymer has with electroless plating catalyst or its precursors reaction and can direct chemical be bonded to functional group on the substrate;

(c) by the use electroless plating solution substrate with polymeric layer is carried out the metal film that electroless plating forms graphic form,

Wherein, before (c) forms metal film or during, use to comprise surface charge improver or 1 * 10 ^-10To 1 * 10 ^-4The solution-treated of the plating catalytic inhibitor of mmol/l has the substrate that polymeric layer is applied in electroless plating catalyst or its precursor.

2. metallic pattern formation method as claimed in claim 1 is characterized in that: electroless plating solution comprises the surface charge improver.

3. metallic pattern formation method as claimed in claim 1 is characterized in that the step of (c) formation metal film comprises:

(c-2) handle substrate with the groove that contains the surface charge improver with polymeric layer; With

(c-3) substrate with polymeric layer is carried out electroless plating, so that form the metal film of graphic form.

4. as claim 2 or 3 described metallic pattern formation methods, it is characterized in that: the surface charge improver is an organic compound, has (i) and substrate and have the group of affinity and (ii) ion leaving group in its molecule.

5. metallic pattern formation method as claimed in claim 1, it is characterized in that: electroless plating solution comprises 1 * 10 ^-10To 1 * 10 ^-4The plating catalytic inhibitor of mmol/l.

6. metallic pattern formation method as claimed in claim 1 is characterized in that (c) forms metal film and comprise:

(c-2 ') substrate with polymeric layer is carried out electroless plating, simultaneously the plating catalytic inhibitor is added in the electroless plating solution, make the concentration of electroplating catalytic inhibitor in the electroless plating solution remain on 1 * 10 ^-10To 1 * 10 ^-4In the scope of mmol/l, so that form the metal film of graphic form.

7. as claim 5 or 6 described metallic pattern formation methods, it is characterized in that: electroplating catalytic inhibitor is a metal ion species, and this metal is selected from the group that is made of Pb, Sn, As, Sb, Bi, Cr, Mo, Cd, In, Ti, W, Nb and Ti.

8. as claim 5 or 6 described metallic pattern formation methods, it is characterized in that: electroplating catalytic inhibitor is inorganic anion, and it is selected from the group that is made of iodine anion, bromine anions and sulphur anion.

9. as claim 5 or 6 described metallic pattern formation methods, it is characterized in that: electroplating catalytic inhibitor is organic compound, has the group that affinity is arranged with plated metal in its molecule.

10. metallic pattern formation method as claimed in claim 9 is characterized in that: electroplate catalytic inhibitor and further have the ion leaving group in its molecule.

11. as any described metallic pattern formation method in the claim 1 to 10, it is characterized in that: the electroless plating solution in electroless plating is selected from the group that is made of plating solution for electroless copper plating, electroless deposition of silver solution and electroless gold plating solution.

12., it is characterized in that: further be included in the step of electroplating after the electroless plating as any described metallic pattern formation method in the claim 1 to 11.

13., it is characterized in that as any described metallic pattern formation method in the claim 1 to 12:

It is 500nm or substrate still less that substrate has surperficial unevenness;

Adhesiveness between substrate and metal film is 0.2kN/m or more; With

At least in (1) to (3) one meets the following conditions:

(1) thickness of metal film is 3 μ m or more;

(q-p)＜and r, the figure live width of p presentation graphic form wherein, q represents that the live width of the metal film that forms by electroless plating and r represent the thickness of the metal film that forms by electroless plating;

(2) polymeric layer has the zone of wherein scattering fine granular, this fine granular comprises electroless plating catalyst particle and at least a by in the metallic particles of electroless deposition, volume content is 25% or more, and 0.05 μ m or more is being extended at this zone autohemagglutination compound layer and metal film interface on the direction of substrate; With

The ratio of metal film and metal film live width is 1 or more;

(3) thickness of metal film is 4 μ m or more;

Polymeric layer has the zone of wherein scattering fine granular, this fine granular comprises electroless plating catalyst particle and at least a by in the metallic particles of electroless deposition, volume content is 25% or more, and this zone is extended 0.05 μ m or more from the interface of polymeric layer and metal film in the direction towards substrate; With

The ratio of thickness of metal film and metal film live width is 1 or bigger.

14. metallic pattern formation method as claimed in claim 13 is characterized in that: substrate has 10nm or surperficial unevenness still less.