CN107532302A - Photonasty electroless plating substrate agent - Google Patents

Abstract

The problem of the application is to provide, new electroless plating substrate agent used in a kind of pretreatment procedure as electroless plating, it considers environment, can easily be handled with few process number, and it is several μm of so fine wirings to be able to easily form width by photoetching.It is a kind of photonasty substrate agent as the method for solving problem of the present invention, metal coating is formed on base material for being handled by electroless plating, it is included：(a) it is 1 that molecular end, which has ammonium and weight average molecular weight; 000~5; 000,000 dissaving polymer, (b) metal particle, (c) intramolecular polymerizable compound, (d) Photoepolymerizationinitiater initiater, (e) amines and (f) multi-functional thiol with more than 1 (methyl) acryloyl group.

Description

Photonasty electroless plating substrate agent

Technical field

The present invention relates to include the photosensitive of dissaving polymer, metal particle, polymerizable compound and Photoepolymerizationinitiater initiater Property substrate agent.

Background technology

In recent years, along with the miniaturization of the devices such as PC, mobile phone, wearable terminal, for the high density of pattern Change, form the high wiring of transmissivity, observability on the transparent substrate, it is desirable to the method for easily forming fine wiring pattern case.

As one of method for forming fine wiring, disclose and electroless plating catalyst is formed by pattern by photoetching, so Implement the method (patent document 1) of electroless plating afterwards.Specifically, following methods are disclosed：Using being mixed in photoresist There is the material of the metal complex, metal ion or metallic colloid as electroless plating catalyst etc., by being covered across light UV exposures, the development of mould, form the substrate of the arbitrary graphic patterns such as clathrate, implement electroless plating to it, so as to obtain electric conductivity figure The method of case.

Furthermore disclosed following examples：By using the combination comprising the dissaving polymer with ammonium and Pd particulates Thing is as electroless plating substrate agent, so as to only directly be impregnated in non-electrolytic plating solution not via coating post activation process Form electroless plating (patent document 2).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 11-170421 publications

Patent document 2：No. 2012/141215 pamphlet of International Publication No.

The content of the invention

Invent problem to be solved

In above-mentioned patent document 1, as the stabilizer of metallic colloid, the protecting colloids such as PVP, detergent alkylate sulphur are used Surfactants such as acid etc., but the not only stability of varnish caused by the decomposition as protecting colloid, aggegation of metallic colloid etc. Troubling, and in process, the situation that catalyst is difficult to wash during development is more.In addition, in electroless plating, in target portion Divide to separate out with serving and also turn into problem.And then due to using water miscible resist, metallic stabilizer, therefore the mould of pattern The pattern forms such as paste, line be thick are maintained as problem.In the patent document, only to the transmissivity of the nesa coating of acquisition Discussed with resistance value, the line width (shape) of the pattern of acquisition is not made in detail.

In addition, the observability of image is required for the transparency electrode used in liquid crystal display cells etc..However, passing through Electroless plating is come in the case of forming metal line, the metal envelope formed has metallic luster, and it reflects exterior light, therefore Be difficult to manufacture metal line unobvious, visibility of image it is high clearly show that the problem of device is such.Therefore, for logical Electroless plating is crossed to form the technology of transparency electrode, it is desirable to by the back side (transparent base face) of metal-plated envelope that is formed It is blackened that metallic luster is suppressed.

Therefore currently invention addresses such problem, its object is to provide a kind of pretreatment procedure as electroless plating Used new electroless plating substrate agent, it considers environmental protection, can easily be handled with few process number, and And width is able to easily form as the so fine wiring of several microns by photoetching.

For solving the method for problem

The present inventor etc. have made intensive studies to achieve these goals, as a result find, have for molecular end The dissaving polymer and metal particle of ammonium, by specific polymerizable compound, Photoepolymerizationinitiater initiater, amines and more Functional thiols are combined in wherein and obtain photonasty substrate agent, and the substrate agent is coated on to the layer obtained on base material to be passed through Photoetching can obtain the basalis of the non-electrolytic metal-plated patterned to form pattern；The plating of the basalis is excellent, is pair In metal coating and layer useful for the raising for the adaptation for being plated base material.It has furthermore been found that in transparent bases such as glass The upper basalis for forming the non-electrolytic metal-plated patterned, when forming metal-plated envelope on the basalis, plating quilt Black is presented in the back side that film forms part.Particularly find, in above-mentioned emulsion substrate agent, by amines and Thiolation The cooperation of compound, it is possible to increase dispersiveness, the reactivity of metal particle, and pattern can be formed in high sensitivity, it is thus complete Into the present invention.

I.e., in the present invention, as the 1st viewpoint, it is related to a kind of photonasty substrate agent, for being handled by electroless plating Metal coating is formed on base material, it includes：

(a) molecular end has the dissaving polymer that ammonium and weight average molecular weight are 1,000~5,000,000,

(b) metal particle,

(c) intramolecular has the polymerizable compound of more than 1 (methyl) acryloyl group,

(d) Photoepolymerizationinitiater initiater,

(e) amines, and

(f) multi-functional thiol.

As the 2nd viewpoint, it is related to the photonasty substrate agent described in the 1st viewpoint, above-mentioned (c) polymerizable compound is intramolecular Compound with more than 3 (methyl) acryloyl groups.

As the 3rd viewpoint, it is related to the 1st viewpoint or the photonasty substrate agent described in the 2nd viewpoint, above-mentioned (c) polymerism chemical combination Thing is compound of the intramolecular with more than 3 (methyl) acryloyl groups and with oxyalkylene.

As the 4th viewpoint, it is related to the photonasty substrate agent described in any one of viewpoint of the 1st viewpoint~the 3rd, above-mentioned (f) Multi-functional thiol is 4 functional thiols.

As the 5th viewpoint, it is related to the photonasty substrate agent described in any one of viewpoint of the 1st viewpoint~the 4th, above-mentioned (e) Amines is the amines with alkoxysilyl.

As the 6th viewpoint, it is related to the photonasty substrate agent described in any one of viewpoint of the 1st viewpoint~the 5th, above-mentioned (a) Dissaving polymer is the dissaving polymer shown in formula [1].

(in formula [1], R¹Hydrogen atom or methyl, R are represented independently of one another²~R⁴Represent that hydrogen atom, carbon are former independently of one another The straight-chain of subnumber 1~20, the alkyl of branched or ring-type, the aryl alkyl or-(CH of carbon number 7~20₂CH₂O)_mR⁵(formula In, R⁵Hydrogen atom or methyl are represented, m represents 2~100 integer.) (abovementioned alkyl and aryl alkyl can be by alkoxy, hydroxyls Base, ammonium, carboxyl or cyano group substitution.), or R²~R⁴In 2 groups represent the Asia of straight-chain, branched or ring-type together Alkyl, or R²~R⁴Ring, X are formed together with the nitrogen-atoms combined with them^-Anion is represented, n is the number of repeat unit structure Mesh, represent 5~100,000 integer, A¹Structure shown in expression [2].)

(in formula [2], A²Expression can include straight-chain, branched or the ring-type of the carbon number 1~30 of ehter bond or ester bond Alkylidene, Y¹~Y⁴Independently of one another represent hydrogen atom, the alkyl of carbon number 1~20, carbon number 1~20 alkoxy, Nitro, hydroxyl, amino, carboxyl or cyano group.)

As the 7th viewpoint, it is related to the photonasty substrate agent described in the 6th viewpoint, above-mentioned (a) dissaving polymer is formula [3] Shown dissaving polymer.

(in formula [3], R¹~R⁴With n respectively with above-mentioned R¹~R⁴Identical meanings are represented with n.)

As the 8th viewpoint, it is related to the photonasty substrate agent described in any one of viewpoint of the 1st viewpoint~the 7th, above-mentioned (b) Metal particle is selected from iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver-colored (Ag), tin (Sn), platinum (Pt) and gold (Au) At least one of metal particulate.

As the 9th viewpoint, it is related to the photonasty substrate agent described in the 8th viewpoint, above-mentioned (b) metal particle is palladium particulate.

As the 10th viewpoint, it is related to the photonasty substrate agent described in any one of viewpoint of the 1st viewpoint~the 9th, above-mentioned (b) Metal particle is 1~100nm of average grain diameter particulate.

As the 11st viewpoint, it is related to the photonasty substrate agent described in any one of viewpoint of the 1st viewpoint~the 10th, it can Formed by photoetching to carry out pattern.

As the 12nd viewpoint, it is related to a kind of electroless plating basalis, is using the patterned layer being lithographically derived, is seen by the 1st Photonasty substrate dosage form described in any one of viewpoint of point~the 11st into.

As the 13rd viewpoint, be related to a kind of metal coating, its as the electroless plating basalis described in the 12nd viewpoint and The electroless plating formed on the electroless plating basalis is formed.

As the 14th viewpoint, it is related to a kind of metal by film base material, it possesses：Base material, the 12nd formed on the substrate are seen Metal coating described in the described electroless plating basalis of point and the 13rd viewpoint formed on the electroless plating basalis.

As the 15th viewpoint, it is related to a kind of metal by the manufacture method of film base material, it includes following A process~C processes.

A processes：Photonasty substrate agent described in any one of viewpoint of 1st viewpoint~the 11st is coated on base material, made It possesses the process of basalis

B processes：Process by being lithographically formed the basalis with expected pattern

C processes：The base material that will be provided with being formed the basalis of pattern is impregnated in non-electrolytic plating bath, forms the work of metal coating Sequence.

Invention effect

By the way that the photonasty substrate agent of the present invention is coated on base material, implement photoetching across mask, so as to easy Ground forms the basalis of the non-electrolytic metal-plated patterned.

Even if in addition, the photonasty substrate agent of the present invention do not formed in the past in order to improve adaptation with metal coating and The priming coat formed on base material, it can also form the basalis with the excellent adhesion of base material.And then photonasty base of the invention Priming agent can form the plate substrate layer of the patterning of μm level, can also be suitable for various wiring techniques.

Particularly photonasty substrate agent of the invention can be combined to form amine by coordinating with metal particle coordinations such as palladiums The amines of complex, so as to improve the dispersion stabilization of the metal particle in substrate agent, and then, add simultaneously Multi-functional thiol not only undertake effect as crosslinking agent, but also undertake the effect as chain-transferring agent, so as to The basalis of the non-electrolytic metal-plated of the patterning with excellent developability is formed during photoetching with high sensitivity.Moreover, this The photonasty substrate agent of invention can be developed using water.

In addition, by the present invention photonasty substrate dosage form into non-electrolytic metal-plated basalis it is non-only by being impregnated in Electrolysis plating bath is just able to easily form metal coating, can be readily available and possess base material, basalis and metal coating Metal is by film base material.

Moreover, the excellent adhesion of above-mentioned metal coating and the basalis of lower floor.

That is, basalis is formed on base material by using the photonasty substrate agent of the present invention, it may be said that can be formed and base The metal coating of the excellent adhesion of material.

And then when forming metal coating in the above-mentioned photonasty substrate agent of the present invention, its back side presentation black, therefore When they are formed on the transparent bases such as glass substrate, the use of the transparency electrode high as visibility of image can be expected.

Brief description of the drawings

Fig. 1 is the dissaving polymer (HPS-Cl) that the molecular end that display is manufactured by Production Example 1 has chlorine atom¹H The figure of NMR spectra.

Fig. 2 is the dissaving polymer (HPS- that the molecular end that display is manufactured by Production Example 2 has dimethyl octyl group ammonium N(Me)₂OctCl)¹³The figure of C NMR spectras.

Fig. 3 is the figure of the digital microscope images for the metal coating that display is obtained by embodiment 7.

Fig. 4 is the figure of the digital microscope images for the metal coating that display is obtained by embodiment 7.

Embodiment

[substrate agent]

＜ (a) dissaving polymers ＞

(a) dissaving polymer used in the photonasty substrate agent of the present invention has ammonium for molecular end and weight is equal Molecular weight is 1,000~5,000,000 polymer, specifically, can enumerate the dissaving polymer shown in following formula [1].

In above-mentioned formula [1], R¹Hydrogen atom or methyl are represented independently of one another.

In addition, R²~R⁴The alkane of hydrogen atom, the straight-chain of carbon number 1~20, branched or ring-type is represented independently of one another The aryl alkyl or-(CH of base, carbon number 7~20₂CH₂O)_mR⁵(in formula, R⁵Hydrogen atom or methyl are represented, m represents 2~100 Arbitrary integer.).Abovementioned alkyl and aryl alkyl can be substituted by alkoxy, hydroxyl, ammonium, carboxyl or cyano group.In addition, R²~R⁴In 2 groups represent the alkylidene of straight-chain, branched or ring-type, or R together²~R⁴And they are combined Nitrogen-atoms form ring together.

In addition, X^-Anion is represented, n is the number of repeat unit structure, represents 5~100,000 integer.

As above-mentioned R²~R⁴In carbon number 1~20 straight-chain alkyl, can enumerate methyl, ethyl, n-propyl, Normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, positive 13 Alkyl, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, positive 20 Alkyl etc., it is not easy from substrate agent in non-electrolytic plating solution from the viewpoint of dissolution, preferably the group of carbon number more than 8, it is special You Xuanwei not n-octyl.As the alkyl of branched, isopropyl, isobutyl group, sec-butyl, tert-butyl group etc. can be enumerated.As ring-type Alkyl, the group etc. with cyclopenta ring, cyclohexyl ring structure can be enumerated.

In addition, as R²~R⁴In carbon number 7~20 aryl alkyl, benzyl, phenethyl etc. can be enumerated.

And then as R²~R⁴In the alkylidene of straight-chain that represents together of 2 groups, methylene, sub- second can be enumerated Base, trimethylene, tetramethylene, hexa-methylene etc..As the alkylidene of branched, methyl ethylidene, butane -1,3- can be enumerated Diyl, 2- methylpropane -1,3- diyls etc..As the alkylidene of ring-type, the monocyclic, polycyclic of carbon number 3~30 can be enumerated The ester ring type fatty group of formula, the cyclic structure of crosslinking ring type.Specifically, can enumerate with carbon number more than 4 it is monocyclic, The group of two rings, three rings, Fourth Ring, five ring structures etc..It is former that these alkylidenes can include nitrogen-atoms, sulphur atom or oxygen in group Son.

Moreover, in the structure shown in formula [1], R²~R⁴And the ring formed together with the nitrogen-atoms that they are combined can To include nitrogen-atoms, sulphur atom or oxygen atom in ring, such as pyridine ring, pyrimidine ring, pyrazine ring, quinoline ring, connection pyrrole can be enumerated Pyridine ring etc..

As these R²~R⁴Combination, can enumerate for example, [methyl, methyl, methyl], [methyl, methyl, ethyl], [first Base, methyl, normal-butyl], [methyl, methyl, n-hexyl], [methyl, methyl, n-octyl], [methyl, methyl, positive decyl], [first Base, methyl, dodecyl], [methyl, methyl, n-tetradecane base], [methyl, methyl, n-hexadecyl], [methyl, methyl, N-octadecane base], [ethyl, ethyl, ethyl], [normal-butyl, normal-butyl, normal-butyl], [n-hexyl, n-hexyl, n-hexyl], [n-octyl, n-octyl, n-octyl] etc., wherein being preferably [methyl, methyl, n-octyl], [n-octyl, n-octyl, n-octyl] Combination.

In addition, as X^-Anion, can preferably enumerate halogen atom, PF₆ ^-、BF₄ ^-Or perfluoroalkane sulfonate radical ion.

In above-mentioned formula [1], A¹Represent the structure shown in following formula [2].

In above-mentioned formula [2], A²Represent to include the straight-chain of the carbon number 1~30 of ehter bond or ester bond, branched or The alkylidene of ring-type.

Y¹~Y⁴Independently of one another represent hydrogen atom, the alkyl of carbon number 1~20, carbon number 1~20 alkoxy, Nitro, hydroxyl, amino, carboxyl or cyano group.

As above-mentioned A²Alkylidene concrete example, methylene, ethylidene, trimethylene, tetramethylene, six sub- can be enumerated The branched alkylenes such as the straight-chain such as methyl alkylidene, methyl ethylidene, butane -1,3- diyls, 2- methylpropane -1,3- diyls Base.In addition, as cyclic alkylidene, monocyclic, polycycle and the cyclic structure for being crosslinked ring type of carbon number 3~30 can be enumerated Ester ring type fatty group.Specifically, monocyclic, two rings with carbon number more than 4, three rings, Fourth Ring, five rings knot can be enumerated The group of structure etc..For example, configuration example (a)~(s) for the ester ring type part being illustrated below in ester ring type fatty group.

In addition, as the Y in above-mentioned formula [2]¹~Y⁴Carbon number 1~20 alkyl, methyl, ethyl, isopropyl can be enumerated Base, n-pentyl, cyclohexyl etc..As the alkoxy of carbon number 1~20, methoxyl group, ethyoxyl, isopropoxy, just can be enumerated Amoxy, cyclohexyloxy etc..As Y¹~Y⁴, the preferably alkyl of hydrogen atom or carbon number 1~20.

As the dissaving polymer used in the present invention, the dissaving polymer shown in following formula [3] can be preferably enumerated.

In above-mentioned formula [3], R¹、R²~R⁴With n respectively with foregoing R¹、R²~R⁴Identical meanings are represented with n.

Above-mentioned molecular end used in the present invention has the dissaving polymer of ammonium can be for example, by making amine compounds Thing is reacted to obtain with the dissaving polymer that molecular end has halogen atom.

In addition, molecular end has the dissaving polymer of halogen atom can be according to International Publication No. 2008/029688 The record of number pamphlet, there is the dissaving polymer of dithiocarbamate groups by molecular end to manufacture.Molecule end Dissaving polymer of the end with dithiocarbamate groups can use commercially available product, can use Nissan Chemical work well Ha イ パ ー テ ッ Network (registration mark) HPS-200 of industry (strain) system etc..

In the amines that can be used in the present reaction, as primary amine, can enumerate methyl amine, ethylamine, n-propyl amine, It is isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentyl amine, n-hexyl amine, n-heptyl amine, just pungent Base amine, n-nonyl amine, positive decyl amine, n-undecane base amine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, just Pentadecyl amine, n-hexadecyl amine, n-heptadecane base amine, n-octadecane base amine, NSC 77136 base amine, n-eicosane base amine etc. Aliphatic amine；The ester ring type amine such as cyclopenta amine, cyclo-hexylamine；The aralkylamines such as benzyl amine, phenethyl amine；Aniline, to normal-butyl Aniline, p-tert-butyl-aniline, to n-octyl aniline, to positive decyl aniline, align dodecyl polyaniline, align myristyl aniline Deng amino anthracenes such as the amino anthracene classes such as the naphthylamines classes such as phenyl amines, naphthalidine, 2- naphthylamines, 1- amino anthracenes, 2- amino anthracenes, 1- amino anthraquinones The aminobiphenylenes such as quinones, 4- aminobphenyls, 2- aminobphenyls, 2- aminofluorenes, 1- amino -9-Fluorenone, 4- amino -9-Fluorenone etc. The aminophenanthrene classes such as the aminoisoquinoline classes such as the aminoidan classes such as aminofluorene class, 5- aminoidans, 5- aminoisoquinolines, 9- aminophenanthrenes Deng aromatic amine.N- (tert-butoxycarbonyl) -1,2- ethylenediamines, N- (tert-butoxycarbonyl) -1,3- the third two can further be enumerated Amine, N- (tert-butoxycarbonyl) -1,4- butanediamine, N- (tert-butoxycarbonyl) -1,5- pentanediamines, N- (tert-butoxycarbonyl) - 1,6- hexamethylene diamines, N- (2- hydroxyethyls) amine, N- (3- hydroxypropyls) amine, N- (2- methoxy ethyls) amine, N- (2- ethyoxyl second Base) amines such as amine.

As secondary amine, dimethyl amine, diethylamide, di-n-propyl amine, diisopropylamine, di-n-butyl amine, two can be enumerated Isobutylamine, di-sec-butyl amine, two n-pentyl amine, ethylmethylamine, methyl-n-propyl amine, methyl-n-butylamine, methyl-just Amylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentyl amine, methyl-n-octylamine, methyl-positive decyl amine, Methyl-dodecyl amine, methyl-n-tetradecane base amine, methyl-n-hexadecyl amine, methyl-n-octadecane base amine, ethyl Isopropylamine, ethyl-n-octylamine, di-n-hexyl amine, di-n-octyl amine, two dodecyl amine, two n-hexadecyl amine, two The aliphatic amines such as n-octadecane base amine；The ester ring type amine such as dicyclohexylamine；The aralkylamines such as dibenzyl amine；The fragrance such as diphenylamine Race's amine；The nitrogenous heterocyclic compound such as phthalimide, pyrroles, piperidines, piperazine, imidazoles.Double (2- hydroxyls can further be enumerated Base ethyl) amine, double (3- hydroxypropyls) amine, double (2- ethoxyethyl groups) amine, double (2- Amongs) amine etc..

As tertiary amine, Trimethylamine, triethylamine, three n-propyl amine, tri-n-butyl amine, three n-pentyl amine, three can be enumerated N-hexyl amine, three n-octylamines, three dodecyl amine, dimethylethyl amine, dimethyl-n-butylamine, dimethyl-n-hexyl Amine, dimethyl-n-octylamine, dimethyl-positive decyl amine, diethyl-positive decyl amine, dimethyl-dodecyl amine, diformazan Base-n-tetradecane base amine, dimethyl-n-hexadecyl amine, dimethyl-n-octadecane base amine, dimethyl-n-eicosane base amine etc. Aliphatic amine；Pyridine, pyrazine, pyrimidine, quinoline, 1- methylimidazoles, 4,4 '-bipyridyl, 4- methyl -4,4 '-bipyridyl etc. are nitrogenous Hetero ring type compound.

As long as the usage amount for the amines that can be used in these reactions has halogen atom relative to molecular end 1 mole of the halogen atom of dissaving polymer be 0.1~20 molar equivalent, be preferably 0.5~10 molar equivalent, more preferably 1~5 molar equivalent.

Molecular end has the reaction of the dissaving polymer and amines of halogen atom can be in water or organic solvent In, carried out under conditions of presence or absence of alkali.Used solvent, which is preferably capable dissolving molecular end, has halogen former The dissaving polymer of son and the solvent of amines.And then if can dissolve molecular end has the super of halogen atom Branched polymer and amines, but insoluble molecular end has the solvent of the dissaving polymer of ammonium, then separating-purifying Become easy, be more suitable for.

As the solvent that can be used in the present reaction, as long as do not hinder the solvent that this reaction is carried out significantly, Water can be used；The alcohols such as isopropanol；The organic acids such as acetic acid；The aromatic series such as benzene,toluene,xylene, ethylbenzene, 1,2- dichloro-benzenes Hydro carbons；The ethers such as tetrahydrofuran (THF), ether；The ketones such as acetone, butanone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), cyclohexanone； The halide such as chloroform, dichloromethane, 1,2- dichloroethanes；The aliphatic hydrocarbons such as n-hexane, normal heptane, hexamethylene；N, N- diformazan The amide-types such as base formamide (DMF), DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE (NMP).These can be used molten 1 kind in agent, two or more can also be used in mixed way.In addition, on usage amount, preferably use has relative to molecular end The quality of the dissaving polymer of halogen atom be 0.2~1,000 times of quality, be preferably 1~500 times of quality, more preferably 5~ The solvent of 100 times of quality, most preferably 5~50 times of quality.

As suitable alkali, typically using alkali metal hydroxide and alkaline earth metal hydroxide (such as sodium hydroxide, hydrogen Potassium oxide, calcium hydroxide), alkali metal oxide and alkaline earth oxide (such as lithia, calcium oxide), alkali metal hydride With alkaline earth metal hydride (such as sodium hydride, hydrofining, calcium hydride), alkali amide salt (such as Sodamide), alkali metal carbon Hydrochlorate and alkaline earth metal carbonate (such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal hydrogencarbonate (such as carbonic acid Hydrogen sodium) etc. inorganic compound and alkali alkyl, magnesium alkyl halide, alkali metal alcoholates, alkaline-earth alkoxides, dimethoxy The organo-metallic compounds such as base magnesium.Particularly preferably potassium carbonate and sodium carbonate.In addition, on usage amount, preferably use relative to There is molecular end 1 mole of the halogen atom of the dissaving polymer of halogen atom to be 0.2~10 molar equivalent, be preferably 0.5 The alkali of~10 molar equivalents, most preferably 1~5 molar equivalent.

In the reaction, the oxygen in reaction system is preferably fully removed before starting the reaction, can use nitrogen, argon gas It will enter line replacement in system Deng non-active gas.As reaction condition, the reaction time suitably selected from 0.01~100 hour, Reaction temperature suitably selects from 0~300 DEG C.Preferred reaction time is 0.1~72 hour, and reaction temperature is 20~150 DEG C.

In the case where having used tertiary amine, no matter alkali in the presence/absence of can obtain hyperbranched shown in formula [1] Polymer.

Make primary amine or secondary amine compound and molecular end that there is the hyperbranched poly of halogen atom under conditions of in the absence of alkali In the case that compound is reacted, the end that can obtain dissaving polymer corresponding with primary amine and secondary amine compound respectively is secondary The ammonium end dissaving polymer that amine and tertiary amine have been protonated.In addition, in the case of being reacted using alkali, By being mixed in organic solvent with sour aqueous solution such as hydrogen chloride, hydrogen bromide, hydrogen iodides, can also obtain corresponding hyperbranched The ammonium end dissaving polymer that the end secondary amine and tertiary amine of polymer have been protonated.

Weight average molecular weight that above-mentioned dissaving polymer is determined using gel permeation chromatography, converting to obtain with polystyrene Mw is 1,000~5,000,000, more preferably 2,000~200,000, most preferably 3,000~100,000.In addition, conduct Decentralization Mw (weight average molecular weight)/Mn (number-average molecular weight) be 1.0~7.0, preferably 1.1~6.0, more preferably 1.2~ 5.0。

＜ (b) metal particles ＞

As (b) metal particle used in the photonasty substrate agent of the present invention, it is not particularly limited, as metal kind Class, can enumerate iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver-colored (Ag), tin (Sn), platinum (Pt), golden (Au) and it Alloy, can be a kind in these metals or of more than two kinds be used in combination.Wherein, as preferable metal particle, Palladium particulate can be enumerated.In addition, as metal particle, the oxide of above-mentioned metal can be used.

Above-mentioned metal particle can be for example, by the side by the aqueous solution of metal salt using high-pressure mercury-vapor lamp progress light irradiation Method, the method for compound (so-called reducing agent) of addition with reduction etc. also obtained metal ion originally in the aqueous solution .For example, by adding the aqueous solution of metal salt in the solution dissolved with above-mentioned dissaving polymer and it being irradiated ultraviolet Line or added in the dissaving polymer solution metal salt the aqueous solution and reducing agent etc. and metal ion is reduced, from And can be while the complex of dissaving polymer and metal particle is formed, modulation is micro- comprising dissaving polymer and metal The substrate agent of grain.

As above-mentioned metal salt, gold chloride, silver nitrate, copper sulphate, copper nitrate, copper acetate, stannic chloride, protochloride can be enumerated Platinum, chloroplatinic acid, Pt (dba)₂[dba=dibenzalacetones], Pt (cod)₂[cod=1,5- cyclo-octadiene], Pt (CH₃)₂ (cod), palladium bichloride, acid chloride (Pd (OC (=O) CH₃)₂), palladium nitrate, Pd₂(dba)₃·CHCl₃、Pd(dba)₂, radium chloride, second Sour rhodium, ruthenic chloride, ruthenium acetate, Ru (cod) (cot) [cot=cyclo-octatrienes], iridium chloride, iridium acetate, Ni (cod)₂Deng.

As above-mentioned reducing agent, it is not particularly limited, various reducing agents can be used, preferably according to the substrate agent of acquisition In the metal species that contain etc. carry out selective reduction agent.As the reducing agent that can be used, can enumerate for example, sodium borohydride, boron hydrogen Change the hydroboration metal salts such as potassium；The hydrogen such as lithium aluminium hydride reduction, aluminum hydride potassium, aluminum hydride caesium, aluminum hydride beryllium, hydrogenation magnalium, calcium aluminum hydride Change aluminium salt；Hydrazine compound；Citric acid and its salt；Butanedioic acid and its salt；Ascorbic acid and its salt；It is methanol, ethanol, isopropanol, more The primary alconols such as first alcohol or secondary alcohol class；Trimethylamine, triethylamine, diisopropyl ethyl amine, diethylmethyl amine, tetramethylethylenediamine (TMEDA), the tertiary amines such as ethylenediamine tetra-acetic acid (EDTA)；Hydroxylamine；Three n-propyl phosphines, tri-n-butyl phosphine, tricyclohexyl phosphine, three Double (diphenylphosphino) ethane (DPPE) of benzyl phosphine, triphenylphosphine, triethoxy phosphine, 1,2-, double (diphenylphosphinos) third of 1,3- Alkane (DPPP), 1,1 '-bis- (diphenylphosphino) ferrocene (DPPF), 2,2 '-bis- (diphenylphosphinos) -1,1 '-dinaphthalenes (BINAP) Etc. phosphine etc..

The average grain diameter of above-mentioned metal particle is preferably 1~100nm.By making the average grain diameter of the metal particle be Below 100nm, so as to which surface area is reduced and must lacked, and sufficient catalytic activity can be obtained.As average grain diameter, it is more preferably Below 75nm, particularly preferably 1~30nm.

The addition of above-mentioned (a) dissaving polymer in the photonasty substrate agent of the present invention is relative to above-mentioned (b) metal The mass parts of particulate 100 are preferably 50~2,000 mass parts.By being more than 50 mass parts, so as to make above-mentioned metal Particulate fully disperses, in addition, by being below 2,000 mass parts, so as to suppress to be made by content of organics increase Into physical property etc. undesirable condition.More preferably 100~1,000 mass parts.

＜ (c) intramoleculars have the polymerizable compound ＞ of more than 1 (methyl) acryloyl group

There is more than 1 (methyl) acryloyl group as (c) intramolecular used in the photonasty substrate agent of the present invention Polymerizable compound (hereinafter also referred to as polymerizable compound), can preferably enumerate intramolecular has more than 3 (methyl) third The compound of enoyl-, wherein can preferably enumerate intramolecular with more than 3 (methyl) acryloyl groups and with oxyalkylene Compound.

As the oxyalkylene of above-mentioned oxyalkylene, preferably carbon number 2~4, wherein preferably oxygen ethylidene [- OCH₂CH₂-] or oxygen propylidene [- OCH₂C(CH₃)H-].Oxyalkylene can be (oxyalkylene) base poly- obtained by multiple connections, In such a case it is possible to individually have a kind of oxyalkylene, or there can be more than two kinds in combination.Sub- with a variety of oxygen In the case of alkyl, their combination can be that block combines and randomly any of combination.

In addition, in the present invention, (methyl) acrylate compounds refer to acrylate compounds and methacrylate Both compounds.Such as (methyl) acrylic acid refers to acrylic acid and methacrylic acid.

As above-mentioned polymerizable compound, urethane acrylates system, epoxy acrylic system, various (methyl) can be enumerated The monomer containing more than 1 (methyl) acryloyl group such as acrylic ester, particularly containing more than 3 above-mentioned (methyl) acryloyls Polyfunctional monomer of base etc..

In these polymerizable compounds, it is however preferred to have more than 3 (methyl) acryloyl groups and with oxyalkylene Compound, polyfunctional carbamate (methyl) acrylate compounds with more than 3 (methyl) acryloyl groups.

Enumerate the compound for being suitable as (c) polymerizable compound of the present invention below one, but (c) polymerism chemical combination Thing is not limited by these illustrations.

[with more than 3 (methyl) acryloyl groups and with the compound of oxyalkylene structure]

(1) 3 function (there are 3 (methyl) acryloyl groups) compound

As the compound (3 functional compound) with 3 (methyl) acryloyl groups and with oxyalkylene structure, can lift Go out for example, ethylene-oxide-modified 1,1,1- trimethylolethane trimethacrylate (methyl) acrylate [ethyleneoxide addition molal quantity 3~ 30], ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate [ethyleneoxide addition molal quantity 3~30], epoxy third Alkane is modified trimethylolpropane tris (methyl) acrylate [expoxy propane addition molal quantity 3~30], ethylene-oxide-modified glycerine Three (methyl) acrylate [ethyleneoxide addition molal quantity 3~30], epoxy pronane modification glycerine three (methyl) acrylate [ring Ethylene Oxide addition molal quantity 3~30], three (2- (acryloxy) ethyl) isocyanuric acid esters, 6-caprolactone be modified three (2- (third Alkene acyloxy) ethyl) isocyanuric acid ester [6-caprolactone addition molal quantity 1~30] etc..

Above-mentioned 3 functional compound can use commercially available product well, and can enumerating such as PVC ス コ ー ト #360, [Osaka is organic Chemical industry (strain) is made]；NK エ ス テ Le A-GLY-9E, NK エ ス テ Le A-GLY-20E, NK エ ス テ Le AT-20E [more than Dou Shixinzhong villages chemical industry (strain) is made]；TMPEOTA, OTA480, EBECRYL (registration mark) 135 [are above ダ イ セ Le オ Le ネ Network ス (strain) make] etc..

(2) 4 functions (there are 4 (methyl) acryloyl groups) compound

As the compound (4 functional compound) with 4 (methyl) acryloyl groups and with oxyalkylene structure, can lift Go out for example, ethylene-oxide-modified double (trimethylolpropane) four (methyl) acrylate [ethyleneoxide addition molal quantity 4~40], Ethylene-oxide-modified pentaerythrite four (methyl) acrylate [ethyleneoxide addition molal quantity 4~40] etc..

Above-mentioned 4 functional compound can be adapted to use commercially available product, can enumerate such as NK エ ス テ Le ATM-4E, NK エ ス テ Le ATM-35E [above Dou Shixinzhong villages chemical industry (strain) system]；[the ダ イ セ Le オ Le ネ of EBECRYL (registration mark) 40 Network ス (strain) makes] etc..

The compound that more than (3) 5 functions (there are more than 5 (methyl) acryloyl groups)

As the compound (change more than 5 functions with more than 5 (methyl) acryloyl groups and with oxyalkylene structure Compound), can enumerate for example, ethylene-oxide-modified dipentaerythritol six (methyl) acrylate [ethyleneoxide addition molal quantity 6~ 60], ethylene-oxide-modified tripentaerythritol eight (methyl) acrylate [ethyleneoxide addition molal quantity 6~60] etc..

Compound more than above-mentioned 5 function can use commercially available product well, can enumerate such as NK エ ス テ Le A-DPH- 12E [Xin Zhong villages chemical industry (strain) system] etc..

[polyfunctional carbamate (methyl) acrylate compounds with more than 3 (methyl) acryloyl groups]

As (c) polymerizable compound of the present invention, by and with carbamate based compound, so as to state after its formation Metal-plated envelope after can realize the blackened of the envelope back side, therefore preferably.

(1) 3 function (there are 3 (methyl) acryloyl groups) carbamate (methyl) acrylate

As the commercially available of polyfunctional carbamate (methyl) acrylate compounds with 3 (methyl) acryloyl groups The concrete example of product, NK オ リ go UA-7100 [Xin Zhong villages chemical industry (strain) system] can be enumerated；EBECRYL (registration mark) 204, EBECRYL 205、EBECRYL 264、EBECRYL 265、EBECRYL 294/25HD、EBECRYL 1259、EBECRYL 4820th, EBECRYL 8311, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, KRM (registration mark) 8296, KRM 8667 [being all ダ イ セ Le オ Le ネ Network ス (strain) systems above]；Purple light (registration mark) UV-7550B, purple light 7000B, purple light 7510B, purple light 7461TE, purple light 2750B [being all Japanese synthetic chemical industry (strain) system above] etc..

(2) 4 functions (there are 4 (methyl) acryloyl groups) carbamate (methyl) acrylate

As the commercially available of polyfunctional carbamate (methyl) acrylate compounds with 4 (methyl) acryloyl groups The concrete example of product, EBECRYL (registration mark) 8210 can be enumerated, EBECRYL8405, KRM (registration mark) 8528 [are above ダ イ セ Le オ Le ネ Network ス (strain) make]；Purple light (registration mark) UV-7650B [Japanese synthetic chemical industry (strain) system] etc..

Carbamate (methyl) acrylate that more than (3) 5 functions (there are more than 5 (methyl) acryloyl groups)

As polyfunctional carbamate (methyl) acrylate compounds (5 with more than 5 (methyl) acryloyl groups Carbamate (methyl) acrylate more than function), it can enumerate for example, (methyl) acrylate of pentaerythrite three and 1,6- The amino first of the carbamate compound of hexamethylene diisocyanate, (methyl) acrylate of pentaerythrite three and toluene di-isocyanate(TDI) Acid esters compound, the carbamate compound of (methyl) acrylate of pentaerythrite three and IPDI, two seasons penta Carbamate compound of (methyl) acrylate of tetrol five and hexamethylene diisocyanate etc..

Carbamate (methyl) acrylate more than above-mentioned 5 function can use commercially available product well, can enumerate example Such as UA-306H, UA-306T, UA-306I, UA-510H [being all common prosperity society chemical (strain) system above]；NKオリゴU-6LPA、NK オリゴU-10HA、NKオリゴU-10PA、NKオリゴU-1100H、NKオリゴU-15HA、NKオリゴUA-53H、NKオリゴ UA-33H [above Dou Shixinzhong villages chemical industry (strain) system]；EBECRYL (registration mark) 220, EBECRYL 1290, EBECRYL 5129, EBECRYL 8254, EBECRYL 8301R, KRM (registration mark) 8200, KRM 8200AE, KRM 8904th, KRM 8452 [being all ダ イ セ Le オ Le ネ Network ス (strain) systems above]；Purple light (registration mark) UV-1700B, purple light 6300B, purple light 7600B, purple light 7605B, purple light 7610B, purple light 7620EA, purple light 7630B, purple light 7640B, purple light 7650B [being all Japanese synthetic chemical industry (strain) system above] etc..

[other compounds with more than 3 (methyl) acryloyl groups]

The above-mentioned compound with more than 3 (methyl) acryloyl groups and with oxyalkylene structure and above-mentioned tool will be removed Have it is beyond polyfunctional carbamate (methyl) acrylate compounds of more than 3 (methyl) acryloyl groups, be suitable as The compound of (c) polymerizable compound of the present invention illustrates as follows.

(1) 3 function (there are 3 (methyl) acryloyl groups) compound

As the compound with 3 (methyl) acryloyl groups, 1,1,1- trimethylolethane trimethacrylate (methyl) third can be enumerated Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, double (trimethylolpropanes) three (methyl) acrylate, pentaerythrite Three (methyl) acrylate, glycerine three (methyl) acrylate etc..

The above-mentioned compound with 3 (methyl) acryloyl groups can use commercially available product well, can enumerate such as PVC ス コ ー ト #295, PVC ス コ ー ト #300 [being all Osaka Organic Chemical Industry (strain) system above]；ライトアクリレートTMP-A、 ラ イ ト ア Network リ レ ー ト PE-3A, ラ イ ト エ ス テ Le TMP [being all common prosperity society chemical (strain) system above]；NKエステルA- 9300、NKエステルA-9300-1CL、NKエステルA-TMM-3、NKエステルA-TMM-3L、NKエステルA- TMM-3LM-N, NK エ ス テ Le A-TMPT, NK エ ス テ Le TMPT [above Dou Shixinzhong villages chemical industry (strain) system]； PETIA, PETRA, TMPTA, EBECRYL (registration mark) 180 [being all ダ イ セ Le オ Le ネ Network ス (strain) systems above] etc..

(2) 4 functions (there are 4 (methyl) acryloyl groups) compound

As the compound with 4 (methyl) acryloyl groups, double (trimethylolpropane) four (methyl) propylene can be enumerated Acid esters, pentaerythrite four (methyl) acrylate etc..

The above-mentioned compound with 4 (methyl) acryloyl groups can use commercially available product well, can enumerate such as PVC ス コ ー ト #300 [Osaka Organic Chemical Industry (strain) system]；ラ イ ト ア Network リ レ ー ト PE-4A [common prosperity society chemistry (strain) system]；NKエ ス テ Le AD-TMP, NK エ ス テ Le A-TMMT [above Dou Shixinzhong villages chemical industry (strain) system]；EBECRYL (registration mark) 140th, EBECRYL 1142, EBECRYL 180 [being all ダ イ セ Le オ Le ネ Network ス (strain) systems above] etc..

The compound that more than (3) 5 functions (there are more than 5 (methyl) acryloyl groups)

As the compound with more than 5 (methyl) acryloyl groups, dipentaerythritol five (methyl) acrylic acid can be enumerated Ester, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate etc..

The above-mentioned compound with more than 5 (methyl) acryloyl groups can use commercially available product well, can enumerate for example PVC ス コ ー ト #802 [Osaka Organic Chemical Industry (strain) system]；ラ イ ト ア Network リ レ ー ト DPE-6A [common prosperity society chemistry (strain) System]；NK エ ス テ Le A-9550, NK エ ス テ Le A-DPH [above Dou Shixinzhong villages chemical industry (strain) system]；DPHA[ダイ セ Le オ Le ネ Network ス (strain) make] etc..

[intramolecular has (methyl) acrylate compounds of 1 or 2 (methyl) acryloyl group]

As (c) polymerizable compound used in the photonasty substrate agent of the present invention, there are 1 or 2 as intramolecular The compound of individual (methyl) acryloyl group, can use the various compounds using commercially available product as representative.

For example, intramolecular has carbamate (methyl) acrylate compounds of 1 or 2 (methyl) acryloyl group As described above, the black of the envelope back side is realized after the metal-plated envelope for helping to state after its formation due to being observed that Color, therefore can be used in combination well.

[intramolecular has carbamate (methyl) acrylate compounds of 1 or 2 (methyl) acryloyl group]

(1) mono-functional amine's formic acid esters (methyl) acrylate

Mono-functional amine's formic acid esters (methyl) acrylate compounds are not particularly limited, for example, can make polyisocyanic acid Ester (isocyanate prepolymer composition) and monohydric alcohol (active hydrogen component) react and obtain isocyanates end prepolymer, make its with (methyl) acryloyl group and reacted with the compound of group that isocyanates has reactivity, obtaining every 1 molecule has Carbamate (methyl) acrylate of average 1 (methyl) acryloyl group.It can replace monohydric alcohol using polyalcohol, but In this case, it is necessary to be grasped in a manner of (methyl) acryloxy is not imported in the part in the terminal hydroxyl of polyalcohol Make.

(2) 2 function carbamate (methyl) acrylate

As 2 function carbamate (methyl) acrylate, (methyl) third for example, phenyl glycidyl ether can be enumerated (methyl) acrylic acid addition of the carbamate compound of olefin(e) acid addition product and hexamethylene diisocyanate, phenyl glycidyl ether Carbamate compound of thing and toluene di-isocyanate(TDI) etc..

Above-mentioned 2 function carbamate (methyl) acrylate can use commercially available product well, can enumerate such as AH- 600th, AT-600 [being all common prosperity society chemical (strain) system above]；NKオリゴU-2PPA、NKオリゴU-200PA、NKオリゴUA- 160TM、NKオリゴUA-290TM、NKオリゴUA-4200、NKオリゴUA-4400、NKオリゴUA-122P、NKオリゴUA- W2A [above Dou Shixinzhong villages chemical industry (strain) system]；EBECRYL (registration mark) 210, EBECRYL 215, EBECRYL 230、EBECRYL 244、EBECRYL 245、EBECRYL 270、EBECRYL 280/15IB、EBECRYL 284、EBECRYL 285、EBECRYL 4858、EBECRYL 8307、EBECRYL 8402、EBECRYL 8411、EBECRYL 8804、EBECRYL 8807th, EBECRYL 9227EA, EBECRYL 9270, KRM (registration mark) 7735 [are above ダ イ セ Le オ Le ネ Network ス (strain) makes]；Purple light (registration mark) UV-6630B, purple light 7000B, purple light 7461TE, purple light 2000B, purple light 2750B, purple Light 3000, purple light 3200B, purple light 3210EA, purple light 3300B, purple light 3310B, purple light 3500BA, purple light 3520TL, purple light 3700B, purple light 6640B [being all Japanese synthetic chemical industry (strain) system above] etc..

In addition, in the photonasty substrate agent of the present invention, intramolecular had into 1 or 2 (methyl) acryloyl group The molecule that carbamate (methyl) acrylate compounds are enumerated with the above-mentioned example as suitable (c) polymerizable compound In the case of inside having the compound of more than 3 (methyl) acryloyl groups and use, its addition has 3 relative to above-mentioned intramolecular The mass parts of compound 100 of (methyl) acryloyl group are preferably below 200 mass parts more preferably 10~200 more than individual Mass parts, more preferably 20~100 mass parts.Even if so that there are 1 or 2 (methyl) propylene less than the addition of 10 mass parts is above-mentioned Carbamate (methyl) acrylate compounds of acyl group, and the black at the metal-plated envelope back side is not contributeed to realize yet Change, if in addition, adding more than 200 mass parts, the pattern of the plate substrate layer favorably carried out with photoetching, which is formed, becomes difficult Worry, it is therefore desirable to pay attention to.

[other intramoleculars have (methyl) acrylate compounds of 1 or 2 (methyl) acryloyl group]

(1) simple function (there is 1 (methyl) acryloyl group) compound

As the above-mentioned compound with 1 (methyl) acryloyl group, such as (methyl) acrylic acid, (methyl) third can be enumerated E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid N-butyl, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) isoamyl acrylate, (methyl) acrylic acid 2- ethylhexyls, (methyl) lauryl acrylate, (methyl) acrylic acid pentadecane base ester, (methyl) stearyl acrylate ester, (first Base) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid benzyl Ester, (methyl) acrylic acid naphthalene ester, (methyl) acrylic acid anthracene ester, (methyl) acrylic acid anthracene methyl esters, (methyl) phenyl acrylate, 2,2, 2- trifluoroethyls (methyl) acrylate, 2- ethylhexyl diglycols (methyl) acrylate (2-ethyl hexyl Diglycol (meth) acrylate), methoxy triglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylic acid Ester, methoxyl group dipropylene glycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, (methyl) acrylic acid 2- methoxies Base ethyl ester, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) ethioxy ethoxyethyl group ester, (methyl) acrylic acid fourth Epoxide ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 3- methoxybutyls, (methyl) acrylic acid 2- methyl -2- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid 2- propyl group -2- Buddha's warrior attendants alkyl ester, gamma-butyrolacton (methyl) acrylate, (methyl) acrylic acid two Ring pentyl ester, (methyl) acrylic acid 8- methyl -8- tricyclodecyls, (methyl) acrylic acid 8- ethyl -8- tricyclodecyls, (methyl) propylene Sour 2- ethylhexyls carbitol ester, (methyl) acrylate, phenoxy group diethylene glycol (DEG) (methyl) acrylate, phenoxy group Polyethylene glycol (methyl) acrylate, nonyl phenol ethoxy (methyl) acrylate, N- dimethyl aminoethyls (methyl) Acrylate, N- diethylaminos ethyl (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- Hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, (methyl) acryloyl Amine, N- methyl (methyl) acrylamide, N- dimethyl (methyl) acrylamide, N- dimethylaminopropyls (methyl) acryloyl Amine, N- methylols (methyl) acrylamide, the acetone of N- bis- (methyl) acrylamide, N, N '-di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylonitrile, (methyl) glycidyl acrylate, (methyl) acryloyl-oxyethyl butanedioic acid, 2- (methyl) acryloyl Epoxide ethylsuccinic acid, 2- (methyl) acryloyl-oxyethyl hexahydro phthalic acid, 2- (methyl) acryloyl-oxyethyls benzene two Formic acid, 2- (methyl) acryloyl-oxyethyl -2- hydroxyethyl phthalic acids etc..

The above-mentioned compound with more than 1 (methyl) acryloyl group can use commercially available product well, can enumerate for example, ライトアクリレートIAA、ライトアクリレートL-A、ライトアクリレートS-A、ライトアクリレートEC-A、 ライトアクリレートMTG-A、ライトアクリレートEHDG-AT、ライトアクリレート130A、ライトアクリレ ートDPM-A、ライトアクリレートPO-A、ライトアクリレートP2H-A、ライトアクリレートP-200A、ライト アクリレートNP-4EA、ライトアクリレートTHF-A、ライトアクリレートIB-XA、ライトエステルHOA (N)、ライトエステルHOP-A(N)、ライトアクリレートHOB-A、エポキシエステルM-600A、HOA-MS (N)、ライトアクリレートHOA-HH(N)、HOA-MPL(N)、HOA-MPE(N)、ライトアクリレートBA-104、ライ トアクリレートP-1A(N)、ライトエステルE、ライトエステルNB、ライトエステルIB、ライトエステ ルTB、ライトエステルEH、ライトエステルID、ライトエステルL、ライトエステルL-7、ライトエ ステルS、ライトエステルBC、ライトエステル130MA、ライトエステル041MA、ライトエステル CH、ライトエステルTHF(1000)、ライトエステルBZ、ライトエステルPO、ライトエステルIB-X、 ライトエステルHO-250(N)、ライトエステルHOP(N)、ライトエステルHOB(N)、ライトエステル DM、ライトエステルDE、ライトエステルDQ-100、ライトエステルHO-MS(N)、ライトエステルHO- HH (N), ラ イ ト エ ス テ Le G, ラ イ ト エ ス テ Le P-1M, ラ イ ト エ ス テ Le M-3F [are common prosperity society chemistry above (strain) makes]；NKエステルA-LEN-10、NKエステルAM-90G、NKエステルAM-130G、NKエステルAMP- 20GY、NKエステルA-SA、NKエステルS-800A、NKエステルCB-1、NKエステルM-90G、NKエステ Le M-230G, NK エ ス テ Le PHE-1G, NK エ ス テ Le S, NK エ ス テ Le SA [above Dou Shixinzhong villages chemical industry (strain) System]；FANCRYL (registration mark) FA-511AS, FANCRYL FA-512AS, FANCRYL FA-513AS, FANCRYL FA- BZA、FANCRYL FA-310A、FANCRYL FA-314A、FANCRYL FA-318A、FANCRYL FA-THFA、FANCRYL FA-512M、FANCRYL FA-512MT、FANCRYL FA-513M、FANCRYL FA-711MM、FANCRYL FA-712HM、 FANCRYL FA-BZM, FANCRYL FA-310M, FANCRYL FA-400M (100), FANCRYL FA-THFM [are above Hitachi's chemical conversion (strain) system]；β-CEA, IBOA-B, ODA-N, EBECRYL (registration mark) 110, [the ダ イ セ of EBECRYL 114 Le オ Le ネ Network ス (strain) make]；HEA、HPA、4-HBA、AIB、TBA、NOAA、IOAA、INAA、LA、STA、ISTA、IBXA、 ビスコート#150、ビスコート#155、ビスコート#160、ビスコート#192、ビスコート#190、ビスコ ー ト #MTG, PVC ス コ ー ト #200,2-MTA, MPE400A, MPE550A, MEDOL-10, OXE-10, OXE-30 [are above big Slope Organic Chemical Industry (strain) is made] etc..

(2) two functions (there are 2 (methyl) acryloyl groups) compound

As the above-mentioned compound with 2 (methyl) acryloyl groups, such as ethylene glycol two (methyl) acrylic acid can be enumerated Ester, diethylene glycol (DEG) two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, new penta Glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 1,4- fourths Glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, 2- Methyl isophthalic acid, 8- ethohexadiols two (methyl) acrylate, 1,10- decanediols two (methyl) acrylate, pentaerythrite two (methyl) Acrylate, three ring [5.2.1.0^2,6] decane dimethanol two (methyl) acrylate, twoAlkane glycol two (methyl) acrylic acid Ester, 2- hydroxyl -1- acryloxy -3- methacryloxies propane, 2- hydroxyls -1,3- two (methyl) acryloxy third Double [4- (2- (methyl) acryloyloxyethoxy) benzene of alkane, trihydroxy ethyl isocyanuric acid two (methyl) acrylate, 9,9- Base] fluorenes, undecenyl epoxide ethylene glycol two (methyl) acrylate, 1,3- adamantane glycol two (methyl) acrylate, 1, 3- adamantane dimethanol two (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylate etc..

The above-mentioned compound with more than 2 (methyl) acryloyl groups can use commercially available product well, can enumerate for example, ライトアクリレート3EG-A、ライトアクリレート4EG-A、ライトアクリレート9EG-A、ライトアクリレー ト14EG-A、ライトアクリレートPTMGA-250、ライトアクリレートNP-A、ライトアクリレートMPD-A、ラ イトアクリレート1.6HX-A、ライトアクリレート1.9ND-A、ライトアクリレートMOD-A、ライトアクリレ ートDCP-A、ライトアクリレートBP-4EAL、ライトアクリレートBP-4PA、ライトアクリレートHPP-A、ラ イトエステルG-201P、ライトエステルP-2M、ライトエステルEG、ライトエステル2EG、ライトエ ステル3EG、ライトエステル4EG、ライトエステル9EG、ライトエステル14EG、ライトエステル 1.4BG、ライトエステルNP、ライトエステル1.6HX、ライトエステル1.9ND、ライトエステルG- 101P, ラ イ ト エ ス テ Le G-201P, ラ イ ト エ ス テ Le BP-2EMK [being all common prosperity society chemical (strain) system above]；NKエ ステル701A、NKエステルA-200、NKエステルA-400、NKエステルA-600、NKエステルA-1000、 NKエステルA-B1206PE、NKエステルABE-300、NKエステルA-BPE-10、NKエステルA-BPE-20、 NKエステルA-BPE-30、NKエステルA-BPE-4、NKエステルA-BPEF、NKエステルA-BPP-3、NKエ ステルA-DCP、NKエステルA-DOD-N、NKエステルA-HD-N、NKエステルA-NOD-N、NKエステル APG-100、NKエステルAPG-200、NKエステルAPG-400、NKエステルAPG-700、NKエステルA- PTMG-65、NKエステル1G、NKエステル2G、NKエステル3G、NKエステル4G、NKエステル9G、NKエ ステル14G、NKエステル23G、NKエステルBPE-80N、NKエステルBPE-100、NKエステルBPE- 200、NKエステルBPE-500、NKエステルBPE-900、NKエステルBPE-1300N、NKエステルDCP、NK エステルDCP-N、NKエステルHD-N、NKエステルNOD-N、NKエステルNPG、NKエステル1206PE、 NK エ ス テ Le 701, NK エ ス テ Le 9PG [above Dou Shixinzhong villages chemical industry (strain) system]；FANCRYL FA-124AS、 FANCRYL FA-129AS、FANCRYL FA-222A、FANCRYL FA-240A、FANCRYL FA-P240A、FANCRYL FA- P270A、FANCRYL FA-321A、FANCRYL FA-324A、FANCRYL FA-PTG9A、FANCRYL FA-121M、 FANCRYL FA-124M、FANCRYL FA-125M、FANCRYL FA-220M、FANCRYL FA-240M、FANCRYL FA- 320M, FANCRYL FA-321M, FANCRYL FA-3218M, FANCRYL FA-PTG9M [are Hitachi's chemical conversion (strain) above System]；DPGDA, HODA, TPGDA, EBECRYL (registration mark) 145, EBECRYL 150, IRR214-K, PEG400DA-D, EBECRYL (registration mark) 11, HPDNA [ダ イ セ Le オ Le ネ Network ス (strain) systems]；ビスコート#195、ビスコー ト#230、ビスコート#260、ビスコート#310HP、ビスコート#335HP、ビスコート#700HV、ビスコー ト #540, PVC ス コ ー ト #802, PVC ス コ ー ト #295 [being all Japanese synthetic chemical industry (strain) system above] etc..

The addition of (c) polymerizable compound in the photonasty substrate agent of the present invention is relative to described later by above-mentioned over-expense Complex (or total quality of above-mentioned dissaving polymer and metal particle) 100 mass that fluidized polymer and metal particle are formed Part is preferably 10~10,000 mass parts.More preferably 100~2,000 mass parts, for example, 500~2,000 mass parts, 800 ~2,000 mass parts.If the addition of polymerizable compound is less than above-mentioned 10 mass parts (c), described later to be entered using photoetching The pattern of capable plate substrate layer, which is formed, becomes difficult, in addition, in the case where addition is more than 10,000 mass parts, has by this Substrate dosage form into basalis on can not form the worry of metal-plated envelope.

In addition, in order that the formative of the patternability and plating envelope of plate substrate layer on the basalis is fitted Close, the intramolecular that can make to be enumerated as the suitable example of (c) polymerizable compound has more than 3 (methyl) acryloyls The mixing ratio of the compound of base is for example more than 30 mass % preferably 50 relative to the gross mass of (c) polymerizable compound More than quality %, it is further the mass % of 75 mass %~100.

＜ (d) Photoepolymerizationinitiater initiaters ＞

As (d) Photoepolymerizationinitiater initiater used in the photonasty substrate agent of the present invention, known photopolymerization can be used Initiator, can enumerate for example, alkylbenzene ketone, benzophenone, acylphosphine oxide class, rice Chi benzoylbenzoic acid esters, Oxime esters, the sulfide-based, thioxanthene ketone class of tetra methylthiuram list etc..

The particularly preferably optical free radical polymerization initiator of optical cleavage type.Optical free radical on optical cleavage type, which polymerize, to be triggered Agent, can enumerate newest UV curing technologies (page 159, publisher：High thin one great, sale room：(strain) technical information association, 1991 Distribution) described in optical cleavage type optical free radical polymerization initiator.

As commercially available optical free radical polymerization initiator, can enumerate for example, IRGACURE (registration mark) 184, IRGACURE 369、IRGACURE 500、IRGACURE 651、IRGACURE 784、IRGACURE 819、IRGACURE 907、IRGACURE 1000、IRGACURE 1300、IRGACURE 1700、IRGACURE 1800、IRGACURE 1850、 IRGACURE 2959、IRGACURE CGI1700、IRGACURE CGI1750、IRGACURE CGI1850、IRGACURE CG24-61, IRGACURE TPO, Darocur (registration mark) 1116, Darocur 1173 [are above BASF ジ ャ パ Application (strain) make], ESACURE KIP150, ESACURE KIP65LT, ESACURE KIP100F, ESACURE KT37, ESACURE KT55, ESACURE KTO46, ESACURE KIP75 [being above ラ Application ベ Le テ ィ societies system] etc., but it is not limited to these.These Polymerization initiator can also combine a variety of use.

The addition of (d) polymerization initiator in the photonasty substrate agent of the present invention is relative to above-mentioned (c) polymerism chemical combination Thing is, for example, 0.1~100 mass %, preferably 1~50 mass %, more preferably 10~30 mass %.

＜ (e) amines ＞

As (e) amines used in the photonasty substrate agent of the present invention, known amines can be used, can Enumerate for example, the aliphatic such as alkyl amine, hydroxyalkylamines amine, amine, aromatic amine (aryl with cyclic substituents Amine) class and the amines with alkoxysilyl etc..In these amines, it is however preferred to have alkoxy first The amines of silylation.

In the present invention, it is micro- so as to obtain metal by the way that (e) amines is matched with photonasty substrate agent Grain, specifically for it is described later by metal particle and the complex that is formed of dissaving polymer with ammonium in substrate agent The effect that dispersion stabilization improves, furthermore contributes to fine plating pattern and is formed.

As abovementioned alkyl amine, ethylamine (CH can be enumerated₃CH₂NH₂), propyl group amine (CH₃(CH₂)₂NH₂), butylamine (CH₃ (CH₂)₃NH₂), amylamine (CH₃(CH₂)₄NH₂), hexyl amine (CH₃(CH₂)₅NH₂), heptyl amine (CH₃(CH₂)₆NH₂), octyl amine (CH₃(CH₂)₇NH₂), nonyl amine (CH₃(CH₂)₈NH₂), decyl amine (CH₃(CH₂)₉NH₂), undecyl amine (CH₃(CH₂)₁₀NH₂)、 Lauryl amine (CH₃(CH₂)₁₁NH₂), tridecyl amine (CH₃(CH₂)₁₂NH₂), tetradecylamine (CH₃(CH₂)₁₃NH₂), 15 Alkylamine (CH₃(CH₂)₁₄NH₂), hexadecylamine (CH₃(CH₂)₁₅NH₂), heptadecyl amine (CH₃(CH₂)₁₆NH₂), octadecyl Amine (CH₃(CH₂)₁₇NH₂), nonadecyl amine (CH₃(CH₂)₁₈NH₂), eicosyl amine (CH₃(CH₂)₁₉NH₂) and their knot The primary amine class such as structure isomers；The secondary amine classes such as N, N- dimethyl amine, N, N- diethylamides, N, N- dipropylamines, N, N- dibutylamines； The tertiary amines such as Trimethylamine, triethylamine, tripropylamine, tri-butylamine.

As above-mentioned hydroxyalkylamines (ethyl alcohol amine), carbinolamine (OHCH can be enumerated₂NH₂), monoethanolamine (OH (CH₂)₂NH₂), Propanolamine (OH (CH₂)₃NH₂), butanolamine (OH (CH₂)₄NH₂), amylalcohol amine (OH (CH₂)₅NH₂), hexanol amine (OH (CH₂)₆NH₂), enanthol amine (OH (CH₂)₇NH₂), octanol amine (OH (CH₂)₈NH₂), nonyl alcohol amine (OH (CH₂)₉NH₂), decyl alcohol amine (OH (CH₂)₁₀NH₂), hendecane hydramine (OH (CH₂)₁₁NH₂), dodecane hydramine (OH (CH₂)₁₂NH₂), tridecane hydramine (OH (CH₂)₁₃NH₂)、 Tetradecane hydramine (OH (CH₂)₁₄NH₂), pentadecane hydramine (OH (CH₂)₁₅NH₂), hexadecane hydramine (OH (CH₂)₁₆NH₂), heptadecane Hydramine (OH (CH₂)₁₇NH₂), octadecane hydramine (OH (CH₂)₁₈NH₂), nonadecane hydramine (OH (CH₂)₁₉NH₂), eicosane hydramine (OH(CH₂)₂₀NH₂) etc. primary amine class；N- carbinol methines amine, N- ethyl carbinols amine, N- propyl carbinols amine, N- butyl carbinols amine, N- Methylethanolamine, N- ehtylethanolamines, N- propyl group monoethanolamine, N- butylethanolamines, N- methyl-props hydramine, N- ethylpropanolamines, N- propyl propanols amine, N- butylpropanols amine, N- methyl butanols amine, N- ethyl butanols amine, N- propyl group butanolamine, N- butyl butanolamines Etc. secondary amine class etc..

In addition, as other aliphatic amines, can enumerate methoxy amine, methoxy ethyl amine, METHOXY PROPYL AMINE, Methoxybutyl amine, ethoxyl methyl amine, ethoxyethyl group amine, ethoxycarbonyl propyl amine, ethoxybutyl amine, propoxy methyl Amine, Among amine, propoxypropyl amine, propyloxybutyl amine, butoxymethyl amine, butoxyethylamine, butoxy third The alkoxyalkyl amines such as base amine, butoxybutyl amine.

As the example of the amine with cyclic substituents, preferably formula R¹¹-R¹²-NH₂Shown amines.

In above-mentioned formula, R¹¹For carbon number 3~10, be preferably carbon number 3~12 monovalence cyclic group, can be alicyclic ring Any of formula base, aromatic series base and combinations thereof.These cyclic groups can be by arbitrary substituent such as carbon atom Alkyl of number 1~10 etc. substitutes.R¹²Represent singly-bound or carbon number 1~17, be preferably carbon number 1~3 alkylidene.

In the present invention, as formula R¹¹-R¹²-NH₂The preferable concrete example of shown amines, can enumerate following formula (A-1) compound shown in~(A-10) etc..

As the concrete example of aromatic amine (aryl amine), aniline, methylphenylamine, o-anisidine, a fennel can be enumerated Fragrant amine or P-anisidine, ortho-aminotoluene, meta-aminotoluene or para-totuidine, o-chloraniline, m-chloroaniline or parachloroanilinum, bromophenyl Amine, m-bromoaniline or para-bromoaniline, adjacent Iodoaniline, an Iodoaniline or paraiodoaniline etc..

As the concrete example of the amines with alkoxysilyl, N, N '-bis- [3- (trimethoxy first can be enumerated Silylation) propyl group] -1,2- ethylenediamines, N, N '-bis- [3- (triethoxysilyl) propyl group] -1,2- ethylenediamines, N- [3- (three Methoxysilyl) propyl group] -1,2- ethylenediamines, N- [3- (triethoxysilyl) propyl group] -1,2- ethylenediamines, it is double - [3- (trimethoxysilyl) propyl group] amine, double-[3- (triethoxysilyl) propyl group] amine, 3- aminopropyl trimethoxies Base silane, APTES, 3- amino propyl methyls dimethoxysilane, 3- amino propyl methyl diethoxies Base silane, trimethoxy [3- (methylamino)] propyl silane, 3- (N- allyl aminos) propyl trimethoxy silicane, 3- (N- Allyl amino) propyl-triethoxysilicane, 3- (diethylamino) propyl trimethoxy silicane, 3- (diethylamino) propyl group The chemical combination such as triethoxysilane, 3- (phenyl amino) propyl trimethoxy silicane, 3- (phenyl amino) propyl-triethoxysilicane Thing.

The content of (e) amines in the photonasty substrate agent of the present invention is relative to described later by above-mentioned hyperbranched polymerization Complex (or total quality of above-mentioned dissaving polymer and metal particle) 100 mass parts that thing and metal particle are formed are preferred For the mass parts of 1 mass parts~100, the mass parts of more preferably 5 mass parts~50, the mass parts of particularly 10 mass parts~15.

In the case where the content of (e) amines is very few compared with above-mentioned number range, it is impossible to obtain described later by upper Dispersiveness, the dissolubility for stating complex that dissaving polymer and metal particle formed and (f) described later multi-functional thiol are steady Surely effect is changed, in addition, in the case of being added significantly exceeding above range (such as 10 mass of above-mentioned complex are measured again), Sometimes bad order occurs for plating envelope.

＜ (f) multi-functional thiols ＞

The multi-functional thiol as (f) composition used in photonasty substrate agent as the present invention, as long as with 2 The compound of above sulfydryl, is just not particularly limited, for example, can enumerate with hydro carbons of more than 2 sulfydryls as substituent, this Outside, as other polyfunctional compounds, the mercapto-carboxylic ester of polyalcohol, such as poly- (mercaptoacetate) of polyalcohol can be enumerated Class, poly- (3-thiopropionate) class of polyalcohol, poly- (2 mercaptopropionic acid ester) class of polyalcohol, poly- (the 3- sulfydryl fourths of polyalcohol Acid esters) class, poly- (the 3- mercaptoisobutanoics acid esters) class of polyalcohol etc..

In the photonasty substrate agent of the present invention, multi-functional thiol not only undertakes the effect as crosslinking agent, but also holds Carry on a shoulder pole the effect as chain-transferring agent, it may be said that help to realize excellent developability with high sensitivity in photoetching.

As the above-mentioned concrete example that there are more than 2 sulfydryls as the hydro carbons of substituent, the sulphur of hexane -1,6- bis- can be enumerated Double (mercapto methyl) benzene of alcohol, the mercaptan of decane -1,10- two, 1,4- dimercaptobenzenes, 1,4- etc..

In addition, the compound as other 2 functions, can enumerate double (the sulfydryl second of ethylene glycol double (mercaptoacetates), propane diols Acid esters), ethylene glycol double (3-thiopropionate), propane diols double (3-thiopropionates), ethylene glycol double (2 mercaptopropionic acid ester), third Glycol double (2 mercaptopropionic acid esters), diethylene glycol (DEG) double (2 mercaptopropionic acid esters), butanediol double (2 mercaptopropionic acid esters), ethohexadiol are double (2 mercaptopropionic acid ester), ethylene glycol double (3- mercaptobutylates), diethylene glycol (DEG) double (3- mercaptobutylates), double (the 3- sulfydryls of butanediol Butyrate), trimethylolpropane tris (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), (3- of dipentaerythritol six Mercaptobutylate), ethylene glycol double (3- mercaptoisobutanoics acid esters), diethylene glycol (DEG) double (3- mercaptoisobutanoics acid esters), double (the 3- sulfydryls of butanediol Isobutyrate), ethohexadiol double (3- mercaptoisobutanoics acid esters) etc..

As the compound of 3 functions, glycerine three (mercaptoacetate), trimethylolpropane tris (TGA can be enumerated Ester), glycerine three (3-thiopropionate), trimethylolpropane tris (3-thiopropionate), trimethylolpropane tris (2- sulfydryls third Acid esters), trimethylolpropane tris (3- mercaptoisobutanoics acid esters) etc..

As the compound of 4 functions, pentaerythrite four (mercaptoacetate), (the 3- mercaptopropionic acids of pentaerythrite four can be enumerated Ester), pentaerythrite four (2 mercaptopropionic acid ester), pentaerythrite four (3- mercaptoisobutanoics acid esters) etc..

As the compound of 6 functions, dipentaerythritol six (mercaptoacetate), (the 3- sulfydryls of dipentaerythritol six can be enumerated Propionic ester), dipentaerythritol six (2 mercaptopropionic acid ester), dipentaerythritol six (3- mercaptoisobutanoics acid esters), double (the 3- mercaptos of ethohexadiol Base butyrate) etc..

In these multi-functional thiols, from the viewpoint of the developability for improving photonasty substrate agent, preferably using 4 functions Mercaptan compound.

In the present invention, (f) multi-functional thiol can be used alone or be used in mixed way two or more.

The use level of (f) multi-functional thiol in the photonasty substrate agent of the present invention is relative to described later by above-mentioned hyperbranched The gross mass for the complex (or total quality of above-mentioned dissaving polymer and metal particle) that polymer and metal particle are formed The mass % of preferably 0.01 mass %~200, it is desired for the mass % of 0.05 mass %~50.If compounding ratio is above range Hereinafter, then it cannot get desired effect, on the other hand, if above range must be exceeded by adding, there is photonasty substrate agent Stability, peculiar smell, sensitivity, resolution ratio, developability, adaptation, plating the deterioration such as precipitation worry.

＜ photonasty substrate agent ＞

The photonasty substrate agent of the present invention, which includes above-mentioned (a) molecular end, has the dissaving polymer of ammonium, (b) metal Particulate, (c) polymerizable compound, (d) Photoepolymerizationinitiater initiater, (e) amines and (f) multi-functional thiol, enter one as needed Step includes other compositions, and now, preferably above-mentioned dissaving polymer forms complex with above-mentioned metal particle.

Here complex refers to connect with metal particle with effect by the ammonium of above-mentioned dissaving polymer end Both tactile or close states coexist, and form the form of particle shape, in other words, refer to there is the ammonium of above-mentioned dissaving polymer Adhere to or be coordinated in metal particle structure complex.

Accordingly, with respect to " complex " in the present invention, not only comprising metal particle as described above and dissaving polymer With reference to and form the situation of a complex, but also metal particle and dissaving polymer can be included and not form joint portion Divide, independently of one another existing situation.

The formation of the complex of dissaving polymer and metal particle with ammonium includes dissaving polymer in modulation It is carried out simultaneously during with the substrate agent of metal particle, as its method, there are following methods：Manufacture is carried out by rudimentary ammonium part Stabilized to a certain degree metal particle, the method that part is then exchanged using dissaving polymer；By with ammonium In the solution of the dissaving polymer of base, method that metal ion direct-reduction is formed to complex.For example, it is also possible to pass through The aqueous solution of metal salt is added in the solution dissolved with above-mentioned dissaving polymer and ultraviolet is irradiated to it, or in the over-expense The aqueous solution and reducing agent of metal salt etc. are added in fluidized polymer solution, metal ion is reduced, so as to form complex.

In ligand exchange method, by the rudimentary ammonium part of raw material and carried out metal particle stabilized to a certain degree can be with Manufactured using the method described in Jounal of Organometallic Chemistry 1996,520,143-162 etc.. The dissaving polymer with ammonium, room temperature (about 25 DEG C) can be dissolved in the reaction mixture of the metal particle of acquisition Or heating stirring, so as to obtain the Metal microparticle composite of target.

As used solvent, as long as can be dissolved to must by metal particle and dissaving polymer with ammonium Solvent more than concentration is wanted, is just not particularly limited, specifically, the alcohols such as ethanol, normal propyl alcohol, isopropanol can be enumerated；Dichloro The halogenated hydrocarbons such as methane, chloroform；The ring-type ethers such as tetrahydrofuran (THF), 2- methyltetrahydrofurans, oxinane；Acetonitrile, butyronitrile Deng nitrile etc. and the mixed liquor of these solvents, tetrahydrofuran can be preferably enumerated.

The temperature that the reaction mixture of metal particle is mixed with the dissaving polymer with ammonium can generally use 0 DEG C~scope of the scope of the boiling point of solvent, preferably room temperature (about 25 DEG C)~60 DEG C.

In addition, in ligand exchange method, by using phosphine system dispersant in addition to amine system dispersant (rudimentary ammonium part) (Phosphine ligands), also metal particle can be stabilized to a certain extent in advance.

As direct reduction process, by the way that metal ion and dissaving polymer with ammonium are dissolved in solvent, Make its reduction with the primary alconols such as methanol, ethanol, isopropanol, polyalcohol or secondary alcohol class, answered so as to obtain the metal particle of target It is fit.

As metal ion source used herein above, above-mentioned metal salt can be used.

As used solvent, as long as can be dissolved to must by metal ion and dissaving polymer with ammonium Solvent more than concentration is wanted, is just not particularly limited, specifically, the alcohols such as methanol, ethanol, propyl alcohol, isopropanol can be enumerated；Two The halogenated hydrocarbons such as chloromethanes, chloroform；The ring-type ethers such as tetrahydrofuran (THF), 2- methyltetrahydrofurans, oxinane；Acetonitrile, fourth The nitriles such as nitrile；The amide-types such as N,N-dimethylformamide (DMF), METHYLPYRROLIDONE (NMP)；The sulfoxides such as dimethyl sulfoxide The mixed liquor of class etc. and these solvents, alcohols, halogenated hydrocarbon, ring-type ethers can be preferably enumerated, can more preferably enumerate ethanol, different Propyl alcohol, chloroform, tetrahydrofuran etc..

The temperature of reduction reaction can generally use the scope of the boiling point of 0 DEG C~solvent, preferably room temperature (about 25 DEG C) ~60 DEG C of scope.

As other direct reduction process, by the way that metal ion and the dissaving polymer with ammonium are dissolved in into solvent In, make its reaction in a hydrogen atmosphere, so as to obtain the Metal microparticle composite of target.

As metal ion source used herein above, above-mentioned metal salt, chromium carbonyl [Cr (CO) can be used₆], five carbonyls Base iron [Fe (CO)₅], cobalt octacarbonyl [Co₂(CO)₈], nickel carbonyl [Ni (CO)₄] etc. metal-carbonyl complex.In addition, The metal-complexing of 0 valencys such as metal olefin complex, metal phosphinate complex, metal nitrogen complex can also be used Compound.

As used solvent, as long as can be dissolved to must by metal ion and dissaving polymer with ammonium Solvent more than concentration is wanted, is just not particularly limited, specifically, the alcohols such as ethanol, propyl alcohol can be enumerated；Dichloromethane, chloroform Deng halogenated hydrocarbon；The ring-type ethers such as tetrahydrofuran, 2- methyltetrahydrofurans, oxinane；Nitriles such as acetonitrile, butyronitrile etc. and this The mixed liquor of a little solvents, can preferably enumerate tetrahydrofuran.

The temperature that metal ion and the dissaving polymer with ammonium are mixed can generally be used into 0 DEG C~solvent Boiling point scope.

It is molten by the way that metal ion and dissaving polymer with ammonium are dissolved in addition, as direct reduction process In agent, it is set to carry out pyrolysis, so as to obtain the Metal microparticle composite of target.

As metal ion source used herein above, above-mentioned metal salt, metal-carbonyl complex, other can be used The metal oxides such as the metal complex of 0 valency, silver oxide.

As used solvent, as long as can be dissolved to must by metal ion and dissaving polymer with ammonium Solvent more than concentration is wanted, is just not particularly limited, specifically, methanol, ethanol, normal propyl alcohol, isopropanol, ethylene glycol can be enumerated Deng alcohols；The halogenated hydrocarbons such as dichloromethane, chloroform；The cyclic ethers such as tetrahydrofuran (THF), 2- methyltetrahydrofurans, oxinane Class；The nitriles such as acetonitrile, butyronitrile；Benzene, toluene etc. is aromatic hydrocarbon etc. and the mixed liquor of these solvents, can preferably enumerate toluene.

The temperature that metal ion and the dissaving polymer with ammonium are mixed can generally be used into 0 DEG C~solvent Boiling point scope, the temperature preferably near solvent boiling point, such as in the case of toluene be 110 DEG C (being heated to reflux).

The dissaving polymer with ammonium and the complex of metal particle for so operating and obtaining can be via sinking again The purification process such as shallow lake, are made the solid forms such as powder.

The photonasty substrate agent of the present invention, which includes above-mentioned (a), has dissaving polymer, (b) metal particle of ammonium (excellent The complex that choosing is formed by (a) and (b)), above-mentioned (c) polymerizable compound, above-mentioned (d) Photoepolymerizationinitiater initiater, (e) amine compounds Thing, (f) multi-functional thiol and further other compositions as needed, the photonasty substrate agent can be to be formed it is aftermentioned [non- Electrolysis plating basalis] when used varnish form.

The other additive ＞ of ＜

As long as the photonasty substrate agent of the present invention does not damage the effect of the present invention, it is possible to is further properly added surface work The additives such as additive, sensitizer, polymerization inhibitor, the polymerization initiators such as property agent, various surface conditioners.

As above-mentioned surfactant, can enumerate for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxy The polyoxyethylene alkyl ether class such as ethene cetyl ether, polyoxyethylene oleyl ether；NONIN HS 240, ethylene nonyl The polyoxyethylene alkylaryl ether class such as phenyl ether；Polyoxyethylene/polyoxypropylene block copolymers class；Anhydrosorbitol list bay Acid esters, sorbitan-monopalmityl ester, sorbitan monosterate, dehydrating sorbitol monooleate, dehydration The sorbitan fatty ester classes such as D-sorbite tristearate, anhydrosorbitol trioleate；Polyoxyethylene sorbitan D-sorbite monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan list are stearic The polyoxyethylene nonionic surfactants such as acid esters, polyoxyethylene sorbitan trioleate；エ Off ト ッ プ (registrars Mark) EF-301, エ Off ト ッ プ EF-303, エ Off ト ッ プ EF-352 [above be Mitsubishi マ テ リ ア Le electronics chemical conversion (strain) system], メ ガ Off ァ ッ Network (registration mark) F-171, メ ガ Off ァ ッ Network F-173, メ ガ Off ァ ッ Network R-08, メ ガ Off ァ ッ Network R-30 [with On, DIC (strain) systems], Novec (registration mark) FC-430, Novec FC-431 [above be Sumitomo ス リ ー エ system (strain) system], ア サ ヒ ガ ー De (registration mark) AG-710 [Asahi Glass (strain)], サ ー Off ロ Application (registration mark) S-382 processed [AGC セ イ ミ ケ ミ カ Le (strain) is made] etc. fluorine system surfactant etc..

In addition, as above-mentioned surface conditioner, SHIN-ETSU HANTOTAI シ リ コ ー Application (registration mark) KP-341 [SHIN-ETSU HANTOTAI's chemistry can be enumerated Industrial (strain) system] etc. silicon-type levelling agent；BYK (registration mark) -302, BYK 307, BYK 322, BYK 323, BYK 330th, the organosilicon such as BYK 333, BYK 370, BYK 375, BYK 378 [being made above for PVC ッ Network ケ ミ ー ジ ャ パ Application (strain)] It is surface conditioner etc..

These additives can be used alone, or can also and with more than two kinds.The usage amount of additive is relative In the mass parts of complex 100 formed by above-mentioned dissaving polymer and metal particle be preferably 0.001~50 mass parts, it is more excellent Elect 0.005~10 mass parts, more preferably 0.01~5 mass parts as.

[electroless plating basalis]

The photonasty substrate agent of the invention described above is coated on base material, film is formed, is carried out photoetching, so as to Obtain the electroless plating basalis for foring pattern.The basalis is also the object of the present invention.

As above-mentioned base material, it is not particularly limited, can preferably uses non-conductive base material or conductive substrate.

As non-conductive base material, can enumerate such as glass, ceramics；Polyvinyl resin, acrylic resin, vinyl chloride tree Fat, nylon (polyamide), polyimide resin, polycarbonate resin, acrylic resin, PEN (poly- naphthalenedicarboxylic acid second two Alcohol ester) resin, PET (polyethylene terephthalate) resin, PEEK (polyether-ether-ketone) resin, ABS (acrylonitrile-butadiene- Styrol copolymer) resin, epoxy resin, polyacetal resin etc.；Paper etc..They are adapted to use in the form of piece or film etc., close In thickness in this case, it is not particularly limited.

In addition, as conductive substrate, such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), FTO can be enumerated (fluorine-doped tin oxide), AZO (aluminium-doped zinc oxide), GZO (Ga-doped zinc oxide) and various stainless steels, aluminium and duralumin Deng copper alloy, nickel and nickel alloy and the silver such as aluminium alloy, iron and ferroalloy, copper and brass, phosphor bronze, copper-nickel alloy and beryllium copper And metal such as silver alloy such as nickeline etc..

It can also further use and form what film formed by these conductive substrates on above-mentioned non-conductive base material Base material.

In addition, above-mentioned base material can be three-dimensionally shaped body.

As by triggering containing the above-mentioned dissaving polymer with ammonium, metal particle, polymerizable compound, photopolymerization Agent, the photonasty substrate dosage form of amines and multi-functional thiol make first into the specific method of electroless plating basalis State the dissaving polymer with ammonium and metal particle (being preferably the complex formed by them), polymerizable compound, light Polymerization initiator, amines and multi-functional thiol are dissolved or dispersed in appropriate solvent to form the form of varnish, profit Use method of spin coating；Scraper plate rubbing method；Dipcoat method；Rolling method；Stick coating method；Die coating method；Spraying process；Ink-jet method；Running water Nano photolithography (fountain pen nanolithography) (FPN), dip in a photoetching such as a nano photolithography (DPN) Method；Typographic printing, flexographic printing, resin relief printing, contact printing, micro-contact printing (μ CP), nano-imprint lithography (NIL), The toppan printings such as nanometer transfer printing (nTP)；The woodburytypes such as intaglio printing (gravure printing), engraving；Lithographic plate prints Brush method；The porous printing method such as silk-screen printing, stencil；Offset printing method etc., the varnish is coated on metal-plated quilt to be formed On the base material of film, then, make solvent evaporation, dry, so as to form thin layer.

In these coating methods, preferably method of spin coating, spraying process, ink-jet method, a photoetching process, contact printing, μ CP, NIL and nTP.In the case of using method of spin coating, it can be coated with the short time, even therefore volatility height Solution can also utilize, in addition, with the advantages of high coating of uniformity is such can be carried out.In the situation using spraying process Under, the high coating of uniformity can be carried out with minimal amount of varnish, industrially becomes favourable in the extreme.Using ink-jet method, In the case of photoetching process, contact printing, μ CP, NIL, nTP, such as it can efficiently form (description) and the fine figure such as connect up Case, industrially become favourable in the extreme.

In addition, as solvent used herein above, as long as dissolving or scattered above-mentioned complex (have the hyperbranched of ammonium Polymer and metal particle), polymerizable compound, Photoepolymerizationinitiater initiater, the solvent of amines and multi-functional thiol, just not by It is particularly limited to, can uses for example, water；Benzene,toluene,xylene, ethylbenzene, chlorobenzene, dichloro-benzenes etc. are aromatic hydrocarbon；Methanol, second The alcohols such as alcohol, normal propyl alcohol, isopropanol, n-butanol, 2- butanol, n-hexyl alcohol, n-octyl alcohol, sec-n-octyl alcohol, 2-Ethylhexyl Alcohol；The molten fibre of methyl The dioxanes such as agent, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether；Propylene glycol monomethyl ether (PGME), propane diols list second Base ether, glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ehter, dipropylene glycol monomethyl ether, triethylene glycol list first Base ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Base ether, diethylene glycol dibutyl ether, diethylene glycol (DEG) ethyl-methyl ether, diethylene glycol (DEG) butyl methyl ether, diethylene glycol (DEG) isopropyl methyl ether, double third The glycol ethers such as glycol dimethylether, triglyme, tripropylene glycol dimethyl；Ethylene glycol single methyl ether acetic acid esters, The diol-lipids such as propylene glycol monomethyl ether (PGMEA)；Tetrahydrofuran (THF), methyltetrahydrofuran, 1,4- bis-Alkane, The ethers such as ether；The esters such as ethyl acetate, butyl acetate；Acetone, butanone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, The ketones such as cyclohexanone；The aliphatic hydrocarbons such as normal heptane, n-hexane, hexamethylene；The halogenated aliphatic hydrocarbons such as 1,2- dichloroethanes, chloroform Class；The amide-types such as METHYLPYRROLIDONE (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide；Diformazan Sulfoxide etc..These solvents can be used alone, and can also mix solvent of more than two kinds.And then to adjust the viscosity of varnish as mesh , the glycols such as ethylene glycol, propane diols, butanediol can be added.

In addition, the concentration for being dissolved or dispersed in above-mentioned solvent is arbitrary, but the above-mentioned compound bulk concentration in varnish is 0.005~90 mass %, preferably 0.01~80 mass %.

As the seasoning of solvent, it is not particularly limited, for example, using electric hot plate, baking oven, it is i.e. big under appropriate atmosphere The non-active gas such as gas, nitrogen, vacuum are medium to evaporate it.Thereby, it is possible to obtain the substrate with uniform film forming face Layer.As long as firing temperature can evaporate solvent, just it is not particularly limited, preferably in 40~250 DEG C of progress.

Then, to the film that is obtained as described above across the mask with predetermined pattern with 10~3,000mJ/cm²It is left Right light exposure is exposed, and is next developed using developer solution, so as to which exposure portion is washed out, can obtain patterning Electroless plating basalis.

In above-mentioned exposure, the ultraviolet such as mercury lamp, far ultraviolet, electron ray or X ray etc. can be used.Make For light source used in ultraviolet irradiation, sunray, chemical lamp, low pressure mercury lamp, high-pressure sodium lamp, metal halide can be used Lamp, xenon lamp, UV-LED etc..

In addition, as developing method, be not particularly limited, can by covering liquid method, paddling process, infusion process, gunite, shake Method known to infusion process etc. is moved to carry out.Development temperature is preferably between 20~50 DEG C, and developing time is such as 10 seconds~10 Minute.

As above-mentioned developer solution, organic solvent or alkaline aqueous solution etc. can be used.As organic solvent, example can be enumerated Such as, the alcohols such as methanol, ethanol, normal propyl alcohol, isopropanol；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, propane diols list first The glycol ethers such as base ether (PGME), MMB；Ether, Di Iso Propyl Ether, dibutyl ethers, tetrahydrofuran (THF), 1,4- bis-The ethers such as alkane；The ether-ether classes such as propylene glycol monomethyl ether (PGMEA)；Ethyl acetate, butyl acetate Etc. esters；The ketones such as acetone, cyclohexanone；The acid amides such as METHYLPYRROLIDONE (NMP), DMAC N,N' dimethyl acetamide (DMAc) Class；Sulfoxide types such as dimethyl sulfoxide etc..

In addition be used as alkaline aqueous solution, can enumerate for example, the alkali metal hydroxide such as potassium hydroxide, sodium hydroxide it is water-soluble Liquid；The aqueous solution of the quaternary ammonium hydroxides such as TMAH, tetraethyl ammonium hydroxide, choline；Monoethanolamine, propyl group amine, second two Amine aqueous solutions such as amine, morpholine etc..

These developer solutions can be used alone, and can also mix two or more.As mixed solution, use example can be adapted to Such as, PGME/PGMEA mixed solutions (mass ratio 7:3) etc..

In these developer solutions, in order to adjust developability, water can be added；The glycol such as ethylene glycol, propane diols, polyethylene glycol Class.And then in order to improve the removability in unexposed portion, surfactant etc. can be added.

In addition, above-mentioned developer solution can use commercially available product well, can enumerate for example, OK73 シ ン ナ ー (diluent) [answering chemical industry (strain) in Tokyo] etc..

It is preferred that after development, implement the washing carried out using water or common organic solvents in such as 20~90 seconds or so.Then, Done using compressed air or compressed nitrogen or by being rotated into sector-style, so as to remove the moisture on base material.As needed using electricity Hot plate or baking oven etc. are thermally dried, and obtain the electroless plating basalis for forming pattern.

[electroless plating processing, metal coating, metal are by film base material]

By carrying out electroless plating to the electroless plating basalis operated as explained above to be formed on the base material that obtains, So as to form metal coating on electroless plating basalis.So operate and obtain metal coating and on base material successively Possess electroless plating basalis, metal coating metal by film base material be also the present invention object.

Electroless plating processing (process) is not particularly limited, and can be handled using commonly known any electroless plating to enter OK, for example, typically using in the past commonly known non-electrolytic plating solution, the electroless plating basalis formed on base material is impregnated Method in the plating solution (bath).

Above-mentioned non-electrolytic plating solution generally mainly contains metal ion (metal salt), complexing agent, reducing agent, except these with Outside, pH adjusting agent, pH buffer, reaction promoter (the second complexing agent), stabilizer, surface work can suitably be included according to purposes Property agent (gloss purposes being assigned to plated film, the wetability of processed surface improves purposes etc.) etc..

As here by electroless plating and metal used in the metal coating that is formed, can enumerate iron, cobalt, nickel, copper, Palladium, silver, tin, platinum, gold and their alloy, suitably selected according to purpose.

In addition on above-mentioned complexing agent, reducing agent, and according to metal ion progress suitably selection.

In addition, non-electrolytic plating solution can use commercially available plating solution, can be adapted to using such as メ Le テ ッ Network ス (strain) systems Process for electroless nickel plating chemicals (メ Le プ レ ー ト (registration mark) NI series), non-electrolytic copper facing chemicals (メ Le プ レ ー ト (notes Volume trade mark) CU series)；Process for electroless nickel plating liquid (ICP ニ U ロ Application (registration mark) series, the ト ッ of wild pharmaceuticals industry (strain) system difficult to understand プ ピ エ Na 650), electroless plating copper liquid (OPC-700 non-electrolytic copper M-K, ATS ア De カ ッ パ ー IW, ATS ア De カ ッ パ ー CT, OPC カ ッ パ ー (registration mark) AF series, OPC カ ッ パ ー HFS, OPC カ ッ パ ー NCA), electroless plating tin liquor (サ Block ス タ ー SN-5), electroless plating gold liquid (Off ラ ッ シ ュ ゴ ー Le De 330, セ Le フ ゴ ー Le De OTK-IT), electroless plating Silvering solution (system デ Application シ ル バ ー)；Electroless plating palladium liquid (パ レ ッ ト II), the electroless plating gold liquid of island chemicals (strain) system (デ ィ ッ プ G series, NC ゴ ー Le De series)；Electroless plating silvering solution (the エ ス ダ イ ヤ AG- of assistant assistant wooden chemistry medicine (strain) system 40)；Process for electroless nickel plating liquid (カ ニ ゼ Application (registration mark) series, the シ ュ ー マ ー (registrars of Japanese カ ニ ゼ Application (strain) system Mark) series, シ ュ ー マ ー (registration mark) カ ニ Block ラ ッ Network (registration mark) series), electroless plating palladium liquid (S-KPD)；ダ Electroless plating copper liquid (キ ュ ー Port ジ ッ ト (registration mark) カ ッ パ ー ミ ッ Network ス series, サ ー キ ュ of ウ ケ ミ カ Le society Port ジ ッ ト (registration mark) series), electroless plating palladium liquid (パ ラ マ ー ス (registration mark) series), process for electroless nickel plating liquid (デ ュ ラ Port ジ ッ ト (registration mark) series), electroless plating gold liquid (オ ー ロ レ Network ト ロ レ ス (registration mark) series), non-electrical Solve tin plating electrolyte (テ ィ Application Port ジ ッ ト (registration mark) series), electroless plating copper liquid (the ス Le カ ッ プ (notes of upper village industrial (strain) system Volume trade mark) ELC-SP, ス Le カ ッ プ PSY, ス Le カ ッ プ PCY, ス Le カ ッ プ PGT, ス Le カ ッ プ PSR, ス Le カ ッ プ PEA), electroless plating copper liquid (プ リ Application ト ガ Application ト (registration mark) PV) of ア ト テ ッ Network ジ ャ パ Application (strain) system etc..

Above-mentioned electroless plating process can be by adjusting the temperature of plating bath, pH, dip time, concentration of metal ions, stirring The presence or absence of, the presence or absence of mixing speed, air/oxygen supply, feed speed etc. control the formation speed of metal envelope, thickness.

Thus, on the sheet formed with metal coating on the basalis obtained using photonasty substrate agent of the invention The metal of invention is by film base material, in the case where using transparent base as base material, can make from that formed with plating envelope Black is presented in the face that can be seen during the opposite sides observation transparent base of side.

Therefore, by that to implementing metal coating on the basalis of pattern using photoetching to be formed, can be patterned Plating envelope form the metal of the back side of part for black by film base material, therefore can using the base material as visibility of image High transparency electrode uses.

Embodiment

The present invention is further specifically described by the following examples, but the present invention is not limited by it.In embodiment, examination The physical property measurement of sample is carried out using following apparatus under the following conditions.

(1) GPC (gel permeation chromatography)

Device：East ソ ー (strain) HLC-8220GPC processed

Post：Showa electrician (strain) Shodex processed (registration mark) GPC KF-804L+Shodex GPC KF-803L

Column temperature：40℃

Solvent：Tetrahydrofuran

Detector：UV (254nm), RI

(2)¹H NMR spectras

Device：JEOL (strain) JNM-L400 processed

Solvent：CDCl₃

Reference peaks：Tetramethylsilane (0.00ppm)

(3)¹³C NMR spectras

Device：JEOL (strain) JNM-ECA700 processed

Solvent：CDCl₃

Relaxation reagent：Praseodynium chromium (Cr (acac)₃)

Reference peaks：CDCl₃(77.0ppm)

(4) ICP luminesceence analyses (inductively coupled plasma luminesceence analysis)

Device：(strain) Shimadzu Seisakusho Ltd. ICPM-8500

(5) TEM (transmission electron microscope) image

Device：(strain) Hitachi Ha イ テ Network ノ ロ ジ ー ズ H-8000

(6) pattern exposure (mask aligner)

Device：ズ ー ス マ イ Network ロ テ ッ Network society MA6

(7) develop

Device：Make small-sized developing apparatus ADE-3000S in ア Network テ ス capital three (strain)

(8) digital microscope images

Device：(strain) キ ー エ Application ス VHX-2000

In addition, used abbreviation is as described below.

HPS：Superbranched polystyrene [Nissan Chemical Industries (strain) Ha イ パ ー テ ッ Network (registration mark) HPS-200 processed]

DP6A-12E：Ethylene-oxide-modified dipentaerythritol acrylate (ethyleneoxide addition molal quantity 12) is [in new Village's chemical industry (strain) NK エ ス テ Le A-DPH-12E processed]

G3A-20E：Ethylene-oxide-modified glycerol tri-acrylate (ethyleneoxide addition molal quantity 20) [Xin Zhong villages chemistry work Industry (strain) NK エ ス テ Le A-GLY-20E processed]

P4A-35E：Ethylene-oxide-modified tetramethylol methane tetraacrylate (ethyleneoxide addition molal quantity 35) [Xin Zhong villages Learn industry (strain) NK エ ス テ Le ATM-35E processed]

T3A-20E：Ethylene-oxide-modified trimethylolpropane trimethacrylate (ethyleneoxide addition molal quantity 20) is [in new Village's chemical industry (strain) NK エ ス テ Le AT-20E processed] UA4200：The function urethane acrylate of polyether skeleton 2 is [in new Village's chemical industry (strain) NK オ リ go UA-4200 processed]

UA7100：The function urethane acrylate of polyether skeleton 3 [Xin Zhong villages chemical industry (strain) NK オ リ go processed UA-7100]

TPO：Diphenyl (2,4,6- trimethylbenzoyls) phosphine oxide (Photoepolymerizationinitiater initiater) [BASF ジ ャ パ Application (strain) IRGACURE (registration mark) TPO processed]

IPA：Isopropanol

IPE：Di Iso Propyl Ether

PGME：Propylene glycol monomethyl ether

PGMEA：Propylene glycol monomethyl ether

PrOH：Normal propyl alcohol

KBM-903：3- TSL 8330s [SHIN-ETSU HANTOTAI of Shin-Etsu Chemial Co., Ltd シ リ コ ー Application (registration mark) KBM-903]

i-PrNH2：Isopropylamine

2-BuNH2：Sec-butylamine

n-OctylNH2：N-octylamine

n-DecylNH2：Positive decyl amine

2EHA：2- DEHAs

2MCHA：2- methylcyclohexyl amine

Aniline：Aniline

o-Toluidine：Ortho-aminotoluene

p-Toluidine：Para-totuidine

o-Anisidine：O-anisidine

PE1：Pentaerythrite four (3- mercaptobutylates) [Showa Denko K. K カ レ Application ズ MT (registration mark) PE1)

BD1：Double (3- sulfydryls butyryl acyloxy) butane [the Showa Denko K. K's カ レ Application ズ MT (registrars of 1,4- Mark) BD1]

TPMB：Trimethylolpropane tris (3- mercaptobutylates) [Showa Denko K. K TPBM]

[Production Example 1] HPS-Cl manufacture

Sulfonic acid chloride [キ シ ダ chemistry (strain) system] 27g and chloroform 50g is added in 500mL reaction flask, is stirred And it is set equably to dissolve.The solution is cooled to 0 DEG C under stream of nitrogen gas.

Molecular end is added in another 300mL reaction flask has the hyperbranched polymerization of dithiocarbamate groups Thing HPS 15g and chloroform 150g, it is stirred under stream of nitrogen gas until becoming uniform.

Under stream of nitrogen gas, into the above-mentioned sulfonic acid chloride/chloroformic solution for being cooled to 0 DEG C, using delivery pump, have from addition In the above-mentioned 300mL of HPS/ chloroformic solutions reaction flask 60 points are lasted in a manner of the temperature of reaction solution is turned into -5~5 DEG C Clock adds the solution.After addition terminates, while the temperature of reaction solution is maintained at into -5~5 DEG C while stirring 6 hours.

And then added in a manner of the temperature of reaction solution is turned into -5~5 DEG C into the reaction solution by cyclohexene [Tokyo Into industrial (strain) system] 16g be dissolved in chloroform 50g obtained by solution.After addition terminates, the reaction solution is added to IPA1, In 200g, precipitate polymer.The white powder that the leaching precipitation is obtained is dissolved in chloroform 100g, is added it to In IPA 500g, make polymer reprecipitation.The sediment is filtered under diminished pressure, is dried in vacuo, is obtained in the form of white powder Obtaining molecular end has dissaving polymer (HPS-Cl) 8.5g (yield 99%) of chlorine atom.

By the HPS-Cl's of acquisition¹H NMR spectras are shown in Figure 1.From the peak of dithiocarbamate groups (4.0ppm, 3.7ppm) disappears, and thus specify that：In the HPS-Cl of acquisition, the dithiocarbamate of HPS molecular ends Base is substantially all to be substituted by a chlorine atom both.In addition, it is that the HPS-Cl obtained is measured using GPC, with polystyrene convert what is obtained Weight average molecular weight Mw is 14,000, and decentralization Mw/Mn is 2.9.

[Production Example 2] HPS-N (Me)₂OctCl manufacture

The HPS-Cl 4.6g manufactured by Production Example 1 are added in the 100mL reaction flask of cooler is provided with (30mmol) and chloroform 15g, it is stirred until becoming uniform.Added into the solution in chloroform 7.5g and be dissolved with dimethyl-octa Base amine [flower king (strain) フ ァ ー ミ Application (registration mark) DM0898 processed] solution obtained by 5.0g (31.5mmol), further addition IPA 7.5g.The mixture is stirred 40 hours in a nitrogen atmosphere, at 65 DEG C.

Fluid temperature is cooled to 30 DEG C, then solvent be distilled off.The residue of acquisition is dissolved in chloroform 60g, The solution is added in IPE 290g and carries out reprecipitation purifying.The polymer of precipitation is filtered under diminished pressure, carried out at 50 DEG C true Sky is dried, and molecular end is obtained in the form of white powder has the dissaving polymer (HPS-N of dimethyl octyl group ammonium (Me)₂OctCl)9.3g。

By the HPS-N (Me) of acquisition₂OctCl's¹³C NMR spectras are shown in Figure 2.By the peak of phenyl ring and the first of octyl group end The peak of base specify that：In the HPS-N (Me) of acquisition₂In OctCl, the chlorine atom of HPS-Cl molecular ends is substantially quantitatively by ammonium Base instead of.In addition, the HPS-N (Me) calculated by HPS-Cl Mw (14,000) and ammonium Drug delivery rate (100%)₂OctCl's Weight average molecular weight Mw is 28,000.

[Production Example 3] HBP-Pd-1 manufacture

Acid chloride is added in the 100mL reaction flask of cooler is provided with and [grinds Off ァ イ Application ケ ミ カ Le products in river (strain) makes] 4.2g and chloroform 40g, it is stirred until becoming uniform.Added using dropping funel into the solution in chloroform The HPS-N (Me) manufactured by Production Example 2 is dissolved in 100g₂Solution obtained by OctCl8.0g.Use 40g pairs of chloroform 20g and ethanol Washed in the dropping funel, cleaning solution is flowed into above-mentioned reaction flask.By the mixture in a nitrogen atmosphere, at 60 DEG C Stirring 8 hours.

Fluid temperature is cooled to 30 DEG C, the solution is then added to IPE/ hexane solutions (mass ratio 10：1)2,000g In, carry out reprecipitation purifying.The polymer of precipitation is filtered under diminished pressure, is dried in vacuo at 50 DEG C, in the form of black powder Obtaining molecular end has the dissaving polymer of ammonium and the complex (Pd [HPS-N (Me) of Pd particles₂OctCl])8.9g (HBP-Pd-1)。

From the result of ICP luminesceence analyses, the Pd [HPS-N (Me) of acquisition₂OctCl] the Pd contents of (HBP-Pd-1) are 20 mass %.In addition, from TEM (transmission electron microscope) image, the Pd particle diameters are about 2~4nm.

The modulation of [reference example 1] process for electroless nickel plating liquid

カ ニ ゼ Application (registration mark) ブ ル ー シ ュ ー マ ー [Japanese カ ニ ゼ Application (strain) are added in 2L beaker System] 100mL, further adds pure water so that the total amount of solution turns into 400mL.The solution is stirred, electroless plating is made Nickel liquid.

[embodiment 1]

[modulation of photonasty substrate agent]

(it is also referred to as the mass parts of HBP-Pd-1 7 manufactured by Production Example 3 of Pd catalyst, as amines below For " amine ") the mass parts of KBM-903 0.875, the mass parts of T3A-20E 80 as polymerizable compound, as multifunctional sulphur The mass parts of PE1 0.8 of alcohol (also referred to as RSH), the mass parts of TPO 20 as polymerization initiator and mixed as the PrOH of solvent Close, modulate the sense of the mass % of non-solvent ingredients (whole compositions after solvent are removed in mixture) concentration 1 electroless plating Photosensitiveness substrate agent.In addition, making each composition dissolve respectively in advance with a part for PrOH usage amount, the liquid of gained is mixed, So as to which easily each composition is equably mixed.

Middle used HBP-Pd-1 is mixed with amines in advance according to following steps and formed in addition, above-mentioned Amine complex, then it is mixed with other compositions of photonasty substrate agent.

＜ amine complex forms ＞

The HBP-Pd-1 500mg manufactured by above-mentioned Production Example 3 are dissolved in PGME (solution 1), turn into solution total amount 5g, then stirred 30 minutes using stirring rotator.

On the other hand, the KBP-903 1.25g as amines are dissolved in PGME (solution 2), make the solution total Amount turns into 5g, is stirred using stirring rotator.The solution 2 is further diluted 10 times using PGME.

The solution 2 (amines) that addition 2.5g diluted into solution 1 (HBP-PD-1), further adds PGME, makes Total amount turns into 10g.

Use the 140mg HBP-PD-1 obtained by this step 5 mass % solution.

[coating]

By above-mentioned photonasty substrate agent 2.4mL rotary coatings (200rpm × 5 second, then 1,000rpm × 25 second) in 4 English On very little wafer shape glass substrate.The base material is dried 1 minute using 65 DEG C of electric hot plate, the whole face on base material that obtains possesses The base material of basalis.

[pattern forms (exposed and developed)]

Using there is provided describe have 3 μm of wide patterns photomask mask aligner, in air atmosphere, with 14.6mW/cm²Illumination to the basalis of acquisition so that light exposure turns into 400mJ/cm²Mode be irradiated and expose.

The base material exposed is developed using the developing apparatus for being provided with spray spout.On development, while making base Material carries out rotation while being washed with water 90 seconds with 300rpm, then improves rotating speed to 2,000rpm and gets rid of water.

The base material is dried 30 seconds using 65 DEG C of electric hot plate, dries 5 minutes, obtains followed by 150 DEG C of electric hot plates Possesses the base material of the electroless plating basalis to form pattern on base material.

[electroless plating]

The base material of acquisition is impregnated 3 minutes in the process for electroless nickel plating liquid modulated by reference example 1 for be heated to 80 DEG C.So Afterwards, the base material of taking-up is washed, dried 3 minutes using 100 DEG C of electric hot plates, so as to obtain plating base.

On the metal coating on the plating base, evaluated by visual observation from glass substrate back side institute according to following benchmark The plating envelope of observation forms the blackened state of part and plating forms state.Result is shown in Table 1 in the lump.

＜ platings form state evaluation benchmark ＞

OK：The substrate layer pattern as mask pattern can be obtained, is separated out in basalis drafting department coating and (forms pattern The plating envelope changed)

NG：The plating envelope of patterning is not formed

The blackened metewand ＞ in the ＜ back sides

A：By fully blackened

B：It was observed that brown

C：Effect is not observed

[embodiment 2~21]

Each composition of photonasty substrate agent is altered to the record of table 1, in addition, operates, enters similarly to Example 1 Evaluation is gone.Result is shown in Tables 1 and 2 in the lump.In addition, in Tables 1 and 2, it is [molten in 5~embodiment of embodiment 11 Agent] numerical value [PGME described in column:PrOH=8:2] represent that 2 kinds of solvent PGME and PrOH is with 8 by used in:2 mass ratio Example uses.

In addition, the digital microscope images of the metal coating obtained by embodiment 7 are shown in Figure 3, will with by embodiment 7 Fig. 3 of the metal coating of acquisition image is compared to digital microscope images (about 1/10 times of Fig. 3 for showing large-scale appearance Rate is so low) it is shown in Figure 4.

[1~comparative example of comparative example 3]

Each composition of photonasty substrate agent is altered to each composition that table 1 records, in addition, similarly to Example 1 Operation, is evaluated.Result is shown in Table 1 in the lump.In addition, comparative example 1 and comparative example 2 are without the plating for forming patterning Envelope, therefore the blackened evaluation in the back side is not carried out.In addition, although comparative example 3 obtains the pattern of plate substrate layer by exposure, But flowed by subsequent development, the pattern of basalis, become whole face plating, therefore do not carry out the blackened evaluation in the back side.

As shown in table 1, basalis is being formed using the photonasty substrate agent of the present invention, it is being exposed across mask Light, the electroless plating basalis patterned is then obtained by development, plated film is formed on the electroless plating basalis In the case of (1~embodiment of embodiment 7), plating envelope (reference picture 3 and Fig. 4) is substantially formd as mask pattern.This Outside, in polyfunctional carbamate (methyl) acroleic acid esterification for having used intramolecular that there is more than 3 (methyl) acryloyl groups Compound (UA7100) is as in the 4~embodiment of embodiment 7 of (c) polymerizable compound, as a result for from glass substrate back side To plating envelope formed part show black or brown.

On the other hand, the comparative example 1 of amine and comparative example 2 are being not added with, is being not added with the comparative example 3 of multi-functional thiol, do not had There is the plate substrate layer to be formed and patterned, do not form the plating envelope patterned.

In addition, in the amine of addition has been carried out into 8~embodiment of embodiment 17 of various changes, figure is all substantially obtained The plating envelope of case.

In addition, in any embodiment, can be developed after the exposure after forming basalis using water.

It specify that by result above：The photonasty substrate agent of the present invention can form the plating patterned by photoetching Basalis, it is favourable in terms of obtaining width and being several μm of so fine metal coatings.

Claims (15)

1. a kind of photonasty substrate agent, metal coating is formed on base material for being handled by electroless plating, it includes：

(a) molecular end has the dissaving polymer that ammonium and weight average molecular weight are 1,000~5,000,000,

(b) metal particle,

(c) intramolecular has the polymerizable compound of more than 1 (methyl) acryloyl group,

(d) Photoepolymerizationinitiater initiater,

(e) amines, and

(f) multi-functional thiol.

2. photonasty substrate agent according to claim 1, (c) polymerizable compound is that intramolecular has more than 3 The compound of (methyl) acryloyl group.

3. photonasty substrate agent according to claim 1 or 2, (c) polymerizable compound be intramolecular have 3 with Upper (methyl) acryloyl group and the compound with oxyalkylene.

4. the photonasty substrate agent according to any one of claims 1 to 3, (f) multi-functional thiol is 4 function sulphur Alcohol.

5. the photonasty substrate agent according to any one of Claims 1 to 4, (e) amines is with alcoxyl The amines of base silicyl.

6. the photonasty substrate agent according to any one of Claims 1 to 5, (a) dissaving polymer is formula [1] Shown dissaving polymer,

In formula [1], R¹Hydrogen atom or methyl are represented independently of one another,

R²~R⁴Alkyl, the carbon atom of hydrogen atom, the straight-chain of carbon number 1~20, branched or ring-type are represented independently of one another The aryl alkyl of number 7~20 or-(CH₂CH₂O)_mR⁵, or R²~R⁴In 2 groups represent straight-chain, branched or ring together The alkylidene of shape, or R²~R⁴Ring is formed together with the nitrogen-atoms combined with them,

Above-mentioned formula-(CH₂CH₂O)_mR⁵In, R⁵Hydrogen atom or methyl are represented, m represents 2~100 integer, abovementioned alkyl and aryl alkane Base can be substituted by alkoxy, hydroxyl, ammonium, carboxyl or cyano group,

X^-Represent anion,

N is the number of repeat unit structure, represents 5~100,000 integer,

A¹Structure shown in expression [2],

In formula [2], A²Represent to include the alkylene of the straight-chain of the carbon number 1~30 of ehter bond or ester bond, branched or ring-type Base, Y¹~Y⁴Independently of one another represent hydrogen atom, the alkyl of carbon number 1~20, the alkoxy of carbon number 1~20, nitro, Hydroxyl, amino, carboxyl or cyano group.

7. photonasty substrate agent according to claim 6, (a) dissaving polymer is hyperbranched shown in formula [3] Polymer,

In formula [3], R¹~R⁴With n respectively with above-mentioned R¹~R⁴Identical meanings are represented with n.

8. the photonasty substrate agent according to any one of claim 1~7, (b) metal particle is selected from iron (Fe), at least one of cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold (Au) metal Particulate.

9. photonasty substrate agent according to claim 8, (b) metal particle is palladium particulate.

10. the photonasty substrate agent according to any one of claim 1~9, (b) metal particle is average grain diameter 1~100nm particulate.

11. the photonasty substrate agent according to any one of claim 1~10, it can carry out pattern by photoetching Formed.

12. a kind of electroless plating basalis, it is using the patterned layer being lithographically derived, by any one of claim 1~11 Described photonasty substrate dosage form into.

13. a kind of metal coating, it is as the electroless plating basalis described in claim 12 and in the electroless plating basalis The electroless plating of upper formation is formed.

14. a kind of metal, by film base material, it possesses：

Base material,

Electroless plating basalis described in the claim 12 formed on the substrate, and

The metal coating described in claim 13 formed on the electroless plating basalis.

15. a kind of metal, by the manufacture method of film base material, it includes following A process~C processes,

A processes：Photonasty substrate agent described in any one of claim 1~11 is coated on base material, it is possessed base The process of bottom,

B processes：Process by being lithographically formed the basalis with expected pattern,

C processes：The base material that will be provided with being formed the basalis of pattern is impregnated in non-electrolytic plating bath, the process for forming metal coating.