CN107532302B - Photonasty electroless plating substrate agent - Google Patents

Photonasty electroless plating substrate agent Download PDF

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Publication number
CN107532302B
CN107532302B CN201680020173.7A CN201680020173A CN107532302B CN 107532302 B CN107532302 B CN 107532302B CN 201680020173 A CN201680020173 A CN 201680020173A CN 107532302 B CN107532302 B CN 107532302B
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methyl
amine
metal
electroless plating
substrate
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CN107532302A (en
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小岛圭介
畑中真
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Abstract

The project 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 being able to easily form width by photoetching is several μm of wirings fine in this way.It is a kind of photonasty substrate agent as the method for solving project of the present invention; metal coating is formed on substrate for handling by electroless plating; it includes: (a) molecular end has ammonium and weight average molecular weight is 1; 000~5; 000,000 dissaving polymer, (b) metal particle, (c) intramolecular have the polymerizable compound of 1 or more (methyl) acryloyl group, (d) Photoepolymerizationinitiater initiater, (e) amine compounds and (f) multi-functional thiol.

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 technique
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, visibility on the transparent substrate, it is desirable that the method for fine wiring pattern case easy to form.
As one of the method for forming fine wiring, discloses and electroless plating catalyst is formed by pattern by photoetching, so Implement the method (patent document 1) of electroless plating afterwards.Specifically, disclosing following methods: using being mixed in photoresist There is the material of metal complex, metal ion or metallic colloid as electroless plating catalyst etc., by covering across light UV exposure, the development of mould, form the substrate of the arbitrary graphic patterns such as clathrate, implement electroless plating to it, to obtain electric conductivity figure The method of case.
Furthermore there is disclosed following examples: by using the combination comprising dissaving polymer and Pd particle with ammonium Object comes as electroless plating substrate agent to only not be impregnated in electroless plating solution directly via coating post activation process It is formed electroless plating (patent document 2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-170421 bulletin
Patent document 2: No. 2012/141215 pamphlet of International Publication No.
Summary of the invention
Problems to be solved by the invention
In above 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 the varnish as caused by the decomposition of protecting colloid, agglutination of metallic colloid etc. Troubling, and in process, it is more to be difficult to the case where washing for catalyst when development.In addition, in electroless plating, in target portion Divide to be precipitated with serving and also becomes problem.In turn, due to using water-soluble resist, metallic stabilizer, 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 transparent conductive film of acquisition It is discussed with resistance value, the line width (shape) of the pattern of acquisition is not made in detail.
In addition, requiring the visibility of image for the transparent electrode used in liquid crystal display element etc..However, passing through Electroless plating in the case where forming metal line, is formed by metal envelope with metallic luster, reflects exterior light, therefore With being difficult to manufacture, metal line is unobvious, visibility of image is high clearly shows that device such problems.Therefore, for logical Electroless plating is crossed to form the technology of transparent electrode, it is desirable that by the back side (transparent substrate face) for being formed by metal-plated envelope It is blackened that metallic luster is inhibited.
Therefore currently invention addresses such projects, and its purpose is to provide a kind of pretreatment procedures as electroless plating Used new electroless plating substrate agent can easily be handled in view of environmental protection with few process number, and And being able to easily form width by photoetching is the wiring fine in this way of several microns.
The method used for solving the problem
The inventors of the present invention have made intensive studies to achieve the goals above, as a result, it has been found that, have for molecular end The dissaving polymer and metal particle of ammonium, by specific polymerizable compound, Photoepolymerizationinitiater initiater, amine compounds and more Functional thiols are combined in wherein and obtain photonasty substrate agent, and the layer which is coated on substrate and is obtained can pass through Photoetching forms pattern, can get the basal layer of the non-electrolytic metal-plated patterned；The plating of the basal layer is excellent, is pair In metal coating and layer useful for the raising for the adaptation for being plated substrate.It has furthermore been found that in transparent substrates such as glass The basal layer of the upper non-electrolytic metal-plated for forming the patterning, when forming metal-plated envelope on the basal layer, plating quilt Black is presented in the back side that film forms part.It especially finds, in above-mentioned emulsion substrate agent, by amine compounds and Thiolation The cooperation for closing object, can be improved dispersibility, the reactivity of metal particle, and can form pattern in high sensitivity, thus complete At the present invention.
That is, in the present invention, as the 1st viewpoint, being related to a kind of photonasty substrate agent, for handling by electroless plating Metal coating is formed on substrate comprising:
(a) dissaving polymer that molecular end has ammonium and weight average molecular weight is 1,000~5,000,000,
(b) metal particle,
(c) intramolecular has the polymerizable compound of 1 or more (methyl) acryloyl group,
(d) Photoepolymerizationinitiater initiater,
(e) amine compounds, and
(f) multi-functional thiol.
As the 2nd viewpoint, it is related to photonasty substrate agent described in the 1st viewpoint, above-mentioned (c) polymerizable compound is intramolecular Compound with 3 or more (methyl) acryloyl groups.
As the 3rd viewpoint, it is related to photonasty substrate agent described in the 1st viewpoint or the 2nd viewpoint, above-mentioned (c) polymerism chemical combination Object is intramolecular with 3 or more (methyl) acryloyl groups and with the compound of oxyalkylene.
As the 4th viewpoint, it is related to photonasty substrate agent described in any one of the 1st viewpoint~the 3rd viewpoint, above-mentioned (f) Multi-functional thiol is 4 functional thiols.
As the 5th viewpoint, it is related to photonasty substrate agent described in any one of the 1st viewpoint~the 4th viewpoint, above-mentioned (e) Amine compounds are the amine compounds with alkoxysilyl.
As the 6th viewpoint, it is related to photonasty substrate agent described in any one of the 1st viewpoint~the 5th viewpoint, above-mentioned (a) Dissaving polymer is dissaving polymer shown in formula [1].
(in formula [1], R1Each independently represent hydrogen atom or methyl, R2~R4It is former to each independently represent hydrogen atom, carbon The aryl alkyl or-(CH of straight-chain, branched or the cricoid alkyl of subnumber 1~20, carbon atom number 7~202CH2O)mR5(formula In, R5Indicate that hydrogen atom or methyl, m indicate 2~100 integer.) (abovementioned alkyl and aryl alkyl can be by alkoxies, hydroxyl Base, ammonium, carboxyl or cyano replace.) or R2~R4In 2 groups indicate straight-chain, branched or cricoid Asia together Alkyl or R2~R4Nitrogen-atoms in conjunction with them is formed together ring, X-Indicate that anion, n are the number of repeat unit structure Mesh indicates 5~100,000 integer, A1Structure shown in expression [2].)
(in formula [2], A2Expression may include straight-chain, branched or the ring-type of the carbon atom number 1~30 of ehter bond or ester bond Alkylidene, Y1~Y4Each independently represent hydrogen atom, the alkyl of carbon atom number 1~20, carbon atom number 1~20 alkoxy, Nitro, hydroxyl, amino, carboxyl or cyano.)
As the 7th viewpoint, it is related to photonasty substrate agent described in the 6th viewpoint, above-mentioned (a) dissaving polymer is formula [3] Shown in dissaving polymer.
(in formula [3], R1~R4With n respectively with above-mentioned R1~R4Identical meanings are indicated with n.)
As the 8th viewpoint, it is related to photonasty substrate agent described in any one of the 1st viewpoint~the 7th viewpoint, 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 particle.
As the 9th viewpoint, it is related to photonasty substrate agent described in the 8th viewpoint, above-mentioned (b) metal particle is palladium particle.
As the 10th viewpoint, it is related to photonasty substrate agent described in any one of the 1st viewpoint~the 9th viewpoint, above-mentioned (b) Metal particle is the particle of 1~100nm of average grain diameter.
As the 11st viewpoint, it is related to photonasty substrate agent described in any one of the 1st viewpoint~the 10th viewpoint, it can It is formed by photoetching to carry out pattern.
As the 12nd viewpoint, it is related to a kind of electroless plating basal layer, is to be seen using the patterned layer being lithographically derived by the 1st Photonasty substrate dosage form described in any one of point~the 11st viewpoint at.
As the 13rd viewpoint, be related to a kind of metal coating, the electroless plating basal layer as described in the 12nd viewpoint and The electroless plating formed on the electroless plating basal layer is constituted.
As the 14th viewpoint, it is related to a kind of metal by film base material, have: substrate, the 12nd formed on the substrate are seen Metal coating described in the point electroless plating basal layer and the 13rd viewpoint formed on the electroless plating basal layer.
As the 15th viewpoint, it is related to a kind of metal by the manufacturing method of film base material comprising following A process~C process.
A process: photonasty substrate agent described in any one of the 1st viewpoint~the 11st viewpoint is coated on substrate, is made It has the process of basal layer
B process: the process by being lithographically formed the basal layer with expected pattern
C process: the substrate that will be provided with being formed the basal layer of pattern is impregnated in non-electrolytic plating bath, forms the work of metal coating Sequence.
Invention effect
By the way that photonasty substrate agent of the invention to be coated on substrate, implement photoetching across mask, so as to be easy Ground forms the basal layer of the non-electrolytic metal-plated patterned.
Even if in addition, photonasty substrate agent of the invention do not formed in the past in order to improve adaptation with metal coating and The priming coat formed on substrate is also capable of forming the basal layer with the excellent adhesion of substrate.In turn, photonasty base of the invention Priming agent is capable of forming the plate substrate layer of the patterning of μm grade, can also be suitable for various wiring techniques.
Photonasty substrate agent especially of the invention can be combined to form amine by cooperation with metal particles coordinations such as palladiums The amine compounds of complex in turn, add simultaneously so as to improve the dispersion stabilization of the metal particle in substrate agent Multi-functional thiol not only undertake the effect as crosslinking agent, but also undertake the effect as chain-transferring agent, so as to With the basal layer of the highly sensitive non-electrolytic metal-plated for forming the patterning with excellent developability when photoetching.Moreover, this The photonasty substrate agent of invention can be developed using water.
In addition, by photonasty substrate dosage form of the invention at non-electrolytic metal-plated basal layer it is non-only by being impregnated in Electrolysis plating bath is just able to easily form metal coating, can be readily available and have substrate, basal layer and metal coating Metal is by film base material.
Moreover, the excellent adhesion of above-mentioned metal coating and the basal layer of lower layer.
That is, forming basal layer on substrate by using photonasty substrate agent of the invention, it may be said that be capable of forming and base The metal coating of the excellent adhesion of material.
In turn, when forming metal coating in above-mentioned photonasty substrate agent of the invention, back side presentation black, therefore When they are formed in the transparent substrates such as glass substrate, the use of the transparent electrode high as visibility of image can be expected.
Detailed description of the invention
Fig. 1 is the dissaving polymer (HPS-Cl) that display is had chlorine atom by the molecular end that Production Example 1 manufactures1H The figure of NMR spectra.
Fig. 2 is the dissaving polymer (HPS- that display is had dimethyl octyl ammonium by the molecular end that Production Example 2 manufactures N(Me)2OctCl)13The figure of C NMR spectra.
Fig. 3 is the figure for showing the digital microscope images of the metal coating obtained by embodiment 7.
Fig. 4 is the figure for showing the digital microscope images of the metal coating obtained by embodiment 7.
Specific embodiment
[substrate agent]
< (a) dissaving polymer >
(a) dissaving polymer used in photonasty substrate agent of the invention is that molecular end has ammonium and weight is equal The polymer that molecular weight is 1,000~5,000,000, specifically, dissaving polymer shown in following formula [1] can be enumerated.
In above-mentioned formula [1], R1Each independently represent hydrogen atom or methyl.
In addition, R2~R4Each independently represent hydrogen atom, the straight-chain of carbon atom number 1~20, branched or cricoid alkane The aryl alkyl or-(CH of base, carbon atom number 7~202CH2O)mR5(in formula, R5Indicate that hydrogen atom or methyl, m indicate 2~100 Arbitrary integer.).Abovementioned alkyl and aryl alkyl can be replaced by alkoxy, hydroxyl, ammonium, carboxyl or cyano.In addition, R2~R4In 2 groups indicate straight-chain, branched or cricoid alkylidene or R together2~R4And they are combined Nitrogen-atoms be formed together ring.
In addition, X-It indicates that anion, n are the number of repeat unit structure, indicates 5~100,000 integer.
As above-mentioned R2~R4In carbon atom 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., being not easy to dissolve out in electroless plating solution from the viewpoint of substrate agent, the preferably group of 8 or more carbon atom number is special It You Xuanwei not n-octyl.As the alkyl of branched, isopropyl, isobutyl group, sec-butyl, tert-butyl etc. can be enumerated.As ring-type Alkyl, can enumerate with cyclopenta ring, group of cyclohexyl ring structure etc..
In addition, as R2~R4In carbon atom number 7~20 aryl alkyl, benzyl, phenethyl etc. can be enumerated.
In turn, as R2~R4In the alkylidene of straight-chain that indicates 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- diyl etc..As cricoid alkylidene, the monocyclic, polycyclic of carbon atom number 3~30 can be enumerated The ester ring type fatty group of formula, the cyclic structure of crosslinking ring type.Specifically, can enumerate the monocycle with 4 or more carbon atom number, The group of two rings, tricyclic, Fourth Ring, five ring structures etc..These alkylidenes can include that nitrogen-atoms, sulphur atom or oxygen are former in group Son.
Moreover, in the structure shown in formula [1], R2~R4And the ring that the nitrogen-atoms in conjunction with them is formed together can To include nitrogen-atoms, sulphur atom or oxygen atom in ring, such as pyridine ring, pyrimidine ring, pyridine ring, quinoline ring, connection pyrrole can be enumerated Phenazine 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], A1Indicate structure shown in following formula [2].
In above-mentioned formula [2], A2Indicate to may include the straight-chain of carbon atom number 1~30 of ehter bond or ester bond, branched or Cricoid alkylidene.
Y1~Y4Each independently represent hydrogen atom, the alkyl of carbon atom number 1~20, carbon atom number 1~20 alkoxy, Nitro, hydroxyl, amino, carboxyl or cyano.
As above-mentioned A2Alkylidene concrete example, methylene, ethylidene, trimethylene, tetramethylene, six sub- can be enumerated The branched alkylenes such as the straight-chains such as methyl alkylidene, methyl ethylidene, butane -1,3- diyl, 2- methylpropane -1,3- diyl Base.In addition, monocyclic, polycycle and the cyclic structure for being crosslinked ring type of carbon atom number 3~30 can be enumerated as cyclic alkylidene Ester ring type fatty group.Specifically, the monocycle with 4 or more carbon atom number, two rings, tricyclic, Fourth Ring, five rings knot can be enumerated The group of structure etc..For example, structural 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 atom number 1~20 alkyl, methyl, ethyl, isopropyl can be enumerated Base, n-pentyl, cyclohexyl etc..As the alkoxy of carbon atom number 1~20, methoxyl group, ethyoxyl, isopropoxy, just can be enumerated Amoxy, cyclohexyloxy etc..As Y1~Y4, preferably hydrogen atom or the alkyl of carbon atom number 1~20.
Dissaving polymer used in the present invention can preferably enumerate dissaving polymer shown in following formula [3].
In above-mentioned formula [3], R1、R2~R4With n respectively with aforementioned R1、R2~R4Identical meanings are indicated 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 Object 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 by molecular end there is the dissaving polymer of dithiocarbamate groups to manufacture.Molecule end It holds the dissaving polymer with dithiocarbamate groups that commercially available product can be used, Nissan Chemical work can be used well Ha イ パ ー テ ッ Network (registered trademark) HPS-200 etc. of industry (strain) system.
In the amine compounds 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 types 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, to dodecyl aniline, to n-tetradecane base aniline The amino anthracenes such as amino anthracenes class, the 1- amino anthraquinones such as naphthylamines class, 1- amino anthracene, the 2- amino anthracenes such as equal phenyl amines, naphthalidine, 2- naphthylamines The aminobiphenylenes such as quinones, 4- aminobphenyl, 2- aminobphenyl, 2- aminofluorene, 1- amino -9-Fluorenone, 4- amino -9-Fluorenone etc. The aminophenanthrenes classes such as the aminoisoquinolines classes such as the aminoidans classes such as aminofluorene class, 5- aminoidan, 5- aminoisoquinoline, 9- aminophenanthrene Equal aromatic amines.N- (tert-butoxycarbonyl) -1,2- ethylenediamine, N- (tert-butoxycarbonyl) -1,3- the third two can further be enumerated Amine, N- (tert-butoxycarbonyl) -1,4- butanediamine, N- (tert-butoxycarbonyl) -1,5- pentanediamine, N- (tert-butoxycarbonyl) - 1,6- hexamethylene diamine, N- (2- hydroxyethyl) amine, N- (3- hydroxypropyl) amine, N- (2- methoxy ethyl) amine, N- (2- ethyoxyl second Base) amine compounds 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-are 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 types amine such as dicyclohexylamine；The aralkylamines such as dibenzyl amine；The fragrance such as diphenylamine Race's amine；The nitrogenous heterocyclics compound such as phthalimide, pyrroles, piperidines, piperazine, imidazoles.Bis- (2- hydroxyls can further be enumerated Base ethyl) amine, bis- (3- hydroxypropyl) amine, bis- (2- ethoxyethyl group) amine, bis- (2- Among) 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- methylimidazole, 4,4 '-bipyridyls, 4- methyl -4,4 '-bipyridyl etc. are nitrogenous Hetero ring type compound.
As long as the usage amount of amine compounds used in can reacting at these has halogen atom relative to molecular end 1 mole of halogen atom of dissaving polymer be 0.1~20 molar equivalent, preferably 0.5~10 molar equivalent, more preferably 1~5 molar equivalent.
Molecular end has the dissaving polymer of halogen atom can be in water or organic solvent with reacting for amine compounds In, it is carried out under conditions of presence or absence of alkali.Used solvent, which is preferably capable dissolution molecular end, has halogen former The dissaving polymer of son and the solvent of amine compounds.In turn, if it is molecular end can be dissolved with the super of halogen atom Branched polymer and amine compounds, but insoluble molecular end has the solvent of the dissaving polymer of ammonium, then separating-purifying It becomes easy, is more suitable for.
As the solvent that can be used in the present reaction, as long as the solvent for indistinctively hindering this reaction to carry out, 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, methylene chloride, 1,2- dichloroethanes；The aliphatic hydrocarbons such as n-hexane, normal heptane, hexamethylene；N, N- diformazan The amides such as base formamide (DMF), DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone (NMP).It is molten that these can be used 1 kind in agent, two or more can also be used in mixed way.In addition, about usage amount, it is preferable to use having relative to molecular end The quality of the dissaving polymer of halogen atom be 0.2~1,000 times of quality, 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, generally 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 compounds 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, about usage amount, it is preferable to use relative to Molecular end has 1 mole of halogen atom of the dissaving polymer of halogen atom for 0.2~10 molar equivalent, is 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 Equal non-active gas will replace in system.As reaction condition, the reaction time suitably selects from 0.01~100 hour, Reaction temperature is suitably selected 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 alkali is not present In the case that conjunction object 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, even if using alkali to be reacted, By being mixed in organic solvent with sour aqueous solutions 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 measured using gel permeation chromatography, being converted with polystyrene Mw is 1,000~5,000,000, more preferably 2,000~200,000, most preferably 3,000~100,000.In addition, conduct Dispersion degree 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 particle >
As (b) metal particle used in photonasty substrate agent of the 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, be also possible to of more than two kinds be used in combination.Wherein, as preferred metal particle, Palladium particle can be enumerated.In addition, the oxide of above-mentioned metal can be used as metal particle.
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, there is method of compound (so-called reducing agent) of reduction etc. also to obtain metal ion originally for addition in the aqueous solution ?.For example, irradiating by the aqueous solution for adding metal salt in the solution dissolved with above-mentioned dissaving polymer and to it ultraviolet Line or added in the dissaving polymer solution metal salt aqueous solution and reducing agent etc. and metal ion is restored, from And can be while forming the complex of dissaving polymer and metal particle, 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=dibenzalacetone], Pt (cod)2[cod=1,5- cyclo-octadiene], Pt (CH3)2 (cod), palladium chloride, 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-octatriene], iridium chloride, iridium acetate, Ni (cod)2Deng.
It as above-mentioned reducing agent, is not particularly limited, various reducing agents can be used, preferably according to the substrate agent of acquisition In the metal species etc. that contain carry out selective reduction agent.As the reducing agent that can be used, can enumerate for example, sodium borohydride, boron hydrogen Change the hydroborations 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；Succinic acid and its salt；Ascorbic acid and its salt；It is methanol, ethyl alcohol, 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 Bis- (diphenylphosphino) ethane (DPPE) of benzyl phosphine, triphenylphosphine, triethoxy phosphine, 1,2-, bis- (diphenylphosphinos) third of 1,3- Alkane (DPPP), 1,1 '-bis- (diphenylphosphino) ferrocene (DPPF), 2,2 '-bis- (diphenylphosphino) -1,1 '-dinaphthalenes (BINAP) Etc. phosphines etc..
The average grain diameter of above-mentioned metal particle is preferably 1~100nm.By the average grain diameter for making the metal particle 100nm is hereinafter, reduce few to surface area, and can get sufficient catalytic activity.As average grain diameter, further preferably 75nm is hereinafter, particularly preferably 1~30nm.
The additive amount of above-mentioned (a) dissaving polymer in photonasty substrate agent of the invention is relative to above-mentioned (b) metal 100 mass parts of particle are preferably 50~2,000 mass parts.By making its 50 mass parts or more, so as to make above-mentioned metal Particle fully disperses, in addition, by making it 2,000 below the mass, so as to inhibit to be made by content of organics increase At physical property etc. undesirable condition.More preferably 100~1,000 mass parts.
< (c) intramolecular has the polymerizable compound > of 1 or more (methyl) acryloyl group
There is 1 or more (methyl) acryloyl group as (c) intramolecular used in photonasty substrate agent of the invention Polymerizable compound (hereinafter also referred to as polymerizable compound) can preferably enumerate intramolecular with 3 or more (methyl) third The compound of enoyl-, wherein can preferably enumerate intramolecular with 3 or more (methyl) acryloyl groups and there is oxyalkylene Compound.
As above-mentioned oxyalkylene, the preferably oxyalkylene of carbon atom 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 two kinds or more in combination.Sub- with a variety of oxygen In the case where alkyl, their combination can be block and combine and randomly any one 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 Acrylic ester etc. contains the monomer of 1 or more (methyl) acryloyl group, especially contains 3 or more above-mentioned (methyl) acryloyls The polyfunctional monomer etc. of base.
In these polymerizable compounds, it is however preferred to have 3 or more (methyl) acryloyl groups and with oxyalkylene Compound, polyfunctional carbamate (methyl) acrylate compounds with 3 or more (methyl) acryloyl groups.
An example for being suitable as the compound of (c) polymerizable compound of the invention, but (c) polymerism chemical combination are enumerated below Object is not limited by these illustrations.
[with 3 or more (methyl) acryloyl groups and with the compound of oxyalkylene structure]
(1) 3 function (there are 3 (methyl) acryloyl groups) compound
As with 3 (methyl) acryloyl groups and with the compound (3 functional compound) of oxyalkylene structure, can lift 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 [propylene oxide addition molal quantity 3~30], ethylene-oxide-modified glycerol Three (methyl) acrylate [ethyleneoxide addition molal quantity 3~30], epoxy pronane modification glycerol three (methyl) acrylate [ring Ethylene Oxide addition molal quantity 3~30], three (2- (acryloxy) ethyl) isocyanuric acid esters, the modified three (2- (third of 6-caprolactone 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 ビ ス コ ー ト #360, [Osaka is organic Chemical industry (strain) system]；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 The village Dou Shixinzhong chemical industry (strain) system]；TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [are ダ イ セ above Le オ Le ネ Network ス (strain) system] etc..
(2) 4 functions (there are 4 (methyl) acryloyl groups) compound
As with 4 (methyl) acryloyl groups and with the compound (4 functional compound) of oxyalkylene structure, can lift Out for example, ethylene-oxide-modified bis- (trimethylolpropanes) 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 suitble to that such as NK エ ス テ Le ATM-4E, NK エ ス テ can be enumerated using commercially available product Le ATM-35E [the above village Dou Shixinzhong chemical industry (strain) system]；[the ダ イ セ Le オ Le ネ of EBECRYL (registered trademark) 40 Network ス (strain) system] etc..
Compound more than (3) 5 functions (with 5 or more (methyl) acryloyl groups)
As with 5 or more (methyl) acryloyl groups and with the compound (change more than 5 functions of oxyalkylene structure Close object), 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 [village Xin Zhong chemical industry (strain) system] etc..
[polyfunctional carbamate (methyl) acrylate compounds with 3 or more (methyl) acryloyl groups]
As (c) polymerizable compound of the invention, by and with urethane compound, to state after its formation Metal-plated envelope after can be realized this by the blackened of back of the membrane, 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 can enumerate NK オ リ go UA-7100 [village Xin Zhong chemical industry (strain) system]；EBECRYL (registered trademark) 204, EBECRYL 205、EBECRYL 264、EBECRYL 265、EBECRYL 294/25HD、EBECRYL 1259、EBECRYL 4820, EBECRYL 8311, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, KRM (registered trademark) 8296, KRM 8667 [being all ダ イ セ Le オ Le ネ Network ス (strain) system above]；Purple light (registered trademark) 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 can enumerate EBECRYL (registered trademark) 8210, EBECRYL8405, KRM (registered trademark) 8528 [is above ダ イ セ Le オ Le ネ Network ス (strain) system]；Purple light (registered trademark) UV-7650B [Japanese synthetic chemical industry (strain) system] etc..
Carbamate (methyl) acrylate more than (3) 5 functions (with 5 or more (methyl) acryloyl groups)
As polyfunctional carbamate (methyl) acrylate compounds (5 with 5 or more (methyl) acryloyl groups Carbamate (methyl) acrylate more than function), it can enumerate for example, pentaerythrite three (methyl) acrylate and 1,6- Carbamate compound, the amino first of pentaerythrite three (methyl) acrylate and toluene di-isocyanate(TDI) of hexamethylene diisocyanate The carbamate compound of acid esters compound, pentaerythrite three (methyl) acrylate and isophorone diisocyanate, two seasons penta (methyl) acrylate of tetrol five and the carbamate compound of 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 [the above village Dou Shixinzhong chemical industry (strain) system]；EBECRYL (registered trademark) 220, EBECRYL 1290, EBECRYL 5129, EBECRYL 8254, EBECRYL 8301R, KRM (registered trademark) 8200, KRM 8200AE, KRM 8904, KRM 8452 [being all ダ イ セ Le オ Le ネ Network ス (strain) system above]；Purple light (registered trademark) 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 3 or more (methyl) acryloyl groups]
There to be 3 or more (methyl) acryloyl groups and with the compound and above-mentioned tool of oxyalkylene structure except above-mentioned Have it is other than polyfunctional carbamate (methyl) acrylate compounds of 3 or more (methyl) acryloyl groups, be suitable as The compound of (c) polymerizable compound of the 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, bis- (trimethylolpropanes) three (methyl) acrylate, pentaerythrite Three (methyl) acrylate, glycerol three (methyl) acrylate etc..
The above-mentioned compound with 3 (methyl) acryloyl groups can use commercially available product well, can enumerate such as ビ ス コ ー ト #295, ビ 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 [the above village Dou Shixinzhong chemical industry (strain) system]； PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [being all ダ イ セ Le オ Le ネ Network ス (strain) system above] etc..
(2) 4 functions (there are 4 (methyl) acryloyl groups) compound
As the compound with 4 (methyl) acryloyl groups, bis- (trimethylolpropanes) 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 ビ 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 [the above village Dou Shixinzhong chemical industry (strain) system]；EBECRYL (registered trademark) 140, EBECRYL 1142, EBECRYL 180 [being all ダ イ セ Le オ Le ネ Network ス (strain) system above] etc..
Compound more than (3) 5 functions (with 5 or more (methyl) acryloyl groups)
As the compound with 5 or more (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 5 or more (methyl) acryloyl groups can use commercially available product well, can enumerate for example ビ 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 [the above village Dou Shixinzhong chemical industry (strain) system]；DPHA[ダイ セ Le オ Le ネ Network ス (strain) system] etc..
[(methyl) acrylate compounds that intramolecular has 1 or 2 (methyl) acryloyl group]
As (c) polymerizable compound used in photonasty substrate agent of the invention, there are 1 or 2 as intramolecular The compound of a (methyl) acryloyl group, can be used 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, realize this by the black of back of the membrane due to being observed that after the metal-plated envelope for helping to state after its formation Color, therefore can be used in combination well.
[carbamate (methyl) acrylate compounds that intramolecular has 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) reacts with monohydric alcohol (active hydrogen component) and obtains isocyanates end prepolymer, makes it and has (methyl) acryloyl group and with isocyanates there is the compound of reactive group to be reacted, obtaining every 1 molecule has Carbamate (methyl) acrylate of average 1 (methyl) acryloyl group.Polyalcohol can be used instead of monohydric alcohol, but In this case, needing to be grasped in a manner of not importing (methyl) acryloxy in a 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 Object and the carbamate compound of toluene di-isocyanate(TDI) etc..
Above-mentioned 2 function carbamate (methyl) acrylate can use commercially available product well, can enumerate such as AH- 600, 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 [the above village Dou Shixinzhong chemical industry (strain) system]；EBECRYL (registered trademark) 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 8807, EBECRYL 9227EA, 9270 EBECRYL, KRM (registered trademark) 7735 [are ダ イ セ Le オ Le ネ Network above ス (strain) system]；Purple light (registered trademark) 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, intramolecular is had 1 or 2 (methyl) acryloyl group in photonasty substrate agent of the invention The molecule that carbamate (methyl) acrylate compounds and the above-mentioned example as suitable (c) polymerizable compound are enumerated In the case where inside having the compound of 3 or more (methyl) acryloyl groups and use, additive amount has 3 relative to above-mentioned intramolecular 100 mass parts of compound of a above (methyl) acryloyl group are preferably 200 below the mass further preferably 10~200 Mass parts, more preferably 20~100 mass parts.Even if 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, do not help to realize metal-plated by the black of back of the membrane yet Change, in addition, if addition more than 200 mass parts, then the pattern formation of the plate substrate layer favorably carried out with photoetching becomes difficult Worry, it is therefore desirable to pay attention to.
[(methyl) acrylate compounds that other intramoleculars have 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- ethylhexyl, (methyl) lauryl acrylate, (methyl) acrylic acid pentadecane base ester, (methyl) stearyl acrylate, (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- trifluoroethyl (methyl) acrylate, 2- ethylhexyl diglycol (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- methoxy Base ethyl ester, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) ethioxy ethoxyethyl group ester, (methyl) acrylic acid fourth Oxygroup ethyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic acid 2- methyl -2- Buddha's warrior attendant alkyl ester, (methyl) acrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, gamma-butyrolacton (methyl) acrylate, (methyl) acrylic acid two Ring pentyl ester, (methyl) acrylic acid 8- methyl -8- tricyclodecyl, (methyl) acrylic acid 8- ethyl -8- tricyclodecyl, (methyl) propylene Sour 2- ethylhexyl carbitol ester, (methyl) phenoxyethyl acrylate, phenoxy group diethylene glycol (DEG) (methyl) acrylate, phenoxy group Polyethylene glycol (methyl) acrylate, nonyl phenol ethoxy (methyl) acrylate, N- dimethyl aminoethyl (methyl) Acrylate, N- diethylamino ethyl (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- Hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyl, (methyl) acryloyl Amine, N- methyl (methyl) acrylamide, N- dimethyl (methyl) acrylamide, N- dimethylaminopropyl (methyl) acryloyl Amine, N- methylol (methyl) acrylamide, N- diacetone (methyl) acrylamide, N, N '-di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylonitrile, (methyl) glycidyl acrylate, (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl Oxygroup ethylsuccinic acid, 2- (methyl) acryloyl-oxyethyl hexahydro phthalic acid, 2- (methyl) acryloyl-oxyethyl benzene two Formic acid, 2- (methyl) acryloyl-oxyethyl -2- hydroxyethyl phthalic acid etc..
The above-mentioned compound with 1 or more (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) system]；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 [the above village Dou Shixinzhong chemical industry (strain) System]；FANCRYL (registered trademark) 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 is melted into (strain) system]；β-CEA, IBOA-B, ODA-N, EBECRYL (registered trademark) 110, [the ダ イ セ of EBECRYL 114 Le オ Le ネ Network ス (strain) system]；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, ビ ス コ ー ト #200,2-MTA, MPE400A, MPE550A, MEDOL-10, OXE-10, OXE-30 [are big above Slope Organic Chemical Industry (strain) system] 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, propylene glycol two (methyl) acrylate, new penta Glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 1,4- fourth Glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, 2- Methyl-1,8- ethohexadiol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, pentaerythrite two (methyl) Acrylate, tricyclic [5.2.1.02,6] decane dimethanol two (methyl) acrylate, twoAlkane glycol two (methyl) acrylic acid Ester, 2- hydroxyl -1- acryloxy -3- methacryloxy propane, 2- hydroxyl -1,3- two (methyl) acryloxy third Bis- [4- (2- (methyl) acryloyloxyethoxy) benzene of alkane, trihydroxy ethyl isocyanuric acid two (methyl) acrylate, 9,9- Base] fluorenes, undecenyl oxygroup 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 2 or more (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 [the above village Dou Shixinzhong 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 (registered trademark) 145, EBECRYL 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [ダ イ セ Le オ Le ネ Network ス (strain) system]；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, ビ ス コ ー ト #802, ビ ス コ ー ト #295 [being all Japanese synthetic chemical industry (strain) system above] etc..
The additive amount of (c) polymerizable compound in photonasty substrate agent of the invention is relative to aftermentioned 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 (c) additive amount of polymerizable compound be less than above-mentioned 10 mass parts, it is aftermentioned using photoetching into The pattern formation of capable plate substrate layer becomes difficult, in addition, having in the case where addition is more than 10 000 mass parts by this Substrate dosage form at basal layer on cannot form the worry of metal-plated envelope.
In addition, in order to keep the formative of the patternability and plating envelope of plate substrate layer on the basal layer suitable It closes, the intramolecular that the suitable example as (c) polymerizable compound can be made to be enumerated has 3 or more (methyl) acryloyls The mixing ratio of the compound of base relative to (c) polymerizable compound gross mass be such as 30 mass % or more, preferably 50 Quality % or more is further 75 mass of mass %~100 %.
< (d) Photoepolymerizationinitiater initiater >
As (d) Photoepolymerizationinitiater initiater used in photonasty substrate agent of the invention, it is able to use well known photopolymerization Initiator, can enumerate for example, alkylbenzene ketone, benzophenone, acylphosphine oxide class, the benzoylbenzoic acid esters of rice Chi, 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 about optical cleavage type, which polymerize, to be caused Agent, can enumerate newest UV curing technology (page 159, publisher: high Bao Yihong, sale room: (strain) technical information association, 1991 Distribution) in record optical cleavage type optical free radical polymerization initiator.
As commercially available optical free radical polymerization initiator, can enumerate for example, IRGACURE (registered trademark) 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 [the above are BASF ジ ャ パ Application by CG24-61, IRGACURE TPO, Darocur (registered trademark) 1116, Darocur 1173 (strain) system], ESACURE KIP150, ESACURE KIP65LT, ESACURE KIP100F, ESACURE KT37, ESACURE KT55, ESACURE KTO46, ESACURE KIP75 [the above are ラ Application ベ Le テ ィ society systems] etc., but it is not limited to these.These Polymerization initiator can also combine a variety of use.
The additive amount of (d) polymerization initiator in photonasty substrate agent of the invention is relative to above-mentioned (c) polymerism chemical combination Object is, for example, 0.1~100 mass %, preferably 1~50 mass %, more preferably 10~30 mass %.
< (e) amine compounds >
As (e) amine compounds used in photonasty substrate agent of the invention, well known amine compounds are able to use, it can It enumerates for example, the aliphatic such as alkyl amine, hydroxyalkylamines amine, the amine with cyclic substituents, aromatic amine (aryl Amine) class and the amine compounds with alkoxysilyl etc..In these amine compounds, it is however preferred to have alkoxy first The amine compounds of silylation.
In the present invention, micro- so as to obtain metal by the way that (e) amine compounds are matched in photonasty substrate agent Grain, the complex specifically formed for the aftermentioned dissaving polymer by metal particle and with ammonium are 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 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；N, N- dimethyl amine, N, N- diethylamide, N, N- dipropylamine, N, the secondary amine class such as N- dibutylamine； The tertiary amines such as Trimethylamine, triethylamine, tripropylamine, tri-butylamine.
As above-mentioned hydroxyalkylamines (ethyl alcohol amine), carbinolamine (OHCH can be enumerated2NH2), ethanol amine (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 methine amine, N- ethyl carbinol amine, N- propyl carbinol amine, N- butyl carbinol amine, N- Methylethanolamine, N- ehtylethanolamine, N- propyl ethanol amine, N- butylethanolamine, N- methyl-prop hydramine, N- ethylpropanolamine, N- propyl propanol amine, N- butylpropanol amine, N- methyl butanol amine, N- ethyl butanol amine, N- propyl butanolamine, N- butyl butanolamine 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 in amine compounds.
In above-mentioned formula, R11For carbon atom number 3~10, the monovalence cyclic group of preferably carbon atom number 3~12, alicyclic ring can be Any one of formula base, aromatic series base and their combination.These cyclic groups can be by arbitrary substituent group such as carbon atom Alkyl of number 1~10 etc. replaces.R12Indicate the alkylidene of singly-bound or carbon atom number 1~17, preferably carbon atom number 1~3.
In the present invention, as formula R11-R12-NH2Shown in amine compounds preferred concrete example, following formula can be enumerated (A-1)~(A-10) compound represented etc..
As the concrete example of aromatic amine (aryl amine), aniline, methylphenylamine, o-anisidine, 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, Iodoaniline or paraiodoaniline etc..
As the concrete example of the amine compounds with alkoxysilyl, N, bis- [3- (the trimethoxy first of N '-can be enumerated Silylation) propyl] -1,2- ethylenediamine, N, N '-bis- [3- (triethoxysilyl) propyl] -1,2- ethylenediamines, N- [3- (three Methoxysilyl) propyl] -1,2- ethylenediamine, N- [3- (triethoxysilyl) propyl] -1,2- ethylenediamine, it is double - [3- (trimethoxysilyl) propyl] amine, double-[3- (triethoxysilyl) propyl] amine, 3- aminopropyl trimethoxy Base silane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldimethoxysilane, 3- amino propyl methyl diethoxy Base silane, trimethoxy [3- (methylamino)] propyl silane, 3- (N- allyl amino) propyl trimethoxy silicane, 3- (N- Allyl amino) propyl-triethoxysilicane, 3- (diethylamino) propyl trimethoxy silicane, 3- (diethylamino) propyl The chemical combination such as triethoxysilane, 3- (phenyl amino) propyl trimethoxy silicane, 3- (phenyl amino) propyl-triethoxysilicane Object.
The content of (e) amine compounds in photonasty substrate agent of the invention is relative to aftermentioned by above-mentioned hyperbranched polymerization Complex (or total quality of above-mentioned dissaving polymer and metal particle) 100 mass parts that object and metal particle are formed are preferred For 1 mass parts~100 mass parts, more preferably 5 mass parts~50 mass parts, especially 10 mass parts~15 mass parts.
In the case where the content of (e) amine compounds is very few compared with above-mentioned numberical range, cannot obtain aftermentioned by upper Dispersibility, the dissolubility for stating complex and aftermentioned (f) multi-functional thiol that dissaving polymer and metal particle are formed are steady Surely change effect, in addition, substantially more than above range to add (such as 10 mass of above-mentioned complex are measured again), Sometimes bad order occurs for plating envelope.
< (f) multi-functional thiol >
As the multi-functional thiol used in photonasty substrate agent of the invention as (f) ingredient, as long as having 2 The compound of the above sulfydryl, is just not particularly limited, for example, the hydro carbons with 2 or more sulfydryls as substituent group can be enumerated, 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 fourth of polyalcohol Acid esters) class, poly- (the 3- mercaptoisobutanoic acid esters) class of polyalcohol etc..
In photonasty substrate agent of the 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 in photoetching with highly sensitive.
As the concrete example of above-mentioned there are 2 or more the sulfydryls hydro carbons as substituent group, bis- sulphur of hexane -1,6- can be enumerated Bis- (mercapto methyl) benzene of alcohol, two mercaptan of decane -1,10-, 1,4- dimercaptobenzene, 1,4- etc..
In addition, the compound as other 2 functions, can enumerate ethylene glycol bis- (mercaptoacetates), bis- (the sulfydryl second of propylene glycol Acid esters), ethylene glycol bis- (3-thiopropionates), propylene glycol bis- (3-thiopropionates), ethylene glycol bis- (2 mercaptopropionic acid esters), third Glycol bis- (2 mercaptopropionic acid esters), diethylene glycol (DEG) bis- (2 mercaptopropionic acid esters), butanediol bis- (2 mercaptopropionic acid esters), ethohexadiol are double (2 mercaptopropionic acid ester), ethylene glycol bis- (3- mercaptobutylates), diethylene glycol (DEG) bis- (3- mercaptobutylates), bis- (the 3- sulfydryls of butanediol Butyrate), trimethylolpropane tris (3- mercaptobutylate), pentaerythrite four (3- mercaptobutylate), six (3- of dipentaerythritol Mercaptobutylate), ethylene glycol bis- (3- mercaptoisobutanoic acid esters), diethylene glycol (DEG) bis- (3- mercaptoisobutanoic acid esters), bis- (the 3- sulfydryls of butanediol Isobutyrate), ethohexadiol bis- (3- mercaptoisobutanoic acid esters) etc..
As the compound of 3 functions, glycerol three (mercaptoacetate), trimethylolpropane tris (thioacetic acid can be enumerated Ester), glycerol three (3-thiopropionate), trimethylolpropane tris (3-thiopropionate), trimethylolpropane tris (2- sulfydryl third Acid esters), trimethylolpropane tris (3- mercaptoisobutanoic acid esters) etc..
As the compound of 4 functions, pentaerythrite four (mercaptoacetate), (the 3- mercaptopropionic acid of pentaerythrite four can be enumerated Ester), pentaerythrite four (2 mercaptopropionic acid ester), pentaerythrite four (3- mercaptoisobutanoic acid esters) etc..
As the compound of 6 functions, dipentaerythritol six (mercaptoacetate), (the 3- sulfydryl of dipentaerythritol six can be enumerated Propionic ester), dipentaerythritol six (2 mercaptopropionic acid ester), dipentaerythritol six (3- mercaptoisobutanoic acid esters), bis- (the 3- mercaptos of ethohexadiol Base butyrate) etc..
In these multi-functional thiols, it is preferable to use 4 functions from the viewpoint of the developability for improving the agent of photonasty substrate 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 photonasty substrate agent of the invention is relative to aftermentioned 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 preferably 0.01 mass % of mass %~200 is desired for 0.05 mass of mass %~50 %.If compounding ratio is above range Hereinafter, then cannot get desired effect, on the other hand, if adding to be more than above range, there is photonasty substrate agent Stability, peculiar smell, sensitivity, resolution ratio, developability, adaptation, plating the deteriorations such as precipitation worry.
< photonasty substrate agent >
Photonasty substrate agent of the invention includes dissaving polymer, (b) metal that above-mentioned (a) molecular end has ammonium Particle, (c) polymerizable compound, (d) Photoepolymerizationinitiater initiater, (e) amine compounds and (f) multi-functional thiol, as needed into one Step includes other ingredients, at this point, it is preferred that above-mentioned dissaving polymer and above-mentioned metal particle form complex.
Here complex, which refers to, to be connect with the effect by the ammonium of above-mentioned dissaving polymer end with metal particle Both touching or close state coexist, and form the form of particle shape, in other words, refer to the ammonium with above-mentioned dissaving polymer Adhere to or be coordinated in metal particle structure complex.
It not only include metal particle as described above and dissaving polymer accordingly, with respect to " complex " in the present invention In conjunction with and the case where form a complex, but also may include metal particle and dissaving polymer does not form engaging portion Point, the case where presence each independently.
The modulation that is formed in of the complex of dissaving polymer and metal particle with ammonium includes dissaving polymer It is carried out simultaneously when with the substrate agent of metal particle, as its method, there is following methods: manufacture is carried out by rudimentary ammonium ligand Stabilized to a certain degree metal particle, then exchanges the method for ligand using dissaving polymer；By with ammonium In the solution of the dissaving polymer of base, metal ion direct-reduction is formed to the method for 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 irradiates ultraviolet light to it, or in the over-expense Aqueous solution and the reducing agent etc. that metal salt is added in fluidized polymer solution, metal ion are restored, to form complex.
In ligand exchange method, having carried out metal particle stabilized to a certain degree by the rudimentary ammonium ligand of raw material can be with It is manufactured using the method recorded 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, to obtain the Metal microparticle composite of target.
As used solvent, as long as can be dissolved to metal particle and dissaving polymer with ammonium must The solvent for wanting concentration or more, is just not particularly limited, specifically, the alcohols such as ethyl alcohol, normal propyl alcohol, isopropanol can be enumerated；Dichloro The halogenated hydrocarbons such as methane, chloroform；The ring-type ethers such as tetrahydrofuran (THF), 2- methyltetrahydrofuran, oxinane；Acetonitrile, butyronitrile The mixed liquor of equal nitriles etc. and these solvents, can preferably enumerate tetrahydrofuran.
The temperature that the reaction mixture of metal particle is mixed with the dissaving polymer with ammonium usually can be used 0 DEG C~range of the boiling point of solvent, the preferably range of room temperature (about 25 DEG C)~60 DEG C.
In addition, in ligand exchange method, by using phosphine system dispersing agent other than amine system dispersing agent (rudimentary ammonium ligand) (Phosphine ligands) also can in advance stabilize metal particle to a certain extent.
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, ethyl alcohol, isopropanol, polyalcohol or secondary alcohol class, is 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 metal ion and dissaving polymer with ammonium must The solvent for wanting concentration or more, is just not particularly limited, specifically, the alcohols such as methanol, ethyl alcohol, propyl alcohol, isopropanol can be enumerated；Two The halogenated hydrocarbons such as chloromethanes, chloroform；The ring-type ethers such as tetrahydrofuran (THF), 2- methyltetrahydrofuran, oxinane；Acetonitrile, fourth The nitriles such as nitrile；The amides such as N,N-dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP)；The sulfoxides such as dimethyl sulfoxide The mixed liquor of class etc. and these solvents can preferably enumerate alcohols, halogenated hydrocarbon, ring-type ethers, can more preferably enumerate ethyl alcohol, different Propyl alcohol, chloroform, tetrahydrofuran etc..
The range of the boiling point of 0 DEG C~solvent, preferably room temperature (about 25 DEG C) usually can be used in the temperature of reduction reaction ~60 DEG C of range.
As other direct reduction process, by the way that metal ion and dissaving polymer with ammonium are dissolved in 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-carbonyls complex.In addition, The metal of 0 valences such as metal olefin complex, metal phosphinate complex, metal nitrogen complex can also be used to be coordinated Compound.
As used solvent, as long as can be dissolved to metal ion and dissaving polymer with ammonium must The solvent for wanting concentration or more, is just not particularly limited, specifically, the alcohols such as ethyl alcohol, propyl alcohol can be enumerated；Methylene chloride, chloroform Equal halogenated hydrocarbons；The ring-type ethers such as tetrahydrofuran, 2- methyltetrahydrofuran, oxinane；Nitriles such as acetonitrile, butyronitrile etc. and this The mixed liquor of a little solvents, can preferably enumerate tetrahydrofuran.
0 DEG C~solvent is usually can be used into the temperature that metal ion and the dissaving polymer with ammonium mix Boiling point range.
It is molten by the way that metal ion and dissaving polymer with ammonium to be 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 metal complex, the silver oxide of 0 valence.
As used solvent, as long as can be dissolved to metal ion and dissaving polymer with ammonium must The solvent for wanting concentration or more, is just not particularly limited, specifically, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol can be enumerated Equal alcohols；The halogenated hydrocarbons such as methylene chloride, chloroform；The cyclic ethers such as tetrahydrofuran (THF), 2- methyltetrahydrofuran, 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.
0 DEG C~solvent is usually can be used into the temperature that metal ion and the dissaving polymer with ammonium mix Boiling point range, the preferably temperature near solvent boiling point, such as be 110 DEG C (being heated to reflux) in the case where toluene.
The complex of the dissaving polymer and metal particle with ammonium for operating and obtaining in this way can be via sinking again The purification process such as shallow lake, are made the solid forms such as powder.
Photonasty substrate agent of the invention includes that 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 Object, (f) multi-functional thiol and further other ingredients as needed, the photonasty substrate agent can be to be formed it is aftermentioned [non- Electrolysis plating basal layer] when used varnish form.
The other additive > of <
As long as photonasty substrate agent of the invention does not damage effect of the invention, so that it may it is living to be further properly added surface The additives such as additives, 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 ethers class such as ethylene cetyl ether, polyoxyethylene oleyl ether；NONIN HS 240, ethylene nonyl The polyoxyethylene alkylaryl ethers class such as phenyl ether；Polyoxyethylene/polyoxypropylene block copolymers class；Anhydrosorbitol list laurel Acid esters, sorbitan-monopalmityl ester, sorbitan monosterate, dehydrating sorbitol monooleate, dehydration The sorbitan fatty esters 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 (registrar Mark) EF-301, エ Off ト ッ プ EF-303, エ Off ト ッ プ EF-352 [the above are Mitsubishi's マ テ リ ア Le electronics chemical conversion (strain) systems], メ ガ Off ァ ッ Network (registered trademark) 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) system], Novec (registered trademark) FC-430, Novec FC-431 [the above are Sumitomo ス リ ー エ system (strain) systems], ア サ ヒ ガ ー De (registered trademark) AG-710 [Asahi Glass (strain)], サ ー Off ロ Application (registered trademark) S-382 processed [AGC セ イ ミ ケ ミ カ Le (strain) system] etc. fluorine system surfactants etc..
In addition, SHIN-ETSU HANTOTAI シ リ コ ー Application (registered trademark) KP-341 [SHIN-ETSU HANTOTAI's chemistry can be enumerated as above-mentioned surface conditioner Industrial (strain) system] etc. organic silicon-types levelling agent；BYK (registered trademark) -302, BYK 307, BYK 322, BYK 323, BYK 330, the organosilicons such as BYK 333, BYK 370, BYK 375, BYK 378 [the above are ビ ッ Network ケ ミ ー ジ ャ パ Application (strain) systems] It is surface conditioner etc..
These additives can be used alone, or also can be used together two kinds or more.The usage amount of additive is opposite In 100 mass parts of complex formed by above-mentioned dissaving polymer and metal particle be preferably 0.001~50 mass parts, it is more excellent It is selected as 0.005~10 mass parts, further preferably 0.01~5 mass parts.
[electroless plating basal layer]
The photonasty substrate agent of aforementioned present invention is coated on substrate, film is formed, is carried out photoetching, so as to Obtain the electroless plating basal layer for foring pattern.The basal layer is also object of the invention.
As above-mentioned base material, it is not particularly limited, non-conductive base material or conductive substrate preferably can be used.
As non-conductive base material, can enumerate such as glass, ceramics；Polyvinyl resin, acrylic resin, vinyl chloride tree Rouge, 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 suitble to use pass in the form of piece or film etc. In thickness in this case, it is not particularly limited.
In addition, such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), FTO can be enumerated as conductive substrate (fluorine-doped tin oxide), AZO (aluminium-doped zinc oxide), GZO (Ga-doped zinc oxide) and various stainless steels, aluminium and duralumin Copper alloys, nickel and nickel alloy and the silver such as equal aluminium alloys, iron and ferroalloy, copper and brass, phosphor bronze, copper-nickel alloy and beryllium copper And metals such as silver alloy such as nickeline etc..
It can also further use and be formd made of film on above-mentioned non-conductive base material as these conductive substrates Substrate.
In addition, above-mentioned substrate can be three-dimensionally shaped body.
As by causing containing the above-mentioned dissaving polymer with ammonium, metal particle, polymerizable compound, photopolymerization The photonasty substrate dosage form of agent, amine compounds and multi-functional thiol makes first at the specific method of electroless plating basal layer State dissaving polymer and metal particle (complex preferably formed by them), polymerizable compound, light with ammonium Polymerization initiator, amine compounds and multi-functional thiol are dissolved or dispersed in solvent appropriate the form for forming varnish, benefit Use method of spin coating；Scraper coating method；Dipcoat method；Rolling method；Stick coating method；Die coating method；Spray coating method；Ink-jet method；Tap water Nano photolithography (fountain pen nanolithography) (FPN) dips 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 letterpress printing methods such as nanometer transfer printing (nTP)；The gravure printing methods such as intaglio printing (gravure printing), engraving；Lithographic plate print Brush method；The porous printings method such as silk-screen printing, stencil；The varnish is coated on metal-plated quilt to be formed by offset printing method etc. On the substrate of film, then, make solvent evaporation, drying, to form thin layer.
In these coating methods, preferably method of spin coating, spray coating method, ink-jet method, photoetching process, contact printing, μ CP, NIL and nTP.It using method of spin coating, can be coated with the short time, even therefore volatility height Solution can also utilize, in addition, having the advantage that being able to carry out uniformity high coating.The case where using spray coating method Under, the high coating of uniformity can be carried out with minimal amount of varnish, industrially become advantageous in the extreme.Using ink-jet method, In the case where photoetching process, contact printing, μ CP, NIL, nTP, such as it can efficiently form (description) and the fine figure such as be routed Case industrially becomes advantageous in the extreme.
In addition, as solvent used herein above, as long as dissolving or dispersing above-mentioned complex (has the hyperbranched of ammonium Polymer and metal particle), polymerizable compound, Photoepolymerizationinitiater initiater, amine compounds and multi-functional thiol solvent, just not by It is particularly limited to, can be used 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), propylene glycol 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 amides such as n-methyl-2-pyrrolidone (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.In turn, to adjust the viscosity of varnish as mesh , the glycols such as ethylene glycol, propylene glycol, 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 atmosphere appropriate 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 be such that solvent evaporates, it is not particularly limited, is preferably carried out at 40~250 DEG C.
Then, to the film 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 that exposure portion is washed out, can be obtained patterning Electroless plating basal layer.
In above-mentioned exposure, the ultraviolet light such as mercury lamp, far ultraviolet, electron ray or X-ray etc. can be used.Make Used light source is irradiated for ultraviolet light, sunray, chemical lamp, low pressure mercury lamp, high-pressure sodium lamp, metal halide can be used Lamp, xenon lamp, UV-LED etc..
In addition, be not particularly limited as developing method, can by covering liquid method, paddling process, infusion process, gunite, shake Method well 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, ethyl alcohol, normal propyl alcohol, isopropanol；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol list first The glycol ethers such as base ether (PGME), 3-Methoxy-3-methyl-1-butanol；Ether, Di Iso Propyl Ether, dibutyl ethers, tetrahydrofuran (THF), 1,4- bis-The ethers such as alkane；The ether-ethers classes such as propylene glycol monomethyl ether (PGMEA)；Ethyl acetate, butyl acetate Etc. esters；The ketones such as acetone, cyclohexanone；The amides such as n-methyl-2-pyrrolidone (NMP), DMAC N,N' dimethyl acetamide (DMAc) Class；Sulfoxide types such as dimethyl sulfoxide etc..
Furthermore be used as alkaline aqueous solution, can enumerate for example, the alkali metal hydroxides such as potassium hydroxide, sodium hydroxide it is water-soluble Liquid；The aqueous solution of the quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline；Ethanol amine, propyl 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 suitble to Such as, PGME/PGMEA mixed solution (mass ratio 7:3) etc..
In these developer solutions, in order to adjust developability, water can be added；The glycol such as ethylene glycol, propylene glycol, polyethylene glycol Class.In turn, 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, implementing the washing carried out using water or common organic solvents in such as 20~90 seconds or so.Then, Using compressed air or compressed nitrogen or by rotation carry out it is air-dried, to remove the moisture on substrate.As needed using electricity Hot plate or baking oven etc. are thermally dried, and obtain the electroless plating basal layer for forming pattern.
[electroless plating processing, metal coating, metal are by film base material]
Electroless plating basal layer, which is formed by, on the substrate obtained and to operation as described above carries out electroless plating, To form metal coating on electroless plating basal layer.In this way operate and obtain metal coating and on substrate successively Having the metal of electroless plating basal layer, metal coating by film base material is also object of the invention.
Electroless plating processing (process) is not particularly limited, can use commonly known any electroless plating processing come into Row impregnates electroless plating basal layer formed on the substrate for example, usually using previous commonly known electroless plating solution Method in the plating solution (bath).
Above-mentioned electroless plating solution generally mainly contains metal ion (metal salt), complexing agent, reducing agent, in addition to these with It outside, depending on the application can suitably include pH adjusting agent, pH buffer, reaction promoter (the second complexing agent), stabilizer, surface work Property agent (assigning gloss purposes to plated film, the wetability of processed surface improves purposes etc.) etc..
As metal used in the metal coating formed by electroless plating here, can enumerate iron, cobalt, nickel, copper, Palladium, silver, tin, platinum, gold and their alloy are suitably selected according to purpose.
Furthermore about above-mentioned complexing agent, reducing agent, and according to metal ion progress suitably selection.
In addition, commercially available plating solution can be used in electroless plating solution, can be suitble to using such as メ Le テ ッ Network ス (strain) system Process for electroless nickel plating chemicals (メ Le プ レ ー ト (registered trademark) NI series), non-electrolytic copper facing chemicals (メ Le プ レ ー ト (note Volume trade mark) CU series)；Process for electroless nickel plating liquid (ICP ニ U ロ Application (registered trademark) series, ト ッ that open country pharmaceuticals industry (strain) difficult to understand is made 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 (registered trademark) 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 drug (strain) system 40)；Process for electroless nickel plating liquid (カ ニ ゼ Application (registered trademark) series, シ ュ ー マ ー (registrar of Japanese カ ニ ゼ Application (strain) system Mark) series, シ ュ ー マ ー (registered trademark) カ ニ Block ラ ッ Network (registered trademark) series), electroless plating palladium liquid (S-KPD)；ダ Electroless plating copper liquid (キ ュ ー Port ジ ッ ト (registered trademark) カ ッ パ ー ミ ッ Network ス series, サ ー キ ュ of ウ ケ ミ カ Le society Port ジ ッ ト (registered trademark) series), electroless plating palladium liquid (パ ラ マ ー ス (registered trademark) series), process for electroless nickel plating liquid (デ ュ ラ Port ジ ッ ト (registered trademark) series), electroless plating gold liquid (オ ー ロ レ Network ト ロ レ ス (registered trademark) series), non-electrical Solve electroless plating copper liquid (the ス Le カ ッ プ (note of tin plating electrolyte (テ ィ Application Port ジ ッ ト (registered trademark) series), 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), the electroless plating copper liquid (プ リ Application ト ガ Application ト (registered trademark) PV) etc. of ア ト テ ッ Network ジ ャ パ Application (strain) system.
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 formation speed, the film thickness of metal envelope.
As a result, about the sheet for being formed with metal coating on the basal layer obtained using photonasty substrate agent of the invention The metal of invention is by film base material, in the case where using transparent substrate as substrate, can make from be formed with plating envelope that The opposite sides of side observe the face that can be seen when transparent substrate and black are presented.
Therefore, implement metal coating on the basal layer for forming pattern and to using photoetching, can be patterned Plating envelope formed part the back side be black metal by film base material, therefore can using the substrate as visibility of image High transparent 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, it tries The physical property measurement of sample is carried out using following apparatus under the following conditions.
(1) GPC (gel permeation chromatography)
Device: Dong ソ ー (strain) HLC-8220GPC processed
Column: Showa electrician (strain) Shodex processed (registered trademark) GPC KF-804L+Shodex GPC KF-803L
Column temperature: 40 DEG C
Solvent: tetrahydrofuran
Detector: UV (254nm), RI
(2)1H NMR spectra
Device: Japan Electronics (strain) JNM-L400 processed
Solvent: CDCl3
Reference peaks: tetramethylsilane (0.00ppm)
(3)13C NMR spectra
Device: Japan Electronics (strain) JNM-ECA700 processed
Solvent: CDCl3
Relaxation reagent: praseodynium chromium (Cr (acac)3)
Reference peaks: CDCl3(77.0ppm)
(4) ICP luminesceence analysis (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: small-sized developing apparatus ADE-3000S is made in the capital three Network テ ス ア (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 (registered trademark) HPS-200 processed]
DP6A-12E: ethylene-oxide-modified dipentaerythritol hexaacrylate (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 the molal quantity 20) [village Xin Zhong chemistry work Industry (strain) NK エ ス テ Le A-GLY-20E processed]
P4A-35E: ethylene-oxide-modified pentaerythritol tetraacrylate (ethyleneoxide addition the molal quantity 35) [village Xin Zhong 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: 2 function urethane acrylate of polyether skeleton is [in new Village's chemical industry (strain) NK オ リ go UA-4200 processed]
UA7100: 3 function urethane acrylate of the polyether skeleton [village Xin Zhong chemical industry (strain) NK オ リ go processed UA-7100]
TPO: diphenyl (2,4,6- trimethylbenzoyl) phosphine oxide (Photoepolymerizationinitiater initiater) [BASF ジ ャ パ Application (strain) IRGACURE (registered trademark) 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 8330 [SHIN-ETSU HANTOTAI, Shin-Etsu Chemial Co., Ltd シ リ コ ー Application (registered trademark) KBM-903]
I-PrNH2: isopropylamine
2-BuNH2: sec-butylamine
N-OctylNH2: n-octylamine
N-DecylNH2: positive decyl amine
2EHA:2- ethylhexylamine
2MCHA:2- methylcyclohexyl amine
Aniline: aniline
O-Toluidine: ortho-aminotoluene
P-Toluidine: para-totuidine
O-Anisidine: o-anisidine
PE1: pentaerythrite four (3- mercaptobutylate) [Showa Denko K. K カ レ Application ズ MT (registered trademark) PE1)
Bis- (the 3- sulfydryl butyryl acyloxy) butane of BD1:1,4- [Showa Denko K. K's カ レ Application ズ MT (registrar Mark) BD1]
TPMB: trimethylolpropane tris (3- mercaptobutylate) [Showa Denko K. K TPBM]
The manufacture of [Production Example 1] HPS-Cl
Sulfonic acid chloride [キ シ ダ chemical (strain) system] 27g and chloroform 50g is added in the reaction flask of 500mL, is stirred And dissolve it equably.The solution is cooled to 0 DEG C under stream of nitrogen gas.
The hyperbranched polymerization that molecular end has dithiocarbamate groups is added in the reaction flask of another 300mL Object HPS 15g and chloroform 150g is stirred until becoming uniform under stream of nitrogen gas.
Under stream of nitrogen gas, Xiang Shangshu is cooled in 0 DEG C of sulfonic acid chloride/chloroformic solution, using delivery pump, is had from addition 60 points are lasted in a manner of making the temperature of reaction solution become -5~5 DEG C in the reaction flask of the above-mentioned 300mL of HPS/ chloroformic solution Clock adds the solution.After addition, stirred while the temperature of reaction solution is maintained at -5~5 DEG C 6 hours.
In turn, it is added into the reaction solution by cyclohexene [Tokyo in such a way that the temperature for making reaction solution becomes -5~5 DEG C At industrial (strain) system] 16g is dissolved in solution obtained by chloroform 50g.After addition, which is added to IPA1, In 200g, precipitate polymer.The white powder that the leaching precipitating 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 Obtained dissaving polymer (HPS-Cl) 8.5g (yield 99%) that molecular end has chlorine atom.
By the HPS-Cl's of acquisition1H NMR spectra is shown in Figure 1.From the peak of dithiocarbamate groups (4.0ppm, 3.7ppm) disappears, and thus specifies: in the HPS-Cl of acquisition, the dithiocarbamate of HPS molecular end 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, converted with polystyrene Weight average molecular weight Mw is 14,000, and dispersion degree Mw/Mn is 2.9.
[Production Example 2] HPS-N (Me)2The manufacture of OctCl
The HPS-Cl 4.6g manufactured by Production Example 1 is added in the reaction flask for the 100mL for being provided with cooler (30mmol) and chloroform 15g is stirred until becoming uniform.It is added into the solution and is dissolved with dimethyl-octa in chloroform 7.5g Solution obtained by base amine [flower king (strain) フ ァ ー ミ Application (registered trademark) DM0898 processed] 5.0g (31.5mmol), is further added 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 is 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, is carried out at 50 DEG C true Sky is dry, and the dissaving polymer (HPS-N that molecular end has dimethyl octyl ammonium is obtained in the form of white powder (Me)2OctCl)9.3g。
By the HPS-N (Me) of acquisition2OctCl's13C NMR spectra is shown in Figure 2.By the peak of phenyl ring and the first of octyl end The peak of base specifies: in the HPS-N (Me) of acquisition2In OctCl, the chlorine atom of HPS-Cl molecular end is substantially quantitatively by ammonium Base instead of.In addition, the HPS-N (Me) calculated by the Mw (14,000) and ammonium Drug delivery rate (100%) of HPS-Cl2OctCl's Weight average molecular weight Mw is 28,000.
The manufacture of [Production Example 3] HBP-Pd-1
Acid chloride is added in the reaction flask for the 100mL for being provided with cooler and [grinds Off ァ イ Application ケ ミ カ Le product in river (strain) system] 4.2g and chloroform 40g, it is stirred until becoming uniform.It is added into the solution in chloroform using dropping funel The HPS-N (Me) manufactured by Production Example 2 is dissolved in 100g2Solution obtained by OctCl8.0g.Use chloroform 20g and 40g couples of ethyl alcohol It is washed in the dropping funel, flows into cleaning solution in 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 solution (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 Obtain the complex (Pd [HPS-N (Me) of dissaving polymer and Pd particle of the molecular end with ammonium2OctCl])8.9g (HBP-Pd-1)。
By the result of ICP luminesceence analysis it is found that the Pd [HPS-N (Me) obtained2OctCl] the Pd content of (HBP-Pd-1) is 20 mass %.In addition, by TEM (transmission electron microscope) image it is found that the Pd partial size is about 2~4nm.
The modulation of [reference example 1] process for electroless nickel plating liquid
カ ニ ゼ Application (registered trademark) ブ ル ー シ ュ ー マ ー [Japanese カ ニ ゼ Application (strain) is added in the beaker of 2L System] 100mL, further adds pure water so that the total amount of solution becomes 400mL.The solution is stirred, electroless plating is made Nickel liquid.
[embodiment 1]
[modulation of photonasty substrate agent]
It (will be also referred to as below as 7 mass parts of HBP-Pd-1 of Pd catalyst manufactured by Production Example 3, as amine compounds For " amine ") 0.875 mass parts of KBM-903, as 80 mass parts of T3A-20E of polymerizable compound, as multifunctional sulphur 0.8 mass parts of PE1 of alcohol (also referred to as RSH), 20 mass parts of TPO as polymerization initiator and the PrOH as solvent are mixed It closes, modulates the sense of the electroless plating of 1 mass % of non-solvent ingredients (removing the whole components after solvent in mixture) concentration Photosensitiveness substrate agent.In addition, dissolving each ingredient respectively with a part of the usage amount of PrOH, resulting liquid is mixed, To be easy equably to mix each ingredient.
In addition, among the above used HBP-Pd-1 being mixed with amine compounds in advance according to the following steps and being formed Then amine complex mixes it with other ingredients of photonasty substrate agent.
< amine complex forms >
The HBP-Pd-1 500mg manufactured by above-mentioned Production Example 3 is dissolved in PGME (solution 1), becomes solution total amount Then 5g is stirred 30 minutes using stirring rotator.
On the other hand, the KBP-903 1.25g as amine compounds is dissolved in PGME (solution 2), keeps the solution total Amount becomes 5g, is stirred using stirring rotator.The solution 2 is further diluted 10 times using PGME.
To the solution 2 (amine compounds) that addition 2.5g diluted in solution 1 (HBP-PD-1), PGME is further added, is made Total amount becomes 10g.
Use 5 mass % solution for the HBP-PD-1 of 140mg obtained by this step.
[coating]
By above-mentioned photonasty substrate agent 2.4mL rotary coating (200rpm × 5 second, then 1,000rpm × 25 second) in 4 English On very little wafer shape glass substrate.The substrate is 1 minute dry using 65 DEG C of electric hot plate, it obtains the whole face on substrate and has The substrate of basal layer.
[pattern forms (exposure and imaging)]
Using the mask aligner for describing the photomask for having 3 μm of wide patterns is provided with, in air atmosphere, with 14.6mW/cm2Illumination to the basal layer of acquisition so that light exposure becomes 400mJ/cm2Mode be irradiated and expose.
Developed using the developing apparatus for being provided with spray spout to the substrate exposed.About development, make base on one side Material is rotated with 300rpm to be washed with water 90 seconds on one side, is then improved revolving speed to 2,000rpm and is got rid of water.
The substrate is 30 seconds dry using 65 DEG C of electric hot plate, it is 5 minutes dry followed by 150 DEG C of electric hot plates, it obtains Has the substrate of the electroless plating basal layer to form pattern on substrate.
[electroless plating]
The substrate of acquisition is impregnated 3 minutes in the process for electroless nickel plating liquid modulated by reference example 1 for being heated to 80 DEG C.So Afterwards, the substrate of taking-up is washed, it is 3 minutes dry using 100 DEG C of electric hot plates, to obtain plating base.
About 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 together.
< plating forms state evaluation benchmark >
OK: can obtain the substrate layer pattern as mask pattern, be precipitated in basal layer drafting department coating and (form pattern The plating envelope changed)
NG: patterned plating envelope is not formed
The blackened evaluation criteria > in the back side <
A: by fully blackened
B: brown is observed
C: effect is not observed
[embodiment 2~21]
The record that each ingredient of photonasty substrate agent is altered to table 1 is operated similarly with example 1 in addition to this, into Evaluation is gone.It will be in result together shown in table 1 and table 2.In addition, in Tables 1 and 2, it is [molten in 5~embodiment of embodiment 11 Agent] numerical value [PGME:PrOH=8:2] documented by column indicates used 2 kinds of solvent PGME and PrOH with the mass ratio of 8:2 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 (about the 1/10 of Fig. 3 times of digital microscope images of the image of Fig. 3 of the metal coating of acquisition compared to the large-scale appearance of display Rate is low in this way) it is shown in Figure 4.
[1~comparative example of comparative example 3]
Each ingredient of photonasty substrate agent is altered to each ingredient that table 1 is recorded, in addition to this, similarly to Example 1 Operation, is evaluated.Result is shown in Table 1 together.In addition, comparative example 1 and comparative example 2 do not form patterned plating 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 by subsequent development, the pattern of basal layer flows, and becomes whole face plating, therefore do not carry out the blackened evaluation in the back side.
As shown in table 1, basal layer is being formed using photonasty substrate agent of the invention, it is being exposed across mask Light forms plated film then by the electroless plating basal layer for obtaining and having patterned that develops on the electroless plating basal layer In the case of (1~embodiment of embodiment 7), plating envelope (referring to Fig. 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 3 or more (methyl) acryloyl groups Object (UA7100) is closed as in the 4~embodiment of embodiment 7 of (c) polymerizable compound, result is from glass substrate back side To plating envelope form part and show black or brown.
In contrast, in the comparative example 1 and comparative example 2 for being not added with amine, the comparative example 3 for being not added with multi-functional thiol, do not have There is the plate substrate layer to be formed and patterned, does not form the plating envelope patterned.
In addition, all substantially obtaining figure in 8~embodiment of embodiment 17 that the amine of addition has been carried out various changes The plating envelope of case.
In addition, in any embodiment, can be developed after forming the exposure after basal layer using water.
Specified by result above: photonasty substrate agent of the invention can form the plating patterned by photoetching Basal layer is advantageous in terms of obtaining width and being several μm of metal coatings fine in this way.

Claims (16)

1. a kind of photonasty substrate agent forms metal coating for handling by electroless plating on substrate comprising:
(a) dissaving polymer that molecular end has ammonium and weight average molecular weight is 1,000~5,000,000,
(b) metal particle,
(c) intramolecular has the polymerizable compound of 1 or more (methyl) acryloyl group,
(d) Photoepolymerizationinitiater initiater,
(e) amine compounds, and
(f) multi-functional thiol.
2. photonasty substrate agent according to claim 1, (c) polymerizable compound is that intramolecular has 3 or more 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. photonasty substrate agent according to claim 1 or 2, (f) multi-functional thiol is 4 functional thiols.
5. photonasty substrate agent according to claim 1 or 2, (e) amine compounds are with alkoxysilyl Amine compounds.
6. photonasty substrate agent according to claim 1 or 2, (a) dissaving polymer is to overspend shown in formula [1] Fluidized polymer,
In formula [1], R1Hydrogen atom or methyl are each independently represented,
R2~R4Each independently represent hydrogen atom, the straight-chain of carbon atom number 1~20, branched or cricoid alkyl, carbon atom The aryl alkyl of number 7~20 or-(CH2CH2O)mR5Or R2~R4Nitrogen-atoms in conjunction with them is formed together ring,
Above-mentioned formula-(CH2CH2O)mR5In, R5Indicate that hydrogen atom or methyl, m indicate 2~100 integer, abovementioned alkyl and aryl alkane Base can be replaced by alkoxy, hydroxyl, ammonium, carboxyl or cyano,
X-Indicate anion,
N is the number of repeat unit structure, indicates 5~100,000 integer,
A1Structure shown in expression [2],
In formula [2], A2Expression may include straight-chain, branched or the cricoid alkylene of the carbon atom number 1~30 of ehter bond or ester bond Base, Y1~Y4Each independently represent hydrogen atom, the alkyl of carbon atom number 1~20, the alkoxy of carbon atom number 1~20, nitro, Hydroxyl, amino, carboxyl or cyano.
7. photonasty substrate agent according to claim 6, in above-mentioned formula [1], R2~R4In 2 groups indicate straight together Chain, branched or cricoid alkylidene.
8. 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 indicated with n.
9. photonasty substrate agent according to claim 1 or 2, (b) metal particle be selected from iron (Fe), cobalt (Co), The particle of at least one of nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold (Au) metal.
10. photonasty substrate agent according to claim 9, (b) metal particle is palladium particle.
11. photonasty substrate agent according to claim 1 or 2, (b) metal particle is 1~100nm's of average grain diameter Particle.
12. photonasty substrate agent according to claim 1 or 2 can be formed by photoetching to carry out pattern.
13. a kind of electroless plating basal layer is using the patterned layer being lithographically derived, by any one of claim 1~12 The photonasty substrate dosage form at.
14. a kind of metal coating, the electroless plating basal layer as described in claim 13 and in the electroless plating basal layer The electroless plating of upper formation is constituted.
15. a kind of metal is had by film base material:
Substrate, and
Metal coating described in claim 14,
The electroless plating basal layer that the metal coating has is formed on the substrate.
16. a kind of metal is by the manufacturing method of film base material comprising following A process~C process,
A process: photonasty substrate agent described in any one of claim 1~12 is coated on substrate, it is made to have base The process of bottom,
B process: the process by being lithographically formed the basal layer with expected pattern,
C process: the substrate that will be provided with being formed the basal layer of pattern is impregnated in non-electrolytic plating bath, the process for forming metal coating.
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