CN101266408A - Laminating body, grafting film forming method using the same and forming method for grafting pattern - Google Patents

Abstract

The invention supplies a laminating body, a grafting film forming method using the laminating body and a forming method of grafting pattern, specifically speaking, relating to a laminating body generating a graft polymer under high sensitivity, and a method using the laminating body to form the grafting film or the grafting pattern. The laminating body has a base material, a polymerization initiating layer, a graft polymer precursor layer orderly. The polymerization initiating layer is obtained through chemically bonding the compound with free radical polymerization initiating part and the part that can be chemically bonded on the base material directly. The graft polymer precursor layer contains a compound which can polymerize the unsaturated part by the free radical, and a compound which can generate free radical through heating or exposing, to fully expose the laminating body or expose in image shape, directly bonding the polymer which can polymerize the unsaturated part by the free radical on the polymerization initiating layer surface, to generate the graft polymer.

Description

Layered product and use its graft copolymer membrane formation method and the formation method of graft pattern

Technical field

The present invention relates to formation method, metal pattern formation method, printed wiring board, thin-layer transistor, device and the photomask of a kind of layered product, graft copolymer membrane formation method, graft pattern.

Background technology

In recent years, the technology that various functions are set on solid surface is prominent, particularly carry out finishing,, on industrial circle, conduct a research just widely because can change character such as wetting state, contaminative, cohesive, mantle friction, cell affinity by polymkeric substance to solid surface.

Wherein, known graft polymer in Direct Bonding on the solid surface carries out finishing: i) have the advantage that can form strong bond between solid surface and graft polymer, ii) by controlling the structure of graft polymer, the various materials high can be adsorbed, and then surperficial various function can be given the affinity of graft polymer.

Like this, when modifying solid surface with graft polymer, for example irradiates light on solid surface makes it generate spike, as basic point, the surface grafting polymerization method of polymerizable compound polymerization is employed (for example referring to Langmuir.2006.22.8571-8575) with this spike.

In this surface grafting polymerization method, there is such problem: the irradiates light in order to generate spike on solid surface, when using visible light laser etc. at the irradiation low light of exposure energy, can not effectively carry out chain polymerization, the finishing that can not expect.

Therefore, a kind of technology of promptly using low-energy exposure also can generate graft polymer effectively of expectation.

On the other hand, be accompanied by the miniaturization of electronic material, require a kind of method of the high-accuracy electrical harnesses that can form easily.

High-accuracy and high conductive fine distribution generally forms by vapor phase methods such as vacuum film formation methods, and this method is difficult to form thickness or membranous even metal film with large tracts of land, and urgent expectation can form the method for distribution with a high credibility, electrode etc.And then the problem that takes place during with gas phase legal system film metal film on large-area panel is: vacuum film formation apparatus that must be subsidiary huge and gas feeding apparatus etc. need huge equipment investment.Also produced such problem in addition: sputtering unit, CVD device equal vacuum film formation device need drive the multinomial electric power such as electric power of the electric power of vacuum pump, the electric power that carries out heated substrates, generation plasma, be accompanied by the gigantism of device, the consuming cost of this manufacturing installation is also strengthening.

And then, when forming metal wiring etc., using vacuum film formation apparatus after forming metal film on the substrate all surfaces at present, remove unnecessary portions by etching, form the electrical harnesses pattern, but the problem that also exists in this method is: the resolution of distribution is restricted, and metal material produces waste.In recent years, consider, require in manufacturing process, to reduce consuming cost that perhaps effectively utilize material resources, requiring more easily is the metal film pattern that forms the resolution of expectation from the angle of environment.

To this, the catalyst layer that pattern arrangement needs on substrate in advance in the electroless plating reaction has for example been proposed, only after the regioselectivity ground that catalyst layer exists forms the electroless plating technology (for example opening the 2000-147762 communique referring to the spy) of metal film or is forming metal oxide film (for example ZnO) on the substrate surface, metal oxide film is formed pattern, on the burning film figure that forms, optionally form the method (for example opening the 2001-85358 communique) of metal film pattern referring to the spy.These methods can form metal wiring with the pattern of expectation, when but the former forms metal film pattern with electroless plating on the substrate of surface smoothings such as glass substrate, substrate and by the adhesiveness of plated film very a little less than, have the problem in the practicality to exist, and then be difficult to increase the thickness of electroplating film.In addition, the latter makes on the substrate all surfaces in the operation that forms the Zinc oxide film patterning, need to use resin against corrosion etc., complex process, and because the resistance to chemical reagents of zinc paste is low, be difficult to the small adjustment of requirement rate of etch, on large-area substrates, be difficult to improve simultaneously the inner evenness of etching speed.

And, as its improving technology, supported catalyst agent material on light-sensitive surface has been proposed, form the catalyst layer of patterning down with ultraviolet exposure, only on this zone, form Zinc oxide film, form the method (for example opening the 2003-213436 communique) of metal pattern as basic point by electroless plating referring to the spy.According to this method, have the advantage that forms the high Zinc oxide film pattern of resolution, but must light-sensitive surface etc. special material, and need comprise 5 operations of the formation of 2 Catalytic Layer, complex process to the formation of metal film.

The applicant has proposed can directly form conductive pattern material of image and forming method thereof (for example opening the 2003-114525 communique referring to the spy) based on numerical data by controlling infrared laser etc. in view of the above.This conductive pattern material uses above-mentioned surface grafting polymerization method, generates graft polymer in the support desired region, generates the structure that has the absorption electrically conductive microparticle in the zone at it.According to this structure, can form conductive pattern (metal pattern) more easily corresponding to the high precision of numerical data.

And, in this technology, consider that from adsorbing electroconductive particle to high-density present situation is a kind of method that effectively and to high-density generates graft polymer on solid surface of requirement.

Summary of the invention

Problem of the present invention is to solve above-mentioned existing problem, realizes following purpose.

That is, first purpose of the present invention is to provide a kind of and can generates the layered product of graft polymer and use this layered product under high sensitive, forms the method for graft copolymer membrane or graft pattern with high sensitive.

Second purpose of the present invention is to provide a kind of formation method of using above-mentioned graft pattern, forms the metal pattern formation method with base material adaptation good metal pattern.

First purpose of the present invention be to provide the metal pattern that a kind of formation method that has by above-mentioned metal pattern forms printed wiring board, thin-layer transistor, photomask, have the device of this printed wiring board and have the device of this thin-layer transistor.

People of the present invention found that by following means and can address the above problem through research.

Promptly, layered product of the present invention is characterized in that having base material successively, polymerization trigger layer, graft polymer precursor layer, described polymerization trigger layer obtains by the compound that has free radical polymerization at chemical bonding on the above-mentioned base material and cause the position and can direct chemical be bonded to the position on this base material, and described graft polymer precursor layer contains compound with unsaturated position that can free radical polymerization and the compound that can produce free radical by heating or exposure.

In layered product of the present invention, the preferred polymeric trigger layer further contains the compound that can produce free radical by heating or exposure.

In addition; the compound that can produce free radical by heating or exposure in polymerization trigger layer among the present invention and the graft polymer precursor layer is preferably selected from more than one in halo oxysalt, trihalomethyl group triazines, acyl group oxime ester, united imidazole and two cyclopentadiene titanium compounds; wherein; be preferably selected from trihalomethyl group triazine, united imidazole and the halo oxysalt more than one, preferred especially halo oxysalt.

Grafting precursor layer of the present invention preferably contains 0.1 quality % is above, 20 quality % are following pass through heating or expose can produce the compound of free radical.

In addition, the polymerization trigger layer contains preferably that 0.1 quality % is above, 20 quality % are following passing through the compound that heating or exposure can produce free radical.

In the layered product of the present invention, especially the viewpoint of using from metal pattern is considered, the polymkeric substance with unsaturated position that can free radical polymerization preferably further has the position of adsorbing metal ions or slaine or the position of absorption chemical plating catalyst or its precursor.

In addition, in the layered product of the present invention, the graft polymer precursor layer contain multiple have can free radical polymerization unsaturated position also be one of preferred version.

Graft copolymer membrane formation method of the present invention is characterised in that with respect to layered product of the present invention, carry out the exposure of all surfaces at the wavelength of 360nm～700nm, the above-mentioned compound with unsaturated position of free redical polymerization of Direct Bonding on above-mentioned polymerization trigger layer surface makes it generate graft polymer.

Graft pattern formation method of the present invention is characterised in that with respect to layered product of the present invention, wavelength at 360nm～700nm carries out the exposure of image shape, the above-mentioned compound with unsaturated position of free redical polymerization of Direct Bonding on above-mentioned polymerization trigger layer surface makes it generate graft polymer.

First scheme of metal pattern formation method of the present invention is characterised in that, after having on the graft polymer that in graft pattern formation method of the present invention, generates adsorbing metal ions or slaine, reduce metal in this metallic ion or the slaine, make the operation of its precipitating metal particle.

And the alternative plan of metal pattern formation method of the present invention is characterised in that, have on the graft polymer that in graft pattern formation method of the present invention, generates absorption chemical plating catalyst or its precursor after, carry out electroless plating, form the operation of electroplating film.

And, in this form, preferably carry out electroless plating after, electroplate again.

Printed wiring board of the present invention has the metal pattern that forms by metal pattern formation method of the present invention.

Thin-layer transistor of the present invention has the metal pattern that forms by metal pattern formation method of the present invention.

And device of the present invention has printed wiring board of the present invention or thin-layer transistor.

And then photomask of the present invention is to use the photomask of the metal pattern that forms by metal pattern formation method of the present invention.

According to the present invention, can provide a kind of and under high sensitive, can generate the layered product of graft polymer and use this layered product, under high sensitive, form the method for graft copolymer membrane or graft pattern.

And, use graft pattern formation method of the present invention, the metal pattern formation method of the good metal pattern of a kind of formation and base material adaptation can be provided.

And then, printed wiring board, thin-layer transistor, photomask with the metal pattern that forms according to metal pattern formation method of the present invention can be provided, have the device of this printed wiring board and have the device of this thin-layer transistor.

Embodiment

＜layered product 〉

At first, layered product of the present invention is elaborated.

Layered product of the present invention has (A) base material, (B) chemical bonding on above-mentioned base material successively and has free radical polymerization and cause position and the polymerization trigger layer that can constitute with the compound at the position of this base material direct chemical bonding and (C) comprise compound with unsaturated position that can free radical polymerization and the graft polymer precursor layer that can produce the compound of free radical by heating or exposure.

Below, explanation constitutes (A) base material, (B) polymerization trigger layer of layered product of the present invention and (C) graft polymer precursor layer successively.

[(A) base material]

The base material that uses among the present invention is so long as have the function or the physical property of the purposes of being adapted to, and then have can form (B) polymerization trigger layer or (C) the graft polymer precursor layer keep roughly shape, be not particularly limited, as the material that constitutes base material, can be any in the composite material of organic material, inorganic material or organic material and inorganic material.

Concrete, as base material, can use organic materials such as PET, polypropylene, polyimide, epoxy resin, acryl resin, carbamate resins, silicone resin, or inorganic material such as glass, quartz, ITO.

In addition, when base material is glass substrate, for example can use silex glass substrate, alkali-free glass substrate, quartz glass substrate, form the substrate of ITO film etc. at glass baseplate surface.

Among the present invention, from can and constitute (B) polymerization trigger layer, have compound that the free radical polymerization that can direct chemical be bonded on the base material causes the position and form the chemical bond aspect easily and consider, preferably use the glass substrate that has functional groups such as hydroxyl on the surface in advance or, implemented the resin substrate of surface-treateds such as corona treatment, aura processing, plasma treatment generation hydroxyl, carboxyl etc.

In addition, the shape of base material is not particularly limited.When for example being plate-like substrate, its thickness can be selected according to application target, generally is about 10 μ m～10cm.

[(B) polymerization trigger layer]

(B) polymerization trigger layer chemical bonding on base material among the present invention has free radical polymerization initiation position and forms with the compound that the energy direct chemical is bonded to the position of base material.In addition, this polymerization trigger layer preferably by exposing, produces the polymerization trigger layer of free radical under the laser of 360nm～700nm wavelength.

In addition, the thickness of this polymerization trigger layer according to use have free radical polymerization cause the position and can direct chemical be bonded to the compound at the position on the base material different and different, the scope of 1nm～1 μ m preferably still.

The following describes (b-1) that constitute the polymerization trigger layer and have the compound (below abbreviate " base material bonding free love base polymerization initiator " as) that free radical polymerization causes the position and can direct chemical be bonded to the position on the base material.

[(b-1) base material bonding free love base polymerization initiator]

Base material bonding free love base polymerization initiator of the present invention so long as in the part of molecule, have by exposure can produce free radical position (free radical polymerization initiation position) and can with the position of base material direct chemical bonding (below the situation that is called the base material binding site is arranged), its form without limits, can be low molecular compound, also can be macromolecular compound.

Concrete, for example can enumerate (1) and have free radical polymerization initiation position at an end of molecule, another end has the low molecular compound of base material binding site, (2) end at molecule has free radical polymerization initiation position, another end has the homopolymer of base material binding site, and (3) have the multipolymer that free radical polymerization causes the monomer at position and has the monomer copolymerization acquisition of base material binding site.

Here, cause the position, for example can enumerate the position that can produce free radical by photodestruciton described later as the free radical polymerization in the base material bonding free love base polymerization initiator.

And, as the base material binding site in the base material bonding free love base polymerization initiator, except silane coupling agent, ring-type ether, isocyanate group, carboxyl etc. can be formed the functional group with base material direct chemical bonding by this site monomer, for example can enumerate the such crosslinking chemicals such as diisocyanate of hydroxyl be used in combination down the functional group that combines with base material (in other words, by with the crosslinking chemical combination can and the crosslinkable groups of base material bonding) etc.

Among the present invention as base material bonding free love base polymerization initiator, for example cause the position as free radical polymerization, the preferred use has the position (Y) that can produce free radical by photodestruciton, so have base material bonding position (Q) compound (below be called " photodestruciton compound (Q-Y).)。

Here, the position (following be called " free radical polymerization of photodestruciton type causes position (Y)) that can produce free radical by photodestruciton is the structure that comprises by the singly-bound of photodestruciton.

As this singly-bound by photodestruciton, the singly-bound of the cleavables such as cracking reaction of the cracking reaction of the α cracking that having of can enumerating utilized carbonyl, βLie Xie reaction, the reaction of light Fourier transform, phenacyl ester, thionyl imide cracking reaction, sulfonyl ester cracking reaction, N-hydroxyl sulfonyl ester cracking reaction, benzyl acid imide cracking reaction, active halogen compound.By these reactions, singly-bound that can cracking by light is disconnected.Singly-bound as this cleavable has C-C key, C-N key, C-O key, C-Cl key, N-O key and S-N key etc.

In addition, the photodestruciton type free radical polymerization that comprises by the singly-bound of this photodestruciton causes position (Y) owing to be the starting point of graft polymerization, so disconnect by the singly-bound of photodestruciton, has the function by this cracking reaction generation free radical.Like this, can enumerate and have the structure that comprises following group as having the structure that causes position (Y) by the singly-bound of photodestruciton and the photodestruciton type free radical polymerization that can produce free radical.

That is, aromatic series ketone group, phenacylate base, thionyl imide base, sulphonyl ester group, N-hydroxyl sulphonyl ester group, benzyl imide, trichloromethyl, benzyl chloride-based etc. are arranged.

Such photodestruciton type free radical polymerization causes position (Y) if by the exposure cracking, produce the words of free radical, exist under the situation of polymerizable compound around this free radical, this free radical can generate graft polymer as the function of graft polymerization reaction starting point.

Therefore, have the base material of the polymerization trigger layer that forms by photodestruciton compound (Q-Y), when generating graft polymer,, need to use the wavelength that can make polymerization cause position (Y) cracking to expose as the means that energy is provided.

In addition, as base material bonding position (Q), crosslinking chemicals such as diisocyanate such as reactive group that use connects with functional group (Z) reaction key that exists with substrate surface or hydroxyl, carboxyl, sulfydryl, isocyanate group, amino, epoxy radicals are also used, the functional group that can connect with the base material key, as this reactive group, concrete passenger train is lifted base material binding groups as follows.

Q; Base material binding groups-Si (OMe) ₃,-SiCl ₃,-NCO ,-CH ₂Cl

(Q) directly key even also can be by connecting base key even for photodestruciton type free radical polymerization initiation position (Y) and base material bonding position (base material bonding radical).The base that is connected that contains the atom that is selected from carbon, nitrogen, oxygen and the sulphur be can enumerate as this connection base, for example saturated hydrocarbyl, aromatic series base, ester group, amide group, uride base, ether, amino, sulfonyl amido etc. specifically can have been enumerated.And this connection base also can further have substituting group, can enumerate alkyl, alkoxy, halogen atom etc. as the substituting group that can introduce.And then polymerization initiation position (Y) and base material binding site (Q) may reside in the two ends of homopolymer, also can be present in the side chain of polymkeric substance respectively.Like this, when photodestruciton compound (Q-Y) is macromolecular compound (polymkeric substance), connecting the backbone structure that base contains polymkeric substance, is the group that connects between polymerization initiation position (Y) and the base material key compound (Q).

Have polymerization and cause the object lesson [enumerating compound T1～T10] of photodestruciton compound (Q-Y) at position (Y) and base material bonding position (Q) and cracking section and illustrate as followsly together, still the invention is not restricted to this.

Can use dissolving or dispersed light cracking compound (Q-Y) in suitable solvent such as toluene, hexane, acetone as the concrete grammar that makes photodestruciton compound (Q-Y) and substrate surface direct chemical bonding, the method of coating this solution or dispersion liquid on substrate surface, or in solution or dispersion liquid the method etc. of dipping base material.By this method, on substrate surface, obtain the polymerization trigger layer in conjunction with photodestruciton compound (Q-Y).

In addition, base material bonding position (Q) in the photodestruciton compound (Q-Y) be with crosslinking chemical and with in can connect with the base material key functional group the time, as above-mentioned solution or dispersion liquid, and then, can add general commercially available crosslinking chemical corresponding to the functional group at this base material bonding position (Q).

As the addition of crosslinking chemical, the total amount of the compound that uses during with respect to formation polymerization trigger layer, preferable range is 0.1～1000 mole of %.

As in the above-mentioned solution or the concentration of the photodestruciton compound (Q-Y) of dispersion liquid, be preferably 0.01 quality %～30 quality %, preferred especially 0.1 quality %～15 quality %.Liquid temperature during as contact is preferably 0 ℃～100 ℃.Be preferably 1 second duration of contact～50 hours, more preferably 10 seconds～10 hours.

And this method is not limited to photodestruciton compound (Q-Y), uses in the time of can key connects other base material bonding free love base polymerization initiators on substrate surface.

[(b-2) can produce the compound of free radical] by heating or exposing

Can further contain (b-2) different with (b-1) base material bonding free love base polymerization initiator can produce free radical by heating or exposure compound (following situation that is called " free-radical generating agent ") in the polymerization trigger layer among the present invention.

As (b-2) free-radical generating agent, can list the macromolecular compound (high molecular free radical generation agent) that hangs down the molecule free-radical generating agent or have the free-radical generating position.

As low molecular free-radical generating agent, for example can use triaizine compounds class, united imidazole and known free-radical generating agent such as two cyclopentadiene titanium compounds and thioxanthones such as halo oxysalt, acetophenones, benzophenone, Michler's keton, benzoylbenzoic acid ester, styrax class, α-acyl group oxime ester, tetra methylthiuram list sulfide, trihalomethyl group triazine.And, to work as free-radical generating agent by illumination because of sulfonium father-in-law salt that produces the agent use as light oxygen or iodonium salt etc. usually, the present invention also can use them.

Wherein, consider from the viewpoint of sensitized reaction efficient; be preferably selected from halo oxysalt, trihalomethyl group triazines, acyl group oxime ester, united imidazole and the thioxanthones compound more than one; wherein; be preferably selected from trihalomethyl group triazine, united imidazole and the halo oxysalt more than one, preferred especially halo oxysalt.

And, among the present invention as the halo oxysalt, can list sodium metaperiodate, potassium metaperiodate, periodic acid tetramethyl ammonium, hyperbromic acid sodium, hyperbromic acid potassium, sodium perchlorate, potassium perchlorate, sodium iodate, Potassiumiodate etc., wherein consider preferred sodium metaperiodate, potassium metaperiodate from high sensitive effect.

Produce agent as high molecular free radical, can use and open flat 9-77891 number [0012]～[0030] section or spy the spy and open the macromolecular compound that on side chain, has active carbonyl group put down in writing in [0020]～[0073] section for flat 10-45927 number etc.

(b-2) content of free-radical generating agent is not particularly limited, but can decide according to the base material bonding free love base polymerization initiator that forms the polymerization trigger layer or the purposes of layered product.

Generally, in the polymerization trigger layer, preferably contain the scope more than the 0.1 quality %, below the 20 quality %, more preferably more than the 0.1 quality %, below the 10 quality %.

For example, as described later, when using layered product of the present invention to form graft pattern, because in the regional remaining free-radical generating agent of the non-formation of the pattern of polymerization trigger layer, there is absorption in this non-formation zone, if preferred pattern then needs to increase the absorption of this free-radical generating agent.Being absorbed in below 1 in the concrete expectation polymerization trigger layer is preferably below 0.5.

In addition, absorption value of the present invention is that the absorption intensity of utilizing general absorptiometer to measure exposure wavelength is tried to achieve.

(b-2), add free-radical generating agent in solution that can when key on base material connects base material bonding free love base polymerization initiator, use or the dispersion liquid and use as the method that in the polymerization trigger layer, contains free-radical generating agent.Adjust the addition of this moment, the content of (b-2) free-radical generating agent in the polymerization trigger layer can be controlled at above-mentioned scope.

[(b-3) sensitive agent]

Polymerization trigger layer of the present invention except (b-1) base material bonding free love base polymerization initiator, preferably contains (b-3) sensitive agent in order further to improve susceptibility.

Sensitive agent is to become excited state by light, acts on free-radical generating position (for example energy shifts, electronics moves etc.), can promote the generation of free radical.

Sensitive agent as using in the present invention is not particularly limited, the exposure wavelength that can select to use when being adapted at generating graft polymer from the known sensitive agent (sensitive agent of preferred 360nm～700nm).

Concrete; for example can list the known polynuclear aromatic same clan (pyrene for example; perylene; three penylenes); oxa anthracenes (fluorescein for example; eosin; erythrosine; rhodamine B; Rose Bengal); cyanine glycoside (indoles carbocyanine glycosides for example; sulfo-carbocyanine glycosides; oxo carbocyanine glycosides); merocyanine class (merocyanine for example; the carbonyl merocyanine); thiazide (thionine for example; methylene blue; toluidine blue); acridine (acridine orange for example; the chloro flavine; acridine yellow); anthraquinone class (for example anthraquinone); spiny dogfish alkanes (for example squalane); acridine ketone (acridone for example; the chloro acridone; N-methylacridine ketone; N-butyl acridone; N-butyl-chloro acridone etc.); Coumarins (3-(2-benzo furoyl base)-7-diethyl amino coumarin for example; 3-(2-benzo furoyl base)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl base)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two positive propoxy cumarins) 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furoyl base)-7-diethyl amino coumarin; 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin; 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarins etc. can list the spy in addition and open flat 5-19475 communique; Te Kaiping 7-271028 communique; the spy opens 2002-363206 number; the spy opens 2002-363207 number; the spy opens 2002-363208 number; the spy opens and waits coumarin compound of putting down in writing in each communique etc. for 2002-363209 number).

Combination as free-radical generating position (polymerization initiator) and sensitive agent, the electronics mobile model that for example can list record in [0013]～[0020] that the spy opens the 2001-305734 communique causes system, and [(1) electronics provides type initiating agent and responsive pigment, (2) electronics reception type initiating agent and responsive pigment, (3) electronics provide type initiating agent, responsive pigment and electronics reception type initiating agent (ternary cause system)] etc. combination.

More specifically, preferred triazine is polymerization initiator and the combination that has the sensitive agent of very big absorption under 360nm～700nm wavelength.

As other sensitive agents, can list sensitive agent, sensitive agent, have the sensitive agent of fluorescer etc., explanation successively below with acid core with alkalescence nuclear.

Have the sensitive agent of alkalescence nuclear so long as in molecule, have the pigment of alkalescence nuclear, be not particularly limited, can suit to select and pigment that the exposure wavelength (for example visible light, visible laser etc.) that uses when generating graft polymer adapts.

Among the present invention, for the laser explosure corresponding to 360～700nm wavelength, the very big absorbing wavelength of preferred sensitive agent is below the 700nm, more preferably below the 500nm, below the preferred especially 450nm.

As above-mentioned pigment with alkalescence nuclear, for example can list cyanine is that pigment, half cyanine are that pigment, styryl pigment are, the chain cyanine is a pigment etc.Above-mentioned various pigment also can contain the pigment of dimorphism, three types, polymer-type etc.And preferred cyanine is that pigment, half cyanine are pigment, styrene base system pigment in them, and more preferably cyanine is that pigment, half cyanine are pigment.

Pigment with above-mentioned alkalescence nuclear is a cyanine when being pigment, and preferably 1 of methylene radix is half cyanine when being pigment, and the methylene radix is preferably below 5.And when being styrene base system pigment, when having the aniline parent nucleus, preferred methene chain number is below 4.

Alkalescence nuclear is meant " the The Theory of the Photographic Process " the 4th edition that James for example compiles, the MacMillan Press Ltd., London and Bastingstoke, 1977, the 8th chapter " sensitizing coloring matter and desensitization pigment " definition, United States Patent (USP) No. 1567719, No. 1575869, No. 1804634, No. 1837862, No. 4002480, No. 4925777, spy the material of record such as open flat 3-167546 number.

As above-mentioned alkalescence nuclear, for example preferred benzoxazole nuclear, benzothiazole nucleus and indolenine nuclear (イ Application De レ ニ Application) etc.

And, alkalescence nuclear that above-mentioned alkalescence nuclear optimization aromatic group replaces or the alkalescence nuclear that contracts ring more than 3 rings.

Here, alkalescence nuclear contract number of rings for example benzoxazole nuclear be that 2 ， naphthoxazoles nuclear is 3.And benzoxazole nuclear replaces with phenyl, and the number of rings that contracts also still is 2.Contract more than 3 rings alkalescence nuclear of ring so long as the polycycle of the ring that contracts more than 3 rings contracts ring-like heterocycle alkalescence nuclear, can, preferred 3 ring types ring-like heterocycle and the 4 ring types ring-like heterocycle that contracts that contracts.

As the 3 ring types ring-like heterocycle that contracts, for example can list naphthalene [2,3-d] oxazole, naphthalene [1,2-d] oxazole, naphthalene [2,1-d] oxazole, naphthalene [2,3-d] thiazole, naphthalene [1,2-d] thiazole, naphthalene [2,1-d] thiazole, naphthalene [2,3-d] imidazoles, naphthalene [1,2-d] imidazoles, naphthalene [2,1-d] imidazoles, naphthalene [2,3-d] selenazoles, naphthalene [1,2-d] selenazoles, naphthalene [2,1-d] selenazoles, indyl [5,6-d] oxazole, indyl [6,5-d] oxazole, indyl [2,3-d] oxazole, indyl [5,6-d] thiazole, indyl [6,5-d] thiazole, indyl [2,3-d] thiazole, coumarone also [5,6-d] oxazole, coumarone also [6,5-d] oxazole, coumarone also [2,3-d] oxazole, coumarone also [5,6-d] thiazole, coumarone also [6,5-d] thiazole, coumarone is [2,3-d] thiazole also, benzothiophene also [5,6-d] oxazole, benzothiophene also [6,5-d] oxazole, benzothiophene also [2,3-d] oxazole etc.

In addition, as the 4 ring types ring-like heterocycle that contracts, for example can list anthracene [2,3-d] oxazole, anthracene [1,2-d] oxazole, anthracene [2,1-d] oxazole, anthracene [2,3-d] thiazole, anthracene [1,2-d] thiazole, phenanthro-[2,1-d] thiazole, phenanthro-[2,3-d] imidazoles, anthracene [1,2-d] imidazoles, anthracene [2,1-d] imidazoles, anthracene [2,3-d] selenazoles, phenanthro-[1,2-d] selenazoles, phenanthro-[2,1-d] selenazoles, carbazole also [2,3-d] oxazole, carbazole also [3,2-d] oxazole, dibenzofurans also [2,3-d] oxazole, dibenzofurans also [3,2-d] oxazole, carbazole is [2,3-d] thiazole also, carbazole is [3,2-d] thiazole also, dibenzofurans also [2,3-d] thiazole, dibenzofurans also [3,2-d] thiazole, coumarone also [5,6-d] oxazole, dibenzothiophene also [2,3-d] oxazole, dibenzothiophene also [3,2-d] oxazole, tetrahydro carbazole also [6,7-d] oxazole, tetrahydro carbazole also [7,6-d] oxazole, dibenzothiophene is [2,3-d] thiazole also, dibenzothiophene also [3,2-d] thiazole, tetrahydro carbazole is [6,7-d] thiazole etc. also.

Alkalescence nuclear as the ring that contracts more than 3 rings, more preferably naphthalene is: naphthalene [2,3-d] oxazole, naphthalene [1,2-d] oxazole, naphthalene [2,1-d] oxazole, naphthalene [2,3-d] thiazole, naphthalene [1,2-d] thiazole, naphthalene [2,1-d] thiazole, indyl [5,6-d] oxazole, indyl [6,5-d] oxazole, indyl [2,3-d] oxazole, indyl [5,6-d] thiazole, indyl [2,3-d] thiazole, coumarone [5,6-d] oxazole, coumarone also [6,5-d] oxazole, coumarone [2,3-d] oxazole, coumarone also [5,6-d] thiazole, coumarone also [2,3-d] thiazole, benzothiophene also [5,6-d] oxazole, anthracene [2,3-d] oxazole, anthracene [1,2-d] oxazole, anthracene [2,3-d] thiazole, anthracene [1,2-d] thiazole, carbazole also [2,3-d] oxazole, carbazole also [3,2-d] oxazole, dibenzofurans also [2,3-d] oxazole, dibenzofurans also [3,2-d] oxazole, carbazole also [2,3-d] thiazole, carbazole is [3,2-d] thiazole also, dibenzofurans [2,3-d] thiazole, dibenzofurans also [3,2-d] thiazole, dibenzothiophene also [2,3-d] oxazole, dibenzothiophene also [3,2-d] oxazole, preferred especially naphthalene [2,3-d] oxazole, naphthalene [1,2-d] oxazole, naphthalene [2,3-d] thiazole, indyl [5,6-d] oxazole, indyl [6,5-d] oxazole, indyl [5,6-d] thiazole, coumarone also [5,6-d] oxazole, coumarone is [5,6-d] thiazole also, coumarone also [2,3-d] thiazole, benzothiophene also [5,6-d] oxazole, carbazole also [2,3-d] oxazole, carbazole also [3,2-d] oxazole, dibenzofurans also [2,3-d] oxazole, dibenzofurans also [3,2-d] oxazole, carbazole is [2,3-d] thiazole also, carbazole is [3,2-d] thiazole also, dibenzofurans also [2,3-d] thiazole, dibenzofurans also [3,2-d] thiazole, dibenzothiophene also [2,3-d] oxazole, dibenzothiophene also [3,2-d] oxazole.

As above-mentioned alkalescence nuclear, the alkaline heterocycle shown in below enumerating.

Here, R represents hydrogen atom, aliphatic group or aromatic group.

Then, the sensitive agent with acid core is described.This sensitive agent is not particularly limited so long as have the pigment of acid core, can select according to exposure wavelength is suitable.

Concrete, for example can list merocyanine element, 3 nuclear merocyanine elements, 4 nuclear merocyanine elements, Luo Dan anthocyanidin, oxonol pigment etc., preferred merocyanine element, Luo Dan anthocyanidin, more preferably merocyanine element in them.

Above-mentioned acid core, for example can enumerate " the The Theory of the PhotographicProcess " the 4th edition that James compiles, the MacMillan Press Ltd., London and Bastingstoke, 1977, the 8th chapter " sensitizing coloring matter and desensitization pigment " definition, United States Patent (USP) No. 1567719, No. 1575869, No. 1804634, No. 1837862, No. 4002480, No. 4925777, spy the material of record such as open flat 3-167546 number.

When above-mentioned acid core is non-ring type, the groups such as activity methene compound of terminal preferred malononitrile, alkanesulfonyl acetonitrile, cyanogen methyl benzofuranone, cyanogen acetophenone, malonate and the methyl substituted ketone of acyl amino etc. of methylene combination.

When the former subgroup that is used to form the needs of above-mentioned acid core is ring type, be preferably formed by carbon, nitrogen, and chalcogen (is typically oxygen, sulphur, selenium and tellurium) 5 yuan or 6 yuan nitrogen heterocyclic ring of atomic building, as above-mentioned nitrogen heterocyclic ring, for example can enumerate the 2-pyrazolin-5-one, pyrazolidine-3, the 5-diketone, imidazoline-5-ketone, hydantoins, the 2-thio-hydantoin, the 4-thio-hydantoin, 2-Ya An Ji oxazolidine-4-ketone, 2-oxazoline-5-ketone, 2-Liu oxazolines-2,4-diketone isoxazoline-5-ketone, 2-thiazoline-4-ketone, thiazolidin-4-one, thiazolidine-2, the 4-diketone, rhodanic acid, thiazolidine-2, the 4-dithione, different rhodanic acid, dihydroindene-1, the 3-diketone, thiophene-3-ketone, thiophene-3-ketone-1, the 1-dioxide, Indolin-2-one, indoline-3-ketone, 2-oxo indazole quaternary ammonium salt, 3-oxo indazole quaternary ammonium salt, 5,7-dioxo-6,7-thiazoline also [3,2-a] pyrimidine, cyclohexane-1, the 3-diketone, 3,4-dihydro-isoquinoline-4-ketone, 1,3-diepoxide for example-4, the 6-diketone, malonyl urea, 2-sulfo-malonyl urea, chroman-2, the 4-diketone, indazole-2-ketone, pyridine [1,2-a] pyrimidine-1, the 3-diketone, pyrazolyl [1,5-b] quinazolinone, pyrazolyl [1,5-a] benzimidazole, the pyrazolyl pyridone, 1,2,3,4-tetrahydroquinoline-2,4-diketone, 3-oxo-2,3-dihydrobenzo [d] thiophene-1, the 1-dioxide, 3-dicyano methylene-2,3-dihydrobenzo [d] thiophene-1, the nuclear of 1-dioxide etc.

And, as above-mentioned acid core, can enumerate below shown in product (acid heterocycle etc.).

Here, R represents hydrogen atom, aliphatic group or aromatic group.

Then, the sensitive agent with fluorescer is described.

As the known above-mentioned fluorescer of " fluorescence albefaction agent " (fluorescent whitening agent) can absorb have near the light of the wavelength visible 300～450nm of ultraviolet～shortwave and can send fluorescence with near the wavelength 400～500nm, colourless～weak painted compound.The physical principle nuclear chemistry description of fluorescer is shown in Ullmann ' s Encyclopedia of IndustrialChemistry, Sixth Edition, and Electronic Release is among the Wiley-VCH 1998.Basically the fluorescer of Shi Heing contains the pi-electron system that comprises carbon-ring type or hetero ring type nuclear.

As the sensitive agent of this form,, can suit to select according to the exposure wavelength that when generating graft polymer, uses, exposure means (for example luminous ray or ultraviolet light, visible light laser etc.) so long as fluorescer is not particularly limited.

As fluorescer, preferably has the compound of nonionic nuclear.As above-mentioned nonionic nuclear, for example be preferably selected from least a in examining of stilbene nuclear, diphenylethyllene benzene nucleus, distyryl biphenyl nuclear and divinyl stilbene.

As compound with above-mentioned nonionic nuclear, be not particularly limited, can select according to purpose is suitable, for example can list pyrazolines, triazines, the stilbene class, the diphenylethyllene benzene class, the distyryl biphenyl class, divinyl stilbene class, the triazinylamino stilbenes class, the stilbenyl triazole type, stibene aphthotriazoles class, two-triazole stilbene class Benzooxazole kind, two Ben base Benzooxazole kinds, the stilbenyl Benzooxazole kind, two-Benzooxazole kinds, furans, benzofurans, two-benzimidazole, the diphenylpyrazoline class, the dipheny oxide diazoles, the naphthalimido class, oxa anthracenes, carbonyl styrene base class, pyrene class and 1,3,5-triazine derivative etc.In them, preferential compound one of at least of selecting to have in styryl, benzoxazolyl, the benzothiazolyl more preferably connects the dibenzoxazine class that obtains, two benzothiazoles etc. by the divalent linking group that comprises diphenylethyllene benzene class, distyryl biphenyl class or vinyl, fragrant cyclic group, heterocyclic radical.

In addition, above-mentioned fluorescer can have substituting group.As this substituting group; can enumerate fatty group; the aromatic series base; heterocyclic radical; carboxyl; sulfo group; cyano group; halogen atom (fluorine atom for example; the chlorine atom; bromine atoms); hydroxyl; carbon number is the alkoxy carbonyl (methoxycarbonyl for example below 30; carbethoxyl group; benzyl oxo carbonyl); carbon number is the alkyl sulfonyl-amino carbonyl below 30; aryl sulfonyl amino carbonyl; alkyl sulphonyl; aryl sulfonyl; carbon number is the acyl amino sulfonyl below 30; carbon number is the alkoxy (methoxyl for example below 30; ethoxy; benzyloxy; the phenoxy group ethoxy; phenethyl oxygen base etc.); carbon number is alkyl thio-base (the methyl thio group for example below 30; the ethylenebis dithiocarbamate group; methyl thio-ethyl thio-ethyl etc.); carbon number is the aryloxy (phenoxy group for example below 30; to toloxyl; the 1-naphthoxy; 2-naphthoxy etc.); nitro; carbon number is the alkyl below 30; alkoxy-carbonyl oxy; aryloxy ketonic oxygen base; carbon number is acyloxy (the acetyl group oxygen base for example below 30; propiono oxygen base etc.); carbon number is the acyl group (acetyl group for example below 30; propiono; benzoyl etc.); carbamyl (carbamyl for example; N; the N-formyl-dimethylamino; morpholino carbonyl; piperidino carbonyl etc.); sulfamoyl (sulfamoyl for example; N, N-dimethylamino sulfonyl; the morpholino sulfonyl; piperidyl sulfonyl etc.); carbon number is the aryl (phenyl for example below 30; the 4-chlorphenyl; the 4-aminomethyl phenyl; Alpha-Naphthyl etc.); the amino that replaces is (for example amino; alkyl amino; dialkyl amido; arylamino; ammonia diaryl base; acyl amino etc.); replace the uride base; replace phosphono etc.

The above-mentioned example of fluorescer of representative respectively can enumerate the former volume in great river for example " pigment handbook ", talk society, 84～145 pages, the compound of record in 432～439 pages.

As above-mentioned triazines, be not particularly limited, can select, for example can enumerate ethylenebis melamine, propylidene-1 according to purpose is suitable, the two melamines of 3-, N, N '-dicyclohexyl ethylenebis melamine, N, N '-dimethyl ethylene glycol bis melamine, N, N '-two [4,6-two-(dimethylamino)-1,3,5-triazinyl] ethylenediamine, N, N '-two (4,6-dipiperidino-1,3,5-triazinyl) ethylenediamine, N, N '-two [4,6-two-(dimethylamino)-1,3, the 5-triazinyl]-N, N '-dimethyl-ethylenediamine etc.The example of the fluorescer of representative is enumerated as following structural formula (1)～(7).

The content of the sensitive agent of these (b-3) generally is contemplated to be 0.01 quality %～20 quality % owing to need make the light of exposure wavelength arrive substrate surface according to absorption value.The mensuration of absorption value can be passed through general absorptiometer, measures the absorption intensity of exposure wavelength.

[(C) precursor layer of graft polymer]

(C) graft polymer precursor layer contains the compound (following is called " polymerizable compound ") that (c-1) have the unsaturated position of free redical polymerization and (c-2) can produce the compound (following is called " free-radical generating agent ") of free radical by heating or exposure among the present invention.

Below to (c-1) that constitute (C) graft polymer precursor layer and (c-2) composition describe.

[(c-1) polymerizable compound]

As (c-1) polymerizable compound that uses among the present invention, can use monomer, big molecule or have any in the macromolecular compound of polymerizable group.These polymerizable compounds can use known material arbitrarily, can use the polymerizable compound with various interaction groups according to purposes.

As useful especially polymerizable compound among the present invention, except the unsaturated position (polymerizable group) of energy free radical polymerizations such as unsaturated double-bond, the functional group that preferably has energy adsorption function material, in metal pattern formation method described later, for the graft polymer that generates, for the efficient that makes conductive material good, and be easy to keep high density, preferred use have can and the direct interactional functional group of formation of conductive material, perhaps can form the polymerizable compound of interactional functional group with the material that is used for effectively keeping conductive material (for example plating catalyst etc.).

Below, the functional group (position of adsorbing metal ions or slaine) that will can direct interaction form with the conductive material that is suitable in the metal pattern formation method, functional group (position of absorption chemical plating catalyst or its precursor) with interacting and form with the material that is used for effectively keeping conductive material is generically and collectively referred to as the interaction group and describes.

As this interaction group, for example can enumerate polar group.In this polar group, the preferred hydrophilic group can be enumerated electronegative functional group such as positively charged functional group such as ammonium, phosphine, sulfonic group, carboxyl, phosphate, phosphonate group more specifically, also have nonionic groups such as hydroxyl, amide group, sulfoamido, alkoxy, cyano group in addition.

Specify the polymerizable compound that is fit to use when forming metal pattern below with interaction group.

As the monomer of the polymerizable compound that uses among the present invention with interaction group, concrete (methyl) acrylic acid or its alkali metal salt and the amine salt for example can enumerated, itaconic acid or its alkali metal salt or amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-thio-ethyl (methyl) acrylate or its alkali metal salt and amine salt, 2-acrylamide-2-methyl propane sulfonic acid or its alkali metal salt and amine salt, acid phosphorus oxygen base polyoxyethylene glycol list (methyl) acrylate or its alkali metal salt and amine salt, polyoxy is for glycol monomethyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, (methyl) acrylamide, N-monomethylol (methyl) acrylamide, N-dihydroxymethyl (methyl) acrylamide, allylamine or its halogen acid salt, the N-vinyl pyrrolidone, vinyl imidazole, vinylpyridine, the vinyl thiophene, styrene, ethyl (methyl) acrylate, carbon numbers such as normal-butyl (methyl) acrylate are (methyl) acrylate with alkyl of 1～24 etc.

As the big molecule of the polymerizable compound that uses among the present invention, can use above-mentioned monomer, prepare by known method with interaction group.The macromolecular manufacture method of using in this programme has for example proposed various preparation methods in putting down into the 2nd chapter " macromolecular synthetic " of being issued " macromolecular chemistry and industry " (hero also under the editor mountain) by IPC bureau of publication on September 20th, 1.

Macromolecular useful weight-average molecular weight like this is in 500～500,000 scopes, and particularly preferred scope is 1000～50,000.

Be meant the polymkeric substance of having introduced ethene addition polymerization unsaturated groups (polymerizable group) such as interaction group and vinyl, allyl, (methyl) acrylic as operable macromolecular compound among the present invention with polymerizable compound of interaction group.This polymkeric substance at least endways or have ethene addition polymerization unsaturated group on the side chain more preferably has ethene addition polymerization unsaturated group on side chain, further preferably have ethene addition polymerization unsaturated group endways with on the side chain.

The useful weight-average molecular weight of such macromolecular compound is 500～500,000 scope, and preferred scope is 1000～50,000.

Synthetic method as macromolecular compound with interaction group and polymerizable group, can enumerate i) will have the monomer of interaction group and have the method for the monomer copolymerization of polymerizable group, the monomer and monomer copolymerizable that ii) will have the interaction group with polymerizable group precursor, then introduce the method for two keys by processing such as alkali, the polymkeric substance and monomer reaction that iii) will have the interaction group with polymerizable group, the method for introducing polymerizable group.

Preferred synthetic method is considered from synthetic adaptability, monomer that ii) will have the interaction group and the monomer copolymerizable with polymerizable group precursor are arranged, then introduce the method for polymerizable group by processing such as alkali, the polymkeric substance and monomer reaction that iii) will have the interaction group with polymerizable group, the method for introducing polymerizable group.

As above-mentioned i) and synthetic method ii) in the monomer that uses with interaction group, (methyl) acrylic acid or its alkali metal salt and amine salt for example can have been enumerated, itaconic acid or its alkali metal salt and amine salt, 2-hydroxyethyl (methyl) acrylate more particularly, (methyl) acrylamide, N-monomethylol (methyl) acrylamide, N-dihydroxymethyl (methyl) acrylamide, allylamine or its halogen acid salt, 3-vinyl propionic acid or its alkali metal salt and amine salt, vinyl sulfonic acid or its alkali metal salt and amine salt, 2-thio-ethyl (methyl) acrylate, polyoxyethylene glycol list (methyl) acrylate, 2-acrylamide-2-methyl propane sulfonic acid, acid phosphine oxygen base (acid phosphoxy) polyoxyethylene glycol list (methyl) acrylate, N-vinyl pyrrolidone (following structure), Sodium styrene sulfonate, vinyl benzoic acids etc. generally can use to have carboxyl, sulfonic group, phosphate, amino or its salt, hydroxyl, amide group, phosphino-, imidazole radicals, pyridine radicals or its salt, monomer with functional groups such as ethers.

As have can with the monomer of the polymerizable group of monomer copolymerization with above-mentioned interaction group, can enumerate allyl (methyl) acrylate, 2-allyl oxygen base ethyl-methyl acrylate.

In addition, can use 2-(3-chloro-1-oxopropoxy) ethyl-methyl acrylate or the special compound put down in writing in the 2003-335814 communique (i-1～i-60), the special preferred compound (i-1) in them opened as the monomer that in above-mentioned ii) synthetic method, uses with polymerizable group precursor.

And then, in the polymkeric substance that uses in the above-mentioned synthetic method (iii) with interaction group, the reaction of utilization and carboxyl, amino or functional groups such as their salt, hydroxyl and epoxy radicals, as introducing the used monomer of polymerizable group, (methyl) acrylic acid, (methyl) glycidyl acrylate, allyl glycidyl ether, 2-isocyanates ethyl (methyl) acrylate etc. are arranged with polymerizable group.

In the above-mentioned synthetic method ii),, handle the method for introducing polymerizable group, for example can use the spy to open the method for putting down in writing in the 2003-335814 communique by alkali etc. about the monomer that will have the interaction group with after having the monomer copolymerization of polymerism precursor.

(C) of the present invention graft polymer precursor layer can contain multiple (c-1) polymerizable compound in order to improve exposure sensitivity or controlling diaphragm character.

Like this, when containing multiple (c-1) polymerizable compound in (C) graft polymer precursor layer, its combination is not particularly limited, and can determine according to purpose is suitable.

Among the present invention, when using multiple (c-1) polymerizable compound, be main polymerizable compound as macromolecular compound with polymerizable group, to this, the low-molecular-weight polymerizable compound of dual-purpose (following suitable be called " low molecular monomer ".) be preferred version.

" low molecular monomer " among the present invention is meant that molecular weight is the compound below 600.

As long as low molecular monomer have more than 1 can free radical polymerization unsaturated position (polymerizable group), and molecular weight satisfies above-mentioned scope and gets final product, also can be as the monomer with polymerizable compound of above-mentioned interaction group, also can be general free-radical polymerised compound.

Be described more specifically low molecular monomer below.

Be not particularly limited about the polymerizable group in the low molecular monomer; the any of polymerizable group in the general free-radical polymerised compound be can use, (methyl) acryloyl group, (methyl) acrylamido, styryl etc. for example can have been enumerated.In them, preferably with main polymerizable compound and free-radical polymerised approaching group.When for example main polymerizable compound has (methyl) acryloyl group, the preferred low molecular monomer that uses with (methyl) acryloyl group.

In addition, the polymerizable group in the low molecular monomer can have in molecule more than 1, but from versatility, security, free-radical polymerised consideration, preferred 2～6 scope is more preferably 2～4 scope.

And then the structure except that the polymerizable group of low molecular monomer is not particularly limited, and this is because by regulating the functional group that molecular length or selection are introduced, can control the rerum natura of low molecular monomer.The selection of low molecular monomer preferably selects to consider the compatibility with the material that constitutes (C) graft polymer precursor layer (mainly have and with the macromolecular compound of polymerizable group), the structure that preferred polarity, hydrophilic and hydrophobic etc. are similar to.

For example, as mentioned above,, use when having the macromolecular compound of interaction group, in low molecular monomer, preferably have above-mentioned interaction group as macromolecular compound with polymerizable group.When particularly considering in metal pattern formation method, to be suitable for layered product of the present invention, can in low molecular monomer, introduce position as the adsorbing metal ions or the slaine of interaction group.Example as the position of adsorbing metal ions or slaine can have been enumerated polar group.In this polar group, hydrophilic radicals such as preferred acidic group or hydroxyl more specifically can have been enumerated electronegative functional groups such as sulfonic acid group, carboxyl, phosphate, phosphonate group.Wherein, consider preferred carboxyl, phosphonate group from energy of adsorption with respect to metallic ion or slaine.By introducing the position of such adsorbing metal ions or slaine, when in metal pattern formation method, being suitable for layered product of the present invention, can increase the amount of metal of absorption, thereby can improve the electric conductivity or the shading energy of the metal pattern that obtains.

The object lesson of low molecular monomer of the present invention is shown below, but the invention is not restricted to this.

Among the present invention, in (C) graft polymer precursor layer, with respect to the macromolecular compound with polymerizable group is main polymerizable compound, and when using low molecular monomer, the addition of low molecular monomer is with respect to main polymerizable compound, preferably 1～100 quality % is more preferably 10～80 quality %, further 30～70 quality % preferably.

[(c-2) free-radical generating agent]

Further contain (c-2) can produce free radical by heating or exposure compound (free-radical generating agent) in (C) of the present invention graft polymer precursor layer.

As (c-2) free-radical generating agent, use and the identical product of (b-2) free-radical generating agent that in above-mentioned polymerization trigger layer, adds, its preferred example is too.

(c-2) content of free-radical generating agent is according to the formation of (B) polymerization trigger layer or (C) formation of graft polymer precursor layer and the suitable decision of purposes of layered product.

For example, when directly the light of the wavelength of absorption uses as exposure light source with (c-2) free-radical generating agent in (b-1) base material bonding free love base polymerization initiator in (B) polymerization trigger layer, (b-2) free-radical generating agent, (C) graft polymer precursor layer, because need make light arrive polymerization trigger layer surface, the absorption of (c-1) free-radical generating agent of adding in the graft polymer precursor layer is preferably below 3, more preferably below 2.(c-1) free-radical generating agent of adding depends on the thickness of graft polymer precursor layer, as solid component concentration be preferably more than the 0.1 quality %, below the 20 quality %, more preferably 0.5 quality % above, below the 10 quality %.

In addition, the absorbing wavelength of (c-2) free-radical generating agent in (b-1) base material bonding free love base polymerization initiator in the exposure wavelength that shines on layered product and (B) the polymerization trigger layer, (b-2) free-radical generating agent, (C) graft polymer precursor layer is used sensitive agent not simultaneously.At this moment, deal as sensitive agent is important because make light arrive polymerization trigger layer surface, its upper limit is restricted (to be absorbed below 3, be preferably below 2), but be not limited for free-radical generating agent, generally be preferably 0.01 quality %～20 quality %, more preferably 0.1 quality %～10 quality % as solid component concentration.

And then, (B) (c-2) free-radical generating agent in (b-2) free-radical generating agent in the polymerization trigger layer, (C) graft polymer precursor layer is when producing the compound of free radical by heating, the content of free-radical generating agent is not subjected to its special restriction, generally be preferably 0.01 quality %～20 quality %, more preferably 0.1 quality %～10 quality % as solid component concentration.At this moment, exposure need be heated to about 40～120 ℃ simultaneously.

[(c-3) sensitive agent]

(C) graft polymer precursor layer among the present invention can further contain (c-3) sensitive agent.

As (c-3) sensitive agent can use with above-mentioned polymerization trigger layer in the same product of (b-3) sensitive agent that adds.

And (C) content of (c-3) sensitive agent in the graft polymer precursor layer considers that as mentioned above light arrives polymerization trigger layer surface and comes suitable decision.

(C) of the present invention graft polymer precursor layer in appropriate solvent, dissolve or disperse above-mentioned (c-1) polymerizable compound, (c-2) free-radical generating agent and further as required (c-3) sensitive agent prepare fluid composition (coating fluid), on above-mentioned (B) polymerization trigger layer, be coated with said composition, dry and form.

Solvent used herein just is not particularly limited so long as can dissolve or disperse each composition, and aqueous solvents such as preferred water, water-soluble solvent can further add surfactant in these potpourris or the solvent.

As operable solvent, for example can enumerate such acid amides series solvent of methyl alcohol, ethanol, propyl alcohol, ethylene glycol, glycerine, propylene glycol monomethyl ether such alkanol series solvent, acetic acid such acid, acetone, cyclohexanone such ketone series solvent, formamide, dimethyl acetamide etc.

In addition, for such fluid composition, the surfactant that can add as required is so long as the product that can be dissolved in the solvent is just passable, as such surfactant, for example can enumerate such anionic surfactant of dodecyl benzene sulfonic acid sodium salt or the such cationic surfactant of dodecyl trimethyl ammonium chloride, polyoxyethylene nonyl phenolic ether (for example has エ マ Le ゲ Application 910 as the commercial goods, KAO. Corp. SA's manufacturing etc.), polyoxyethylene sorbitan monolaurate (, trade name " Star イ-Application 20 " etc. for example being arranged) as the commercial goods, the nonionic surfactant that the polyoxyethylene lauryl ether is such etc.

Use is coated with the fluid composition that contains polymerizable compound when forming the method for filming on polymerization trigger layer surface, its coating weight is considered from the viewpoint of abundant acquisition coated film, is converted into solid constituent and is preferably 0.1～10g/m ², be preferably 0.5～5g/m especially ²

In addition, (C) thickness of graft polymer precursor layer preferably in the scope of 0.01～20 μ m, more preferably in the scope of 0.05～10 μ m, more preferably in the scope of 0.1～5 μ m.

As mentioned above, on the polymerization trigger layer, form the graft polymer precursor layer, can obtain layered product of the present invention.

Layered product of the present invention is the effect by the free-radical generating agent in the graft polymer precursor layer, high sensitive ground generation graft polymer.

The formation method of＜graft copolymer membrane formation method and graft pattern 〉

Graft copolymer membrane formation method of the present invention is characterised in that with respect to layered product of the present invention, wavelength period at 360nm～700nm is comprehensively exposed, Direct Bonding has the compound at unsaturated position that can free radical polymerization on polymerization trigger layer surface, generates graft polymer.

And, the formation method of graft pattern of the present invention is characterised in that it is with respect to layered product of the present invention, carry out the exposure of image shape in the wavelength period of 360nm～700nm, Direct Bonding has the polymkeric substance at the unsaturated position of energy free radical polymerization on polymerization trigger layer surface, generates graft polymer.

The following describes blanket exposure operation and pattern exposure.

In blanket exposure operation and the pattern exposure, being used for generating the exposure of graft polymer one of any all is free-radical generating agent or the sensitive agent that acts in polymerization trigger layer base material bonding free love base polymerization initiator or the graft polymer precursor layer, can produce the exposure of free radical, the light of the wavelength of concrete preferred 360nm～700nm.The selection of sensitive agent considers from the manufacture view of laser explosure device etc., more preferably the scope of 360nm～550nm.

Can use the constant light of comprehensive scan exposure of sending by LASER Light Source or high-pressure mercury-vapor lamp etc. in the blanket exposure operation.

In addition, in the pattern exposure operation, the preferred image shape that utilizes laser scanning exposure or pass through photomask that uses exposes.And, for example also can use the scan exposure of cathode ray tube (CRT).The cathode-ray tube (CRT) that uses in this image shape exposure shows luminous various luminophors in SPECTRAL REGION as required.For example any or mixing use more than 2 kinds of emitting red light body, green emitting body, blue-light emitting body.SPECTRAL REGION is not limited to above-mentioned redness, green and blue, also can use the fluorophor of jaundice look, orange, purple light.

And in this operation, pattern exposure can use various laser beams to carry out.For example, as pattern exposure, preferably laser such as using gases laser, light emitting diode, semiconductor laser, semiconductor laser or in excitation source, use the Solid State Laser of semiconductor laser and the scan exposure mode of the second higher hamonic wave illuminating source monochromatic high density light such as (SHG) of non-linearity optical crystal combination.And then also can use KrF excimer laser, ArF excimer laser, F2 laser etc.

Pattern resolution formed according to the present invention is influenced by conditions of exposure.In other words, the pattern exposure that is used to generate graft polymer forms the pattern of high definition by implementing the pattern exposure of high definition according to exposure.As the exposure method of the pattern that is used to form high definition, can enumerate the beam flying exposure of using optics, use the exposure of mask etc., it is also passable to carry out exposure method according to the pattern resolution of expectation.

Specifically can enumerate such exposure device exposure of i line exposing device (stepper, ス テ Star パ one), g line exposing device, KrF exposure device, ArF exposure device etc. as the exposure of the pattern of high definition.

" pattern " among the present invention is meant by giving the matrix that energy forms in the optional position of base material.This pattern can determine aptly according to purposes.For example can be that the spy opens the Wiring pattern shown in 12 among Fig. 6 of 2001-349949 communique, also can be that the spy opens the conductive pattern shown in 11 among Fig. 5 of 2004-207275 communique.

The base material that as above carries out the graft polymer generation is the processing of carrying out solvent impregnated or solvent cleaning etc., removes remaining homopolymer etc., makes with extra care.Specifically can enumerate by water or acetone cleaning, drying etc.Consider from removing property viewpoints such as homopolymer, also can use means such as ultrasound wave.Its remaining homopolymer in surface of base material after refining is removed fully, only has the graft polymer of tying bonding securely with base material.

The formation method (2) of＜graft pattern 〉

The formation method (2) of graft pattern of the present invention be characterised in that carry out successively on support key connect have by photodestruciton can produce the compound at the free-radical generating position of free radical and base material bonding position operation (below be called the compound bond sequence.) and carry out pattern exposure, make this free-radical generating position inactivation of exposure area operation (below be called the inactivation operation.), on the above-mentioned base material contact polymerizable compound after, carry out blanket exposure, when above-mentioned pattern exposure, cause photodestruciton at this remaining free-radical generating position of unexposed area, beginning free radical polymerization generate graft polymer operation (below be called graft polymer and generate operation.)。

The above-claimed cpd bond sequence is the manufacture method that can be suitable for above-mentioned (d) base material.

Then, implement the inactivation operation for having the base material that is introduced into passing through of obtaining of this method compound (photodestruciton compound (Q-Y)) that photodestruciton can produce the free-radical generating position and the base material bonding position of free radical.

In other words, the inactivation operation is to introducing the base material of photodestruciton compound (Q-Y), in advance along not wishing that the zone that generates graft polymer carries out pattern exposure, make free-radical generating position (Y) photodestruciton of exposure area, free-radical generating ability inactivation forms free-radical generating zone and free-radical generating ability inactivation zone at substrate surface.

Here, the pattern exposure in the inactivation operation can be suitable for the pattern exposure in the formation method (1) of graft pattern.

And, generate in the operation at graft polymer, after contacting polymerizable compound on the substrate surface that forms free-radical generating zone and free-radical generating ability inactivation zone, blanket exposure, only generate graft polymer on the free-radical generating zone, the result generates the graft polymer of pattern-like.

As method at substrate surface contact polymerizable compound, can be in containing the fluid composition of polymerizable compound, to flood base material, but consider from the viewpoint of operability or manufacturing efficient, preferably former state contacts polymerizable compound on substrate surface, or be coated with the fluid composition that contains polymerizable compound, form the method for filming, and then, dry this filmed, and forms the graft polymer precursor layer on polymerization trigger layer surface.

As mentioned above, by the formation method of graft copolymer membrane of the present invention, can be on base material Direct Bonding graft polymer comprehensively, make graft copolymer membrane.

In addition, by formation method (1) or (2) of graft pattern of the present invention, on base material, can make graft pattern with pattern-like Direct Bonding graft polymer.

In addition, the preferred thickness of film (graft polymer membrane) that is made of the graft polymer of gained is 0.1～2.0g/m ²Scope, 0.3～1.0g/m more preferably ², most preferably be 0.5～1.0g/m ²Scope.

The application of＜graft copolymer membrane, graft pattern 〉

As mentioned above gained pass through graft copolymer membrane that graft copolymer membrane formation method of the present invention obtains, by the graft pattern that graft pattern formation method of the present invention obtains, the interaction group that utilizes the graft polymer of generation to have can carry out various finishinges.

For example, when the graft polymer of combination has polar group, hydrophilic radical, ionic group on base material, provide the electric conductivity operation, can form conducting film or metal pattern by adhering to means such as conductive material.

The formation method of＜metal pattern 〉

Metal pattern formation method of the present invention has following 2 kinds of schemes.

Promptly, after first scheme of metal pattern formation method of the present invention is characterised in that and has on the graft polymer that generates adsorbing metal ions or slaine in graft pattern formation method of the present invention, reduce metallic ion in this metallic ion or the slaine, the operation of precipitating metal particle.

And, the alternative plan of the formation method of metal pattern of the present invention be characterised in that have form on the graft polymer that method generates absorption chemical plating catalyst or its precursor by graft pattern of the present invention after, carry out the operation that electroless plating forms electroplating film.

Below, this two kinds of schemes are described.

(first scheme: the formation of metal microparticle dispersion membrane)

First scheme is behind the interaction group adsorbing metal ions or slaine with respect to graft polymer, reduces this metallic ion or slaine, forms the method for metal microparticle dispersion membrane.

More particularly this first scheme is the interaction group that has with respect to above-mentioned graft polymer, ionic group especially preferably, according to its polarity, behind the metallic ion or slaine that ionic adsorption the following describes, reduce metallic ion in this metallic ion or the slaine, the precipitating metal monomer, the method for formation metal microparticle dispersion membrane.In addition, according to the form of separating out of metal monomer, it is the situation of metallic film that the metal microparticle dispersion membrane has.By this method, can form the electric conductivity that constitutes by the metal dispersion membrane and find layer.

Here, the metal microparticle of form the metal microparticle dispersion membrane, separating out is because the interaction group of energy and graft polymer interacts, absorption, the adaptation with base material and metal microparticle dispersion membrane is good, can bring into play the advantage of sufficient electric conductivity simultaneously.

(metallic ion and slaine)

At first, metallic ion and the slaine that uses in this programme is described.

Among the present invention,,,, dissociate the material of metallic ion and alkali (negative ion), be not particularly limited, can enumerate M (NO so long as can be dissolved in appropriate solvent in order to be provided to the generation zone of graft polymer as slaine ₃) _n, MCl _n, M _2/n(SO ₄), M _3/n(PO ₄) (M represents the metallic atom of n valency) etc.Can be suitable for the ion that above-mentioned slaine dissociates as metallic ion.Object lesson can have been enumerated for example Ag, Cu, Al, Ni, Co, Fe, Pd, wherein preferred Ag, Cu.

Slaine or metallic ion are just not a kind of, can multiplely be used in combination as required yet.And,, can be pre-mixed multiple material and use for the electric conductivity that obtains to expect.

(metallic ion and slaine provide method)

When metallic ion or slaine were provided on graft polymer, (1) used the method for adsorbing metal ions on this ionic group when graft polymer has ionic group.At this moment, dissolve above-mentioned slaine, comprised the metal ion solution of dissociating in the regional coating of the generation of graft polymer, perhaps the base material that the dipping graft polymer generates in this solution with appropriate solvent.Contact with containing metal ion solution, can ionic ground adsorbing metal ions on the above-mentioned ionic group.Consider that from the viewpoint of fully carrying out this absorption the concentration of metal ions of contact solution is preferably in 1～50 quality % scope, more preferably in 10～30 weight % scopes.And be preferably 10 seconds duration of contact～about 24 hours, about more preferably 1 minute～180 minutes.

When metallic ion or slaine are provided on the graft polymer, when (2) graft polymer contains the high structure of metal affinity such as polyvinyl pyrrolidone, above-mentioned slaine directly adheres to finely particulate, or use the appropriate solvent of energy dispersed metal salt to prepare dispersion liquid, at this dispersion liquid of generation zone coating of graft polymer, or the base material that the dipping graft polymer generates in this solution.

When graft polymer has as the hydrophilic radical of interaction group,, utilize this high water-retaining property, preferably the dispersion liquid of infiltration dispersed metal salt in graft polymer membrane because graft polymer has high water-retaining property.Consider that from the infiltration of fully carrying out dispersion liquid the metal salt concentrations of the dispersion liquid of contact is preferably the scope of 1～50 quality %, more preferably the scope of 10～30 weight %.And, as duration of contact, preferred about 10 seconds～24 hours, about more preferably 1 minute～180 minutes.

When providing metallic ion or slaine to graft polymer, (3) during graft polymer possess hydrophilic property group, on the generation zone of graft polymer, be coated with the solution that has disperseed the dispersion liquid of slaine or dissolved slaine, perhaps the base material that the dipping graft polymer generates in this dispersion liquid or solution.

With the above-mentioned the same high-moisture-retention that utilizes graft polymer membrane to have, dispersion liquid or solution can infiltrate in this graft polymer membrane in this method.Consider that from the abundant infiltration of dispersion liquid or solution the concentration of metal ions of the dispersion liquid of contact or the concentration of slaine are preferably the scope of 1～50 quality %, the more preferably scope of 10～30 quality %.And preferred about 10 seconds～24 hours of duration of contact is about more preferably 1 minute～180 minutes.

Especially, according to the method for these (3), no matter the characteristic of the interaction group that has of graft polymer, can provide the metallic ion or the slaine of expectation.

(reductive agent)

Then, the reductive agent that is used for reducing slaine that graft polymer (film) absorption or infiltration exist or metallic ion and uses is described.

The reductive agent that uses among the present invention is so long as have the physical property of reducing metal ion, precipitating metal monomer, just be not particularly limited, for example can have enumerated hypophosphites, tetraphydro-borate, hydrazine, formaldehyde, dialkyl amido borine (dimethylamino borine) etc.

These reductive agents can suit according to the relation with the slaine that uses, metallic ion to select, for example as the aqueous metal salt that metallic ion, slaine are provided, being fit to when using silver nitrate aqueous solution etc. is Sodium Borohydride, formaldehyde, dialkyl amido borine, but when being to use the palladium chloride aqueous solution, suitable is hydrazine.

Adding method as above-mentioned reductive agent, for example can enumerate behind adhesion metal ion or slaine on the substrate surface that generates graft polymer, after metal remained salt, metallic ion are removed in washing, dipping has this surperficial base material in water such as ion exchange water, add the method for reductive agent then, or on this substrate surface, directly be coated with or drip method of certain density reductive agent aqueous solution etc.And, as the addition of reductive agent, preferably use excess quantity more than the equivalent, more preferably 10 times more than the equivalent with respect to metallic ion.

The relation of graft polymer interaction group and metallic ion or slaine in first scheme is described here.

The interaction group of graft polymer is when having the such anionic property ionic group of the polar group of negative charge or carboxyl, sulfonic group or phosphonate group etc., graft polymer membrane is because optionally have negative charge, here absorption has the metallic ion of positive charge, reduce the metallic ion of this absorption, the precipitating metal monomer.

In addition, the interaction group of graft polymer is spy when opening the ionic group of the cationic groups of putting down in writing in the flat 10-296895 communique such as ammonium, and graft polymer membrane optionally has positive charge, and metallic ion is not with original shape absorption.Therefore, utilization comes from the water wettability of the ionic group of interaction group, infiltration has disperseed the dispersion liquid of slaine or has dissolved the solution of slaine in graft polymer membrane, reduces the solution metal ion of this infiltration or the metallic ion in the slaine, the precipitating metal monomer.

As mentioned above, the precipitating metal monomer forms the metal microparticle dispersion membrane.

The existence of the metal monomer (metal microparticle) of separating out in the metal microparticle dispersion membrane can be confirmed with visual by the metallic luster on surface, but be to use TEM or AFM (atomic force microscope) to observe the surface, can confirm its structure (form).And the thickness of metal pattern can pass through conventional method, for example carries out at an easy rate with the method for electron microscope observation section etc.

Like this, with the precipitation state of above-mentioned microscopic examination metal monomer, can confirm to be full of in the graft polymer membrane disperse state of metal microparticle.At this moment, as the size of the metal microparticle of separating out, particle diameter is about 1 μ m～1nm.

In addition, among the present invention, use this metallics of separating out, also can carry out electroless plating described later as plating catalyst.

In the metal microparticle dispersion membrane, metal microparticle disperses closeer, when forming metallic film in appearance, can be used as it is, but considers from the excellent in efficiency of guaranteeing electric conductivity, preferably with the further heat treated of metal microparticle dispersion membrane.

As the heating-up temperature in the heating treatment step, be preferably more than 100 ℃, more preferably more than 150 ℃, be preferably especially about 200 ℃.Heating-up temperature is considered the dimensional stability of treatment effeciency or base material etc., is preferably below 400 ℃.And, for being preferably heat time heating time more than 10 minutes, about more preferably 30 minutes～60 minutes.

The mechanism of action of heat treated is also indeterminate, but thinks the fusion mutually each other of part adjacent metal particulate, the reason that electric conductivity is improved.

(alternative plan: the formation of electroplating film)

Alternative plan is after adsorbing chemical plating catalyst or its precursor with respect to the interaction group that graft polymer has, to carry out electroless plating, forms the method for electroplating film.According to this method, form the conductive layer that constitutes by electroplating film.

Like this, electroplating film is owing to being that the catalyzer that adsorbs on the interaction group to graft polymer or its precursor carry out electroless plating and form, therefore electroplating film and graft polymer combination securely, when consequently having the cohesive excellence of base material and electroplating film, can adjust the advantage of electric conductivity according to the plating condition.

The method that provides of chemical plating catalyst in this alternative plan or its precursor at first, is described.

The chemical plating catalyst that uses in the present embodiment mainly is the metal of 0 valency, can enumerate Pd, Ag, Cu, Ni, Al, Fe, Co etc.Among the present invention, Pd, Ag operability are good, and catalysis can be high, so preferred especially.As the method for fixing 0 valency metal in the interaction zone, the method for the metallic colloid of for example can use on the graft polymer surface and provide interactional, adjusting is charged with the interaction group of graft polymer.The common metal colloid can prepare by reducing metal ion in the solution that charged surfactant or charged protective agent exist.The electric charge of metallic colloid can be regulated by surfactant used herein or protective agent; regulated the interaction group that charged metallic colloid and graft polymer have like this and interacted, can be on graft polymer adhesion metal colloid (chemical plating catalyst).

The chemical plating catalyst precursor that uses in this programme is so long as become the material of chemical plating catalyst, the use that can be not particularly limited by chemical reaction.Mainly can use the metallic ion of the 0 valency metal that in above-mentioned chemical plating catalyst, uses.The metallic ion of chemical plating catalyst precursor is 0 a valency metal by the reduction reaction chemical plating catalyst.After chemical plating catalyst precursor metal ion offers in the generation zone of graft polymer, before being impregnated in the chemical plating bath, make it become 0 valency metal by other reduction reactions, also can be used as chemical plating catalyst, perhaps also chemical plating catalyst precursor former state can be immersed in the chemical plating bath, make metal change (chemical plating catalyst) by the reductive agent in the chemical plating bath.

In fact, the metallic ion of electroless plating precursor offers graft polymer with the state of slaine.Slaine as using so long as dissolve, is dissociated into the material of metallic ion and alkali (negative ion) in appropriate solvent, be not particularly limited, and can enumerate M (NO ₃) _n, MCl _n, M _2/n(SO ₄), M _3/n(PO ₄) (M represents n valency metallic atom) etc.The ion that can suitably use above-mentioned slaine to dissociate as metallic ion.As object lesson, can enumerate for example Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, Pd ion, consider preferred Ag ion, Pd ion from catalytic performance.

Offer the method for graft polymer as chemical plating catalyst metallic colloid or electroless plating precursor metal salts, it can be dispersed metal colloid in suitable dispersion medium, or in appropriate solvent dissolved metal salt, preparation contains the metal ion solution of dissociating, this solution of coating on the generation zone of graft polymer, or the base material that the dipping graft polymer generates in this solution.Contact contains under the metal ion solution, utilizes ion-ionic interaction or dipole-ionic interaction on the interaction group that graft polymer has, the adhesion metal ion, and perhaps the impregnating metal ion also can in the interaction zone.From fully carrying out such adhering to or the consideration of infiltrating, contact solution metal ion concentration or metal salt concentrations are preferably 0.01～50 quality % scope, more preferably 0.1～30 quality % scope.In addition, be preferably 1 minute duration of contact～24 hours scopes, about more preferably 5 minutes～1 hour.

The method of electroless plating in this alternative plan then, is described.

For the base material that chemical plating catalyst or its precursor are provided, carry out electroless plating, form plated film.

Electroless plating is meant that the metal ion solution of using dissolving to separate out is by the operation of chemical reaction precipitating metal as electroplating.

In this operation electroless plating for example is to have adhered to the base material of chemical plating catalyst by washing, remove residual chemical plating catalyst (metal) after, be immersed in and carry out in the chemical plating bath.As the chemical plating bath of using, generally can use known chemical plating bath.

In addition, the base material of giving the chemical plating catalyst precursor adheres to the chemical plating catalyst precursor or the state in graft polymer of infiltrating when being immersed in the chemical plating bath, the washing base material, remove residual precursor (slaine etc.) after, in chemical plating bath, flood.At this moment, in chemical plating bath, carry out the reduction of precursor, then carry out electroless plating.Chemical plating bath used herein equally can be used known chemical plating bath usually with above-mentioned.

As the composition of common chemical plating bath, mainly contain 1, electroplate and use metallic ion, 2, reductive agent, 3, the adjuvant (stabilizing agent) of raising metal ion stability.Except mentioned component, also can contain the known additives such as stabilizing agent of electrobath in this electrobath.

As the kind of the metal that uses in the chemical plating bath, known have copper, tin, lead, nickel, gold, palladium, a rhodium, wherein considers special preferably copper, gold from electric conductivity.

And, only reductive agent, additive are arranged corresponding to above-mentioned metal.

For example in the chemical plating bath of copper, as mantoquita, so long as being not particularly limited of copper ion can be provided.Copper sulphate (CuSO is for example arranged ₄), cupric chloride (CuCl ₂), copper nitrate (Cu (NO ₃) ₂), Kocide SD (Cu (OH) ₂), cupric oxide (CuO), stannous chloride (CuCl) etc.The amount of the copper that exists in bath is generally 0.005M～0.1M, is preferably 0.01M～0.07M.As reductive agent, so long as copper ion can be reduced into the material of metallic copper, be not particularly limited, what be fit to is formaldehyde and derivant and such polymkeric substance, or derivatives thereof or the precursor of paraformaldehyde.It is more than the 0.05M that the amount of reductive agent is converted into formaldehyde, is preferably in 0.05M～0.3M scope.

The PH correctives is not particularly limited so long as can change the material of change pH values, according to purpose can suit to select the to use compound that improves pH value, the compound of reduction pH value.NaOH, KOH, HCl, H if can have been enumerated as pH regulator agent concrete example ₂SO ₄, HF etc.

The pH of chemistry plating bath is generally 12.0～13.4 (25 ℃), and expectation is in 12.4～13.0 (25 ℃) scope.As adjuvant, the stabilizing agent that contains copper ion is EDTA, sodium potassium tartrate tetrahydrate, trialkanolamine etc., but considers preferred trialkanolamine from the adaptation of glass baseplate and electroplating film.The addition of these stabilizing agents is 1.2 times～30 times of copper ion, is preferably 1.5 times～20 times.And the absolute magnitude of the stabilizing agent that exists in bath is 0.006～2.4M, in the scope particularly preferably in 0.012～1.6M.

Can enumerate trimethanolamine, triethanolamine, triisopropanolamine, tripropanol amine etc. as the trialkanolamine that stabilization agent uses, but consider, preferred especially triethanolamine from the adaptation of glass baseplate and electroplating film.

And, for the stabilization that improves bath or the adjuvant of electroplating the flatness of epithelium can have been enumerated poly-(Port チ) ethylene glycol, potassium ferrocyanide, bipyridine etc.The concentration of these adjuvants that exist in bath is 0.001～1M, is preferably especially in 0.01～0.3M scope.

In the electrobath that in the electroless plating of CoNiP, uses, contain cobaltous sulphate, nickelous sulfate, as the sodium hypophosphite of reductive agent, as sodium malonate, natrium malicum, the sodium succinate of complexing agent as slaine.And the chemical plating bath of palladium contains the (Pd (NH as metallic ion ₃) ₄) Cl ₂, as the NH of reductive agent ₃, H ₂NNH ₂, as the EDTA of stabilization agent.Also can add mentioned component composition in addition in these electrobaths.

The temperature of dip time in slaine that the thickness of the plated film of Xing Chenging can be by electrobath or concentration of metal ions, the electrobath or electrobath waits and controls like this, considers from electric conductivity, is preferably more than the 0.5 μ m, more preferably more than the 3 μ m.And, the dip time in electrobath, be preferably 1 minute～about 3 hours, about more preferably 1 minute～1 hour.

As above the plated film of Huo Deing can be by the cross-section of SEM, and the atomic of chemical plating catalyst or plated metal disperses fullly in graft polymer membrane, and then confirms to separate out bigger ion thereon.The interface is because be the state of graft polymer and atomic mixing, even the mean roughness of substrate surface (Rz) is below the 3 μ m, the adaptation of base material (organic principle) and inorganics (chemical plating catalyst or plated metal) is also fine.

And in this alternative plan, electroless plating also can be electroplated after stopping.That is, plating is that the plated film that above-mentioned electroless plating obtains is carried out as electrode.Thus with the adaptation excellent in chemical plated film of base material as the basis, can form electroplating film thereon easily with new any thickness.By adding this operation, can form the conductive film of purpose thickness.

As the electric plating method in this programme, can use present known method.In addition,, copper, chromium, lead, nickel, gold, silver, tin, zinc etc. be can enumerate, preferably copper, gold, silver, more preferably copper considered from electric conductivity as the metal that uses in electroplating.

For thickness by the electroplating film that electroplate to obtain, can be according to purposes and difference can be controlled by being adjusted in metal concentration, dip time or the current density etc. that contain in the electrobath.In addition, when conducting film that the present invention obtains or metal pattern were applicable to printed wiring board, the thickness of electroplating film was considered to be preferably more than the 0.3 μ m from electric conductivity, more preferably more than the 3 μ m.

2 kinds of schemes by above explanation can form metal pattern.

Distribution or electrode that this metal pattern can be suitable as electronic material use, and are suitable for the application of thin-layer transistor etc.

In addition, when above-mentioned two kinds of schemes are applicable to the graft copolymer membrane of comprehensive generation graft polymer, provide electric conductivity comprehensively, can form conducting film.

[other application]

The graft copolymer membrane that the formation method of the graft copolymer membrane of the present invention by above-mentioned gained obtains, the graft pattern that obtains by graft pattern formation method of the present invention are when the graft polymer of combination has polar group, hydrophilic radical, ionic group on base material, the method of dyestuff etc. can be adhered to by use, coloring film or colored pattern can be formed.

Dyestuff used herein preferably has the material of electric charge, further preferably has the material of the structure that can adsorb by specific intermolecular interaction.

Concrete, when graft polymer has anionic property functional group, use the methylene blue of cationic etc., when graft polymer has cationic functional group, use the erythrosine of anionic property etc., dyestuff is adsorbed in the functional group of graft polymer, can form the coloring film or the colored pattern of expectation.

＜printed wiring board, thin-layer transistor 〉

The feature of printed wiring board of the present invention or thin-layer transistor is to have the metal pattern that uses metal pattern formation method of the present invention to form.

The metal pattern that thin-layer transistor of the present invention is to use the formation method of above-mentioned metal pattern to form preferably has gate electrode, drain electrode, source electrode or metal wiring.

Thin-layer transistor can obtain large-area high conductive fine distribution in high definition ground by having the metal pattern that uses metal pattern formation method of the present invention to form, and is formed uniformly thickness, membranous.Thus, can make thin-layer transistor with the high distribution of reliability, electrode.

＜device 〉

Device of the present invention is characterised in that and has printed wiring board of the present invention or thin-layer transistor.

As such device, liquid crystal indicator (LCD), field emission display device (FED), electrophoretic display apparatus (EPD), plasma display system (PDP), electrochromic display device (ECD), el display device flat-panel monitors such as (ELD) can have been enumerated.

Come constituent apparatus by having printed wiring board of the present invention or thin-layer transistor, can be implemented under the resolution of expectation also good with the adaptation of substrate, the miniaturization of device and highly integrated.

As device of the present invention, except having above-mentioned printed wiring board or thin-layer transistor, be not particularly limited, can have known inscape, wherein preferred display device.

More than has the gate electrode that has used the metal pattern that obtains by the present invention, drain electrode, the liquid crystal indicator of source electrode or metal wiring (LCD), field emission display device (FED), electrophoretic display apparatus (EPD), plasma display system (PDP), electrochromic display device (ECD), el display device flat-panel monitors such as (ELD), can easily form good electrode or the distribution of the adaptation with substrate under the expectation resolution, in the miniaturization of using for TFT, high performance, or be effective during the conductive layer of the low resistanceization of the distribution of liquid crystal indicator etc.

The liquid crystal indicator that is fit among the present invention is replacing the dry type film forming, when requiring to form electrode or distribution by the wet type film forming or very useful when requiring the large tracts of land of display area.In addition, the active matrix type display that is fit among the present invention can not only be applicable to flat-panel monitor, also go for the plate type image inductor, the active-matrix substrate of having assembled thin-layer transistor of the present invention (being also referred to as the TFT element) can be suitable in the various liquid crystal indicators.

＜photomask 〉

Photomask of the present invention is characterised in that and uses the metal pattern that forms by metal pattern formation method of the present invention.

Photomask of the present invention is that its light shielding part forms by metal pattern.This light shielding part (metal pattern) thickness, membranously evenly formed bigger area, and then and the adaptation of base material (glass substrate) also good, so can obtain shading performance and the good photomask of environmental suitability.

In addition, the light shielding part of photomask of the present invention considers that from its shading performance the metal pattern that is got by silvery is preferred scheme.

Photomask of the present invention can be used in flat-panel monitor, the photo-mask process of CRT with fields such as shadow mask, printing distributing board, semiconductors.

And, be particularly suitable in the field of using large-size glass substrates such as plasma display (PDP) or LCD as photomask.

Embodiment

(synthesis example 1: base material bonding free love base polymerization initiator enumerate the synthetic of compound T1)

4-cyano group-4 '-xenol of dissolving 29.3g in the N,N-dimethylacetamide of 75mL, the sal tartari of adding 22.8g.Be heated to 80 ℃, drip the 11-bromo-1-undecylene of 38.8g, after all dripping, be warmed up to 100 ℃, reacted 3 hours.Then, with the distilled water that adds 250mL in the liquid, filter the solid of separating out,, obtain white yellow solid with acetonitrile crystallization again in reaction.

This white yellow solid of dissolving 20.0g adds the 1.54g aluminium bromide in the Tritox of 150mL.Seethed with excitement 4 hours with hydrogen chloride gas to the inside, and then left standstill 4 hours.Removal of solvent under reduced pressure is used ethyl acetate extraction, and is refining with the silica dioxide gel post, obtains yellow solid.

This yellow solid of dissolving 10.0g is cooled to 0 ℃ with ice-water bath in the THF of 20mL, adds the chloroplatinic acid hexahydrate of 1.0mg, adds the trichlorosilane of 30mL.At room temperature stirred 12 hours, removal of solvent under reduced pressure obtains yellow solid (the example compound T1 of base material bonding free love base polymerization initiator, said structure) then.

(synthesis example 2: the example compound T2's of base material bonding free love base polymerization initiator is synthetic)

In the THF of 200mL, dissolve 40.0gN-[4-[4, two (the trichloromethyl)-1,3,5-triazines of 6--2-yl]-the 4-hydroxybenzamide] (Fujiphoto manufacturing).Add the triethylamine of 15.8mL, the pyridine of 0.60mL, be cooled to 0 ℃ with ice-water bath.Drip the 12.3g methacrylic anhydride, at room temperature stirred 12 hours, removal of solvent under reduced pressure obtains grease then.With this grease of hexane crystallization,, obtain yellow solid with the acetonitrile washing.

Then, this yellow solid of dissolving 8g adds the glycidyl methacrylate of 1.91g, the methacrylic acid benzyl ester of 7.12g, the AIBN of 116mg in the N,N-dimethylacetamide of 67.4mL, is heated to 70 ℃, reacts 6 hours.The THF that adds 50mL then in reaction solution at last with the hexane precipitation, obtains the example compound T2 (said structure) of base material bonding free love base polymerization initiator.

(synthesis example 3: the example compound T3's of base material bonding free love base polymerization initiator is synthetic)

N at 84.0mL, the yellow solid that dissolving 10.0g is obtained by above-mentioned synthesis example 2 base material bonding free love base polymerization initiator T2 in the N-dimethyl acetamide, add the 2-methylol ethyl acrylate of 4.37g, the methacrylic acid benzyl ester of 5.92g, the AIBN of 138mg, be heated to 70 ℃, reacted 6 hours.The THF that adds 50mL then in reaction solution at last with the hexane precipitation, obtains the example compound T3 (said structure) of base material bonding free love base polymerization initiator.

(synthesis example 4: the example compound T6's of base material bonding free love base polymerization initiator is synthetic)

2-hydroxyl-4 (2-hydroxyl-oxethyl)-2-methyl phenyl ketone (Irgacure2959 of dissolving 9.00g in the THF of 30mL, イ Le ガ キ ユ ア 2959) (チ バ ガ イ ギ manufacturing), add the p methoxy phenol of 20mg, the 2-methacryloxyethyl isocyanates of 6.28g, the dibutyltin dilaurate of 81mg, reacted 4 hours down at 50 ℃.Removal of solvent under reduced pressure with the crystallization again of ethyl acetate-hexane, obtains white solid.

Then, this white solid of dissolving 10g adds the glycidyl methacrylate of 15.7g, the AIBN of 140mg in the MEK of 50mL, is heated to 70 ℃, reacts 6 hours.Then, use hexane precipitation reaction solution at last, obtain the example compound T6 (said structure) of base material bonding free love base polymerization initiator.

(synthesis example 5: hydrophilic polymer P1's is synthetic)

N at 200mL, polyacrylic acid (the mean molecular weight 25 of dissolving 30g in the N-dimethyl acetamide, 000), adds 2-ethyl-4-ethyl-imidazoles of 0.9g, the di-tert-butyl amyl group quinhydrones of 50mg, the monomer A of the following structure of 27g, flow down at nitrogen, 100 ℃ of reactions 5 hours.

Then, get the 50g reactant liquor, add the 4N NaOH of 11.6mL in ice-water bath, precipitate with ethyl acetate again, filter the back water and clean, drying obtains the hydrophilic polymer P1 of following structure.

(synthesis example 6: hydrophilic polymer P2's is synthetic)

N at 300mL, polyacrylic acid (the mean molecular weight 25 of dissolving 18g in the N-dimethyl acetamide, 000), adds the quinhydrones of 0.41g, the 2-methacryloxyethyl isocyanates of 3.53g, the dibutyltin dilaurate of 0.25g, flow down at nitrogen, reacted 4 hours for 65 ℃ times.

Then,, precipitate again, clean behind the filtering reacting liquid, drying, obtain the hydrophilic polymer P2 of following structure with ethyl acetate with in the 1N sodium hydrate aqueous solution and carboxyl.

Hydrophilic polymer P2

(synthesis example 7: monomers B synthetic)

Dissolving 10.2g 2 in the THF of 200mL, two (methylol) propionic acid (Tokyo changes into manufacturing) of 2-.To the pyridine of the triethylamine that wherein adds 31.6mL, 1.20mL, in ice bath, be cooled to 0 ℃.Then, drip the methacrylic anhydride of 24.6g, at room temperature stirred 12 hours, removal of solvent under reduced pressure then, the grease of acquisition uses the dioxide/silica gel post refining, obtains the monomers B of the following structure of 14.3g.

[embodiment 1]

(the polymerization trigger layer forms operation)

UV ozone treatment that go up to use UV ozone clean agent (UV42, Japanese electronic laser company makes) to carry out 5 minutes at glass substrate (NHTechno).The methyl ethyl ketone solution of the above-mentioned example compound T1 of spin coating 1 quality % on this substrate surface.Spin coating carried out for 5 seconds with 300rpm earlier, then with 750rpm rotation 20 seconds.Then,, use the MEK clean surface, use the air gun drying, form the polymerization trigger layer 100 ℃ of following glass substrate 10 minutes.The glass substrate that forms the polymerization trigger layer is as base material A1.

(graft polymer generation operation)

0.5g is dissolved in the distilled water of 4.2mL, the N of 0.05mL with the synthetic hydrophilic polymer P1 of said method, in the mixed solution of the acetonitrile of N-dimethyl acetamide, 1.5mL, the sodium bicarbonate of 0.3g, and then add the following compound S 1 of the sensitive agent of 0.03g, the sodium metaperiodate of 7mg, make coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of base material A1.Spin coating carried out for 5 seconds with 300rpm earlier, then with 750rpm rotation 20 seconds.Then that this base material is following dry 5 minutes at 80 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.Form the glass substrate of graft polymer precursor layer like this as substrate A2.

-exposure-

The base material A2 (layered product) that will have the graft polymer precursor layer is with having the laser explosure machine pattern according to the rules of the wavelength that sends 405nm with light quantity 50mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, with air gun (air gun) drying.

Thus, obtain to form with pattern-like the base material A3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Results verification has formed the pattern of L/S=10/10 μ m, thickness 0.9 μ m.

[embodiment 2]

(the polymerization trigger layer forms operation)

Go up use UV ozone clean agent (NL-UV42 at glass substrate (NHTechno), Japan electronic laser company makes) carry out 5 minutes UV ozone treatment, on this substrate surface, in the 1 quality % solution of the MEK of the above-mentioned example compound T2 of spin coating T2 is added the solution of the following compound S 2 of 20 quality %.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then,, use the MEK clean surface,, form the polymerization trigger layer with air gun (air gun) drying 170 ℃ of following glass substrate 1 hour.The glass substrate that forms the polymerization trigger layer is as base material B1.

(graft polymer generation operation)

0.5g is dissolved in the distilled water of 4.2mL, the N of 0.05mL with the synthetic hydrophilic polymer P2 of said method, in the mixed solution of the acetonitrile of N-dimethyl acetamide, 1.5mL, the sodium bicarbonate of 0.3g, and then the sensitive agent that adds 0.03g is the potassium metaperiodate of following compound S 1,7mg, makes coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of base material B1.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then that this base material is following dry 5 minutes at 80 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.The glass substrate that forms the graft polymer precursor layer is as base material C2.

-exposure-

The substrate B2 (layered product) that will have the graft polymer precursor layer is with having the laser explosure machine pattern according to the rules of the wavelength that sends 405nm with light quantity 20mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, with air gun (air gun) drying.

Thus, obtain to form with pattern-like the substrate B3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Results verification has formed the pattern of L/S=10/10 μ m, thickness 0.9 μ m.

[embodiment 3]

(the polymerization trigger layer forms operation)

Go up use UV ozone clean agent (NL-UV42 at glass substrate (NHTechno), Japan electronic laser company makes) carry out 5 minutes UV ozone treatment, on this substrate surface 2 of the above-mentioned example compound T3 of spin coating 0.05g, 12mg, the 4-toluene diisocyanate is dissolved in 1 quality % solution of MEK.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then,, use the MEK clean surface, use the air gun drying, form the polymerization trigger layer 120 ℃ of following glass substrate 10 minutes.The glass substrate that forms the polymerization trigger layer is as substrate C1.

(graft polymer generation operation)

The above-mentioned hydrophilic polymer P1 of 0.5g is dissolved in the distilled water of 4.2mL, the N of 0.05mL, in the mixed solution of the acetonitrile of N-dimethyl acetamide, 1.5mL, the sodium bicarbonate of 0.3g, and then the sensitive agent that adds 0.03g is the potassium metaperiodate of following compound S 1,7mg, makes coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of substrate C1.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then that this substrate is following dry 5 minutes at 80 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.Form the glass substrate of graft polymer precursor layer like this as substrate C2.

-exposure-

The substrate C2 (layered product) that will have a graft polymer precursor layer with have send the 405nm wavelength laser explosure machine pattern according to the rules with light quantity 20mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, with air gun (air gun) drying.

Thus, obtain to form with pattern-like the substrate C3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Results verification has formed the pattern of L/S=10/10 μ m, thickness 0.9 μ m.

[embodiment 4]

(the polymerization trigger layer forms operation)

At the UV ozone treatment that glass substrate (NHTechno) go up to use UV ozone clean agent (NL-UV42, Japanese electronic laser company makes) to carry out 5 minutes, 1 quality % solution of the MEK of the above-mentioned example compound T6 of spin coating on this substrate surface.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then,, use the MEK clean surface, use the air gun drying, form the polymerization trigger layer 170 ℃ of following glass substrate 1 hour.The glass substrate that forms the polymerization trigger layer is as base material D1.

(graft polymer generation operation)

The above-mentioned hydrophilic polymer P2 of 0.5g is dissolved in the N,N-dimethylacetamide of 6.2mL, and then adds the potassium metaperiodate of 7mg, make coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of substrate D 1.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then that this substrate is following dry 5 minutes at 110 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.Form the glass substrate of graft polymer precursor layer like this as base material D2.

-exposure-

The substrate D 2 (layered product) that will have the graft polymer precursor layer uses high-pressure mercury-vapor lamp exposure machine (manufacturing of ウ シ オ motor company) pattern according to the rules with light quantity 20mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, and uses the air gun drying.

Thus, obtain to form with pattern-like the base material D3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Its results verification has formed the pattern of L/S=10/10 μ m, thickness 0.9 μ m.

[embodiment 5]

(the polymerization trigger layer forms operation)

Go up use UV ozone clean agent (NL-UV42 at glass substrate (NHTechno), Japan electronic laser company makes) carry out 5 minutes UV ozone treatment, on this substrate surface 2 of the above-mentioned example compound T3 of spin coating 0.05g, 12mg, the 4-toluene diisocyanate is dissolved in 1 quality % solution of MEK.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then,, use the MEK clean surface, use the air gun drying, form the polymerization trigger layer 170 ℃ of following glass substrate 1 hour.The glass substrate that forms the polymerization trigger layer is as base material E1.

(graft polymer generation operation)

The above-mentioned hydrophilic polymer P2 of 0.5g is dissolved in the N,N-dimethylacetamide of 6.2mL, and then adds 25mg Photoepolymerizationinitiater initiater (above-claimed cpd S2), the preparation coating fluid.This coating fluid of spin coating on glass baseplate E2 surface.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then that this base material is following dry 5 minutes at 110 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.The glass substrate that forms the graft polymer precursor layer is as base material E2.

-exposure-

The substrate E2 (layered product) that will have the graft polymer precursor layer uses high-pressure mercury-vapor lamp exposure machine (manufacturing of ウ シ オ motor company) pattern according to the rules with light quantity 20mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, and uses the air gun drying.

Thus, obtain to form with pattern-like the base material E3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Its results verification has formed the pattern of L/S=10/10 μ m, thickness 0.9 μ m.

[embodiment 6]

At first, as the base material F1 among the embodiment 6, use the base material A1 of the polymerization trigger layer that in embodiment 1, uses with compound T1 that bonding is enumerated on glass substrate.

(graft polymer generation operation)

The synthetic hydrophilic polymer P1 of dissolving 0.5g said method in 3.1g1-methoxyl-2-propyl alcohol, and then interpolation 3.0g MEK, then add 0.03g sensitizer (above-claimed cpd S2), 0.03g Photoepolymerizationinitiater initiater (above-claimed cpd S2), 0.25g1,3-dimethyl allene acid glyceride (with the pure medicine manufacturing of light), the preparation coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of base material F1.Spinner is at first to rotate for 5 seconds with 300rpm, then rotates for 20 seconds with 750rpm.Descended dry these substrates 5 minutes at 80 ℃ then.

The thickness of the graft polymer precursor layer that obtains is 1.0 μ m.The glass substrate of the graft polymer precursor layer of Xing Chenging is as base material F2 like this.

-exposure-

The base material F2 (layered product) that will have a graft polymer precursor layer with the laser explosure machine of emission wavelength with 405nm according to certain pattern with light quantity 50mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, and uses the air gun drying.

Thus, obtain to form with pattern-like the base material F3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Its results verification has formed the pattern of L/S=10/10 μ m, thickness 1.2 μ m.

[embodiment 7]

At first, as the base material G1 among the embodiment 7, use having had on glass substrate bonding and enumerating the base material A1 of the polymerization trigger layer of compound T1 of using among the embodiment 1.

(graft polymer generation step)

The hydrophilic polymer P2 that dissolving 0.5g synthesizes with said method in 3.1g1-methoxyl-2-propyl alcohol, and then add the 3.0g MEK.Then add 0.03g sensitizer (above-claimed cpd S1), 0.03g Photoepolymerizationinitiater initiater (above-claimed cpd S2), 0.25g with the synthetic monomers B of said method, make coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of base material G1.Spinner at first rotated for 5 seconds with 300rpm, then rotated for 20 seconds with 750rpm.Descended dry these substrates 5 minutes at 80 ℃ then.

The thickness of the graft polymer precursor layer that obtains is 0.8 μ m.The glass substrate that forms such graft polymer precursor layer is as base material G2.

-exposure-

The base material G2 (laminated body) that will have a graft polymer precursor layer with the laser explosure machine of emission wavelength with 405nm according to certain pattern with light quantity 50mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, and uses the air gun drying.

Thus, obtain to form with pattern-like the base material G3 of graft polymer on polymerization trigger layer surface.

The pattern that obtains uses atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe.Results verification has formed the pattern of L/S=10/10 μ m, thickness 1.0 μ m.

[comparative example 1]

(the polymerization trigger layer forms operation)

At the UV ozone treatment that glass substrate (NHTechno) go up to use UV ozone clean agent (NL-UV42, Japanese electronic laser company makes) to carry out 5 minutes, 1 quality % solution of the MEK of the above-mentioned example compound T2 of spin coating on this substrate surface.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then,, use the MEK clean surface, use the air gun drying, form the polymerization trigger layer 170 ℃ of following glass substrate 1 hour.The glass substrate that forms the polymerization trigger layer is as base material H1.

(graft polymer generation operation)

The hydrophilic polymer P2 that 0.5g is obtained by said method is dissolved in the mixed solution of N,N-dimethylacetamide, 1.5mL acetonitrile, 0.3g sodium bicarbonate of 4.2mL distilled water, 0.05mL, makes coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of base material H1.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then that this substrate is following dry 5 minutes at 80 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.The glass substrate that forms the graft polymer precursor layer is as base material H2.

-exposure-

The base material H2 (layered product) that will have the graft polymer precursor layer uses high-pressure mercury-vapor lamp exposure machine (manufacturing of ウ シ オ motor company) pattern according to the rules with light quantity 50mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, and uses the air gun drying.

But, can not obtain to tolerate the curing of the film of development degree in this operation, the graft polymer precursor layer all dissolves, peels off during development.And, use atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe, can not confirm to form graft pattern.

[comparative example 2]

At first, base material I 1 in 2 has as a comparative example been used a kind of embodiment to have on glass substrate bonding and has been enumerated the base material A1 of the polymerization trigger layer of compound T1.

(graft polymer generation operation)

0.5g is dissolved in the N of 4.2mL distilled water, 0.05mL by the synthetic hydrophilic polymer P1 of said method, in the mixed solution of N-dimethyl acetamide, 1.5mL acetonitrile, 0.3g sodium bicarbonate, and then adding the 0.03g sensitive agent is above-claimed cpd S1, makes coating fluid.This coating fluid of spin coating on the polymerization trigger layer surface of the substrate A1 that the foregoing description 1 is put down in writing.Spin coating at first carried out for 5 seconds with 300rpm, then with 750rpm rotation 20 seconds.Then that this substrate is following dry 5 minutes at 80 ℃.

The thickness of the graft polymer precursor layer that obtains is 0.9 μ m.The glass substrate that forms the graft polymer precursor layer is as substrate G2.

-exposure-

The substrate G2 (layered product) that will have a graft polymer precursor layer with have send the 405nm wavelength laser explosure machine pattern according to the rules with light quantity 50mJ/cm ²Exposure.After the exposure, dipping is 1 minute in 1 quality % aqueous sodium carbonate, develops, and uses the air gun drying.

But, can not obtain to tolerate the curing of the film of development degree in this operation, the graft polymer precursor layer all dissolves, peels off during development.And, use atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe, can not confirm to form graft pattern.

＜estimate

In the foregoing description 1～5 and the comparative example 1,2, exposure such as following table 1 when generating graft polymer change, for the generation of exposure energy and graft polymer as the evaluation of getting off.

Except generation state, observe with atomic force microscope AFM (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes, and uses the DFM cantilever) by visualization graft polymer behind the methylene blue staining graft polymer.And, use atomic force microscope AFM to measure the thickness of the film (graft polymer membrane) that constitutes by graft polymer simultaneously, the Film Thickness Ratio of this thickness and graft polymer precursor layer is.The results are shown in the following table 1.

In addition, evaluation index is as follows.

Zero: generate and the same or thicker graft polymer membrane of graft polymer precursor layer

△: generated graft polymer membrane, but thickness is perhaps inhomogeneous less than the thickness of graft polymer precursor layer

*: do not generate graft polymer membrane.

[embodiment 8]

(operation of chemical plating catalyst is provided)

The base material B3 that obtains in the foregoing description 2 was flooded 1 minute in the silver nitrate aqueous solution of 1 quality %, and water cleans then, uses the air gun drying.

(electroless plating)

Then, dipping is 90 minutes in the commercially available chemical plating bath ATS ア De カ Star パ-IW (pH:12.7) of following composition, carries out electroless plating.After the electroless plating, water cleans, and uses the air gun drying.

The composition of＜chemical plating bath 〉

Water 258mL

ATSアドカツパ-IW-A 15mL

ATSアドカツパ-IW-M 24mL

ATSアドカツパ-IW-C 3mL

Should the surface with atomic force microscope observation, can confirm to form the metal pattern of L/S=12/8 μ m, thickness 3.0 μ m.

Using ロ レ ス -FP (LORESTA-FP: Mitsubishi Chemical Ind makes) to utilize four probe method to measure the surface conductivity of metal pattern part, is 7 μ Ω cm, and electric conductivity is good.

The metal pattern that employing and above-mentioned same method form 10mm * 200mm based on the lattice adhesive tape method of drawing of JIS 5400, with respect to the grid of well cutting, carries out the disbonded test of paper tape, estimates the adaptation of metal pattern.The result peels off for 0 with respect to 100 grids, and adaptation is abundant.

[embodiment 9]

(adsorption of metal ions operation)

The substrate B3 that obtains in the foregoing description 2 flooded 1 hour in 1 quality % silver nitrate aqueous solution, and water cleans, and uses the air gun drying.

(metallics formation operation)

Then, dipping is 1 minute in the glyoxalic acid solution (pH=12.5) of following composition, and the reduction silver ion forms metallics, and water cleans then, uses the air gun drying.

The composition of＜glyoxalic acid solution 〉

Water 100mL

NaOH 1.0mg

Glyoxalic acid 1.0mL

Should the surface with atomic force microscope observation, can confirm to form the metal pattern that absorption is arranged on 250nm～900nm of L/S=10/10 μ m, thickness 0.9 μ m.

With forming the metal pattern of 10mm * 200mm with above-mentioned same method, based on the check paper tape method of drawing of JIS 5400,, carry out the disbonded test of paper tape with respect to the grid of well cutting, estimate the adaptation of metal pattern.The result peels off for 0 with respect to 100 grids, and adaptation is abundant.

[embodiment 10]

(adsorption of metal ions operation)

The substrate B3 that obtains in the foregoing description 2 flooded 1 minute in 1 quality % silver nitrate aqueous solution, and water cleans, and uses the air gun drying.

(metallics formation operation)

Then, dipping is 1 minute in the formalin (pH=13.0) of following composition, and the reduction silver ion forms metallics, and water cleans, and uses the air gun drying.

The composition of＜formalin 〉

Water 100mL

NaOH 1.4mg

Formaldehyde 1.0mL

(electroless plating operation)

Then, dipping is 20 minutes in the chemical plating bath (pH:7.0) of following composition, carries out electroless plating.After the electroless plating, water cleans, and uses the air gun drying.

The composition of＜chemical plating bath 〉

NaOH-nitric acid buffer solution 988mL

Silver nitrate 2.0g

Succinimide 5.9g

Glyoxalic acid 3.7g

Should the surface with atomic force microscope observation, can confirm to form the metal pattern that absorption is arranged on 250nm～900nm of L/S=10/10 μ m, thickness 1.1 μ m.

And, use ロ レ ス -FP (LORESTA-FP: Mitsubishi Chemical Ind makes) to utilize four probe method to measure the surface conductivity of metal pattern part, be 40 μ Ω cm, electric conductivity is good.

With forming the metal pattern of 10mm * 200mm with above-mentioned same method, based on the ruled paper band method of drawing of JIS 5400,, carry out the disbonded test of adhesive tape with respect to the grid of well cutting, estimate the adaptation of metal pattern.The result peels off for 0 with respect to 100 grids, and adaptation is abundant.

[embodiment 11]

(operation of chemical plating catalyst is provided)

The substrate B3 that obtains in the foregoing description 2 was flooded 1 minute in the nickel sulfate solution of 1 quality %, and water cleans, and uses the air gun drying.

(electroless plating operation)

Then, (nickel-chromium: dipping is 10 minutes the manufacturing of woods electroplating industry), carries out electroless plating in chemical plating bath.After the electroless plating, water cleans, and uses the air gun drying.

Should the surface with atomic force microscope observation, can confirm to form the metal pattern that absorption is arranged on 250nm～900nm of L/S=10/10 μ m, thickness 1.5 μ m.

And, use ロ レ ス -FP (LORESTA-FP: Mitsubishi Chemical Ind makes) to measure metal pattern surface conductivity partly by four probe method, be 100 μ Ω cm, electric conductivity is good.

With forming the metal pattern of 10mm * 200mm with above-mentioned same method, based on the lattice adhesive tape method of drawing of JIS 5400,, carry out the disbonded test of adhesive tape with respect to the grid of well cutting, estimate the adaptation of metal pattern.The result peels off for 0 with respect to 100 grids, and adaptation is abundant.

[embodiment 12]

(adsorption of metal ions operation)

The base material F3 of dipping embodiment 6 acquisitions in 2 minutes in 1 quality % silver nitrate aqueous solution, water cleans then, uses the air gun drying.

(metallics formation operation)

Then, 1 minute base material F3 of dipping in the dimethyamine borane aqueous solution (pH=12.1) of following composition, reduction silver ion, precipitating metal particle.Water cleans base material F3 then, uses the air gun drying.

The composition of＜dimethyamine borane aqueous solution 〉

Water 100mL

NaOH 400mg

Dimethyamine borane 295mg

Use atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) when observing to the surface of precipitating metal particle, confirm to have formed L/S=10/10 μ m, thickness is the metal pattern of 1.5 μ m.

With forming the metal pattern of 10mm * 200mm with above-mentioned the same method, based on the lattice adhesive tape method of drawing of JIS 5400,, carry out the disbonded test of adhesive tape with respect to the grid of well cutting, estimate the adaptation of metal pattern.The result peels off for 0 with respect to 100 grids, and adaptation is abundant.

And, for the film that contains metallics, use Hitachi's high resolving power field emission scanning electron microscope (FESEM) S-4700 (manufacturing of Ha イ テ Network company of Hitachi) to carry out surface observation (50000 times of magnifications), confirm that having volume average particle size is the metallics of 20nm.This film that contains metallics has strong absorption at 250nm～600nm, can be used for light screening material (photomask) as can be known.

[embodiment 13]

(adsorption of metal ions operation)

The base material G3 of dipping embodiment 7 acquisitions in 1 minute in 10 quality % silver nitrate aqueous solutions, water cleans then, uses the air gun drying.

(metallics formation operation)

Then, dipping is 1 minute in the formalin (pH=13.0) of following composition, the reduction silver ion, and the precipitating metal particle, water cleans then, uses the air gun drying.

The composition of＜formalin 〉

Water 100mL

NaOH 1.4mg

Formaldehyde 1.0mL

Use atomic force microscope (Nanopix1000: セ イ コ-イ Application ス Le メ Application Star company makes) to observe for the surface of precipitating metal particle, confirm to have formed L/S=10/10 μ m, thickness is the metal pattern of 1.1 μ m.

With forming the metal pattern of 10mm * 200mm with above-mentioned the same method, based on the lattice adhesive tape method of drawing of JIS 5400,, carry out the disbonded test of adhesive tape with respect to the grid of well cutting, estimate the adaptation of metal pattern.The result peels off for 0 with respect to 100 grids, and adaptation is abundant.

And, for the film that contains metallics, use Hitachi's high score resolution field emission scanning electron microscope (FESEM) S-4700 (manufacturing of Ha イ テ Network company of Hitachi) to carry out surface observation (50000 times of magnifications), confirm that having volume average particle size is the metallics of 30nm.This film that contains metallics has strong absorption at 250nm～600nm, can be used for light screening material (photomask) as can be known.

Claims (20)

1, a kind of layered product, it is characterized in that having base material successively, polymerization trigger layer, graft polymer precursor layer, described polymerization trigger layer obtains by the compound that has free radical polymerization at chemical bonding on the above-mentioned base material and cause the position and can direct chemical be bonded to the position on this base material, and described graft polymer precursor layer contains compound with unsaturated position that free radical can polymerization and the compound that can produce free radical by heating or exposure.

2, the layered product described in claim 1 is characterized in that above-mentioned polymerization trigger layer further contains the compound that can produce free radical by heating or exposure.

3,, it is characterized in that the above-mentioned compound that can produce free radical by heating or exposure is selected from more than one in halo oxysalt, trihalomethyl group triazines, acyl group oxime ester, united imidazole and two cyclopentadiene titanium compounds as the layered product of record in claim 1 or 2.

4,, it is characterized in that the above-mentioned compound that can produce free radical by heating or exposure is to be selected from more than one of trihalomethyl group triazines, united imidazole and halo oxysalt as the layered product of record in claim 1 or 2.

5,, it is characterized in that above-mentioned is the halo oxysalt by the heating and the compound that can produce free radical that exposes as the layered product of record in the claim 1.

6, as the layered product of record in the claim 1, it is characterized in that above-mentioned grafting precursor layer contains that 0.1 quality % is above, the following scope of 20 quality % pass through the compound that above-mentioned heating and exposure can produce free radical.

7,, it is characterized in that above-mentioned polymerization trigger layer contains the compound that 0.1 quality % is above, the following scope of 20 quality % can produce free radical by above-mentioned heating and exposure as the layered product of record in the claim 2.

8,, it is characterized in that above-mentioned polymkeric substance with unsaturated position that can free radical polymerization further has the position of adsorbing metal ions or slaine as the layered product of record in the claim 1.

9,, it is characterized in that above-mentioned polymkeric substance with unsaturated position that can free radical polymerization further has the position of adsorbable electroless plating catalyzer or its precursor as the layered product of record in the claim 1.

10,, it is characterized in that above-mentioned graft polymer precursor layer contains multiple compound with above-mentioned unsaturated position that can free radical polymerization as the layered product of record in the claim 1.

11, a kind of graft copolymer membrane formation method, it is characterized in that for having base material successively, the layered product of polymerization trigger layer and graft polymer precursor layer carries out blanket exposure at the wavelength of 360nm～700nm, the above-mentioned compound of Direct Bonding on above-mentioned polymerization trigger layer surface with unsaturated position of free redical polymerization, make it generate graft polymer, above-mentioned polymerization trigger layer is to obtain by have the compound that free radical polymerization causes the position and can direct chemical be bonded to the position on this base material at chemical bonding on the above-mentioned base material, and above-mentioned graft polymer precursor layer contains the compound at the unsaturated position with free redical polymerization, with the compound that can produce free radical by heating or exposure.

12, a kind of graft pattern formation method, it is characterized in that for having base material successively, the layered product of polymerization trigger layer and graft polymer precursor layer carries out the exposure of image shape at the wavelength of 360nm～700nm, the above-mentioned compound of Direct Bonding on above-mentioned polymerization trigger layer surface with unsaturated position of free redical polymerization, make it generate graft polymer, above-mentioned polymerization trigger layer is to obtain by have the compound that free radical polymerization causes the position and can direct chemical be bonded to the position on this base material at chemical bonding on the above-mentioned base material, and above-mentioned graft polymer precursor layer contains the compound at the unsaturated position with free redical polymerization, with the compound that can produce free radical by heating or exposure.

13, a kind of formation method of metal pattern, it is characterized in that having after the graft pattern by record in the claim 12 forms on the graft polymer that generates in the method adsorbing metal ions or slaine, reduce metallic ion in this metallic ion or the slaine, make the operation of its precipitating metal particle.

14, a kind of metal pattern formation method is characterized in that having after the graft pattern by record in the claim 12 forms on the graft polymer that generates in the method absorption chemical plating catalyst or its precursor, carries out electroless plating, forms the operation of electroplating film.

15, as the formation method of metal pattern of record in the claim 14, it is characterized in that above-mentioned carry out electroless plating after, further electroplate.

16, a kind of printed wiring board, it has the metal pattern that forms according to the metal pattern formation method of putting down in writing in any one of claim 13～15.

17, a kind of thin-layer transistor, it has the metal pattern that forms according to the metal pattern formation method of putting down in writing in any one of claim 13～15.

18, a kind of device, it has the printed wiring board as record in the claim 16.

19, a kind of device, it has the thin film transistor (TFT) as record in the claim 17.

20, a kind of photomask, its use as any one of claim 13～15 in the metal pattern of the metal pattern formation method formation put down in writing.