JPWO2017154913A1 - Photosensitive electroless plating base material - Google Patents

Abstract

A new non-electrolytic plating pretreatment process that can be easily processed with a small number of processes and that can easily form fine wiring with a width of several μm by printing or photolithography in consideration of the environment. To provide an electrolytic plating base material.
A base agent for forming a metal plating film on a substrate by electroless plating,
(A) a hyperbranched polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000,
(B) metal fine particles,
(C) a polymerizable compound having one or more (meth) acryloyl groups in the molecule;
(D) A photosensitive base agent comprising a photopolymerization initiator and (e) a surfactant.
[Selection] Figure 1

Description

  The present invention relates to a photosensitive base material comprising a hyperbranched polymer, metal fine particles, a polymerizable compound and a photopolymerization initiator.

  In recent years, with the miniaturization of devices such as personal computers, mobile phones, and wearable terminals, it is easy to form fine wiring patterns in order to form high-density patterns and wiring with high transmittance and visibility on a transparent substrate. There is a need for a technique to do this.

  As one of means for forming fine wiring, a method of performing electroless plating after patterning an electroless plating catalyst by photolithography is disclosed (Patent Document 1). Specifically, a material in which a metal complex, metal ion, or metal colloid that serves as a catalyst for electroless plating is mixed with a photosensitive resin is used, and UV exposure and development through a photomask can be used to form an arbitrary lattice shape or the like. A method for obtaining a conductive pattern by forming a base of a pattern and applying electroless plating thereto is disclosed.

  In addition, by using a composition containing an ammonium group-containing hyperbranched polymer and Pd fine particles as an electroless plating base agent, the electroless plating can be directly immersed in the electroless plating solution without going through an activation process after coating. An example in which plating is formed is disclosed (Patent Document 2).

JP-A-11-170421 International Publication No. 2012/141215 Pamphlet

  In Patent Document 1, protective colloids such as PVP and surfactants such as dodecylbenzenesulfonic acid are used as metal colloid stabilizers. Stability of varnish due to decomposition of protective colloids and aggregation of metal colloids is used. In the process, it is often difficult to clean the catalyst during development. In addition, when the electroless plating is performed, it is a problem that the plating is deposited in addition to the target portion. Furthermore, since a water-soluble resist or metal stabilizer is used, there is a problem in maintaining pattern shapes such as pattern bleeding and line thickening. In this patent document, only the transmittance and resistance value of the obtained transparent conductive film are discussed, and the line width (shape) of the obtained pattern is not described in detail.

  Moreover, the visibility of an image is requested | required of the transparent electrode used for a liquid crystal display element. However, when metal wiring is formed by electroless plating, the formed metal film has a metallic luster and reflects external light, so that the metal wiring is not conspicuous and a clear display device with high image visibility is manufactured. There is a problem that it is difficult to do. Therefore, in the technique of forming a transparent electrode by electroless plating, suppression of metallic luster due to blackening on the back surface (transparent substrate surface) of the formed metal plating film is required.

  Therefore, the present invention pays attention to such problems, considers the environment, can be easily processed with a small number of steps, and can be easily formed with a fine wiring having a width of several μm by photolithography. The object is to provide a new electroless plating base material to be used.

  As a result of diligent studies to achieve the above object, the present inventors have found that a hyperbranched polymer and metal fine particles having an ammonium group at the molecular end, a specific polymerizable compound, a photopolymerization initiator, an amine compound, A layer obtained by combining a functional thiol with a photosensitive thiol and applying it onto a substrate can be patterned by photolithography, and a patterned electroless metal plating underlayer can be obtained. The present inventors have found that the underlayer has excellent plating properties and becomes a useful layer for improving the adhesion between the metal plating film and the substrate to be plated. At that time, by adding a surfactant to the composition for forming a plating underlayer, it was found that the plating deposition property with fine wires was improved, and the present invention was completed.

That is, the present invention, as a first aspect, is a base agent for forming a metal plating film on a substrate by electroless plating treatment,
(A) a hyperbranched polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000,
(B) metal fine particles,
(C) a polymerizable compound having one or more (meth) acryloyl groups in the molecule;
The present invention relates to a photosensitive base material containing (d) a photopolymerization initiator and (e) a surfactant.
As a 2nd viewpoint, the said (c) polymeric compound is related with the photosensitive base agent as described in a 1st viewpoint which is a compound which has a 3 or more (meth) acryloyl group in a molecule | numerator.
As a third aspect, the photosensitive compound according to the first aspect or the second aspect, in which the polymerizable compound (c) is a compound having three or more (meth) acryloyl groups and an oxyalkylene group in the molecule. Relates to an adhesive base material.
As a fourth aspect, the present invention relates to the photosensitive base material according to any one of the first aspect to the third aspect, further comprising (f) a compound having an amino group.
As a fifth aspect, the present invention relates to the photosensitive base material according to any one of the first aspect to the fourth aspect, further containing (g) a polyfunctional thiol.
As a sixth aspect, the present invention relates to the photosensitive base material according to the fourth aspect or the fifth aspect, wherein the compound (f) having an amino group is an alkoxysilane compound having an amino group.
As a seventh aspect, the present invention relates to the photosensitive base material according to the fifth aspect or the sixth aspect, wherein the polyfunctional thiol (g) is a tetrafunctional thiol.
As an eighth aspect, the present invention relates to the photosensitive base material according to any one of the first aspect to the seventh aspect, in which the (a) hyperbranched polymer is a hyperbranched polymer represented by the formula [1].
(In the formula, each R ¹ independently represents a hydrogen atom or a methyl group, and R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , An arylalkyl group having 7 to 20 carbon atoms or — (CH ₂ CH ₂ O) _m R ⁵ (wherein R ⁵ represents a hydrogen atom or a methyl group, and m represents an integer of 2 to 100). (The alkyl group and the arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group), or ^two of R ^{2 to} R ⁴ may be bonded together. Represents a linear, branched or cyclic alkylene group, or R ^{2 to} R ⁴ may form a ring together with the nitrogen atom to which they are bonded, and X ⁻ represents an anion. N is repeated A number of unit structures represents an integer of 5 to 100,000, ^{A 1} represents a structure represented by the formula [2].)
(In the formula, A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ^{1 to} Y ⁴ are each independently hydrogen. And represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group, or a cyano group.
As a ninth aspect, the present invention relates to the photosensitive base material according to the eighth aspect, wherein the (a) hyperbranched polymer is a hyperbranched polymer represented by the formula [3].
(In the formula, R ^{1 to} R ⁴ and n represent the same meaning as described above.)
As a tenth aspect, (b) the metal fine particles are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum ( The photosensitive base agent according to any one of the first to ninth aspects, which is fine particles of at least one metal selected from the group consisting of Pt) and gold (Au).
As an eleventh aspect, the present invention relates to the photosensitive base material according to the tenth aspect, in which the metal fine particles (b) are palladium fine particles.
As a twelfth aspect, the present invention relates to the photosensitive base material according to any one of the first aspect to the eleventh aspect, wherein the metal fine particles (b) are fine particles having an average particle diameter of 1 to 100 nm.
As a thirteenth aspect, the present invention relates to the photosensitive base material according to any one of the first aspect to the twelfth aspect for forming a layer capable of forming a pattern by photolithography.
As a 14th viewpoint, it is related with the electroless-plating base layer obtained using the photosensitive base agent as described in any one of a 1st viewpoint thru | or a 13th viewpoint.
As a 15th viewpoint, it is related with the metal plating film formed on the electroless-plating base layer as described in a 14th viewpoint.
As a sixteenth aspect, the base material, the electroless plating base layer according to the fourteenth aspect formed on the base material, and the metal plating film according to the fifteenth aspect formed on the electroless plating base layer And a metal-coated substrate.
As a 17th viewpoint, it is related with the manufacturing method of a metal film base material containing the following A process thru | or C process.
Step A: Step of applying the photosensitive base agent according to any one of the first to thirteenth aspects on a substrate and providing a base layer Step B: under a desired pattern by printing or photolithography Step C for forming a base layer: a step of immersing a base material provided with a patterned underlayer in an electroless plating bath to form a metal plating film.

The photosensitive base material of the present invention can be easily obtained by drawing a pattern directly on a substrate by printing such as ink jet and photocuring, or by applying it on the substrate and performing photolithography through a mask. A patterned underlayer of electroless metal plating can be formed.
In addition, the photosensitive base agent of the present invention is a base layer that has excellent adhesion to a base material without forming a primer layer that has been conventionally formed on the base material in order to improve the adhesion to a metal plating film. Can be formed. Furthermore, the photosensitive base material of the present invention can form a plating base layer patterned on the order of μm, and can be suitably used for various wiring techniques.

FIG. 1 is a diagram showing a ¹ H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end produced in Production Example 1. FIG. 2 is a diagram showing a ¹³ C NMR spectrum of a hyperbranched polymer (HPS-N (Me) ₂ OctCl) having a dimethyloctylammonium group at the molecular end produced in Production Example 2.

[Base material]
<(A) Hyperbranched polymer>
The (a) hyperbranched polymer used in the photosensitive base material of the present invention is a polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000, specifically Examples include hyperbranched polymers represented by the following formula [1].
In the above formula [1], R ¹ represents a hydrogen atom or a methyl group independently.
R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or-( CH ₂ CH ₂ O) _m R ⁵ (wherein R ⁵ represents a hydrogen atom or a methyl group, and m represents an arbitrary integer of 2 to 100). The alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group. And two groups of R ^{2 to} R ⁴ are taken together to represent a linear, branched or cyclic alkylene group, or R ^{2 to} R ^{4 and} the nitrogen atom to which they are bonded together To form a ring.
X ⁻ represents an anion, n represents the number of repeating unit structures, and represents an integer of 5 to 100,000.

Examples of the linear alkyl group having 1 to 20 carbon atoms in R ^{2 to} R ⁴ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned, and a group having 8 or more carbon atoms is preferable in that the base agent is difficult to elute into the electroless plating solution. Octyl groups are preferred. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure.
Examples of the arylalkyl group having 7 to 20 carbon atoms in R ^{2 to} R ⁴ include a benzyl group and a phenethyl group.
Furthermore, examples of the linear alkylene group in which ^two of R ^{2 to} R ⁴ are combined include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Examples of the branched alkylene group include a methylethylene group, a butane-1,3-diyl group, and a 2-methylpropane-1,3-diyl group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms. These alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
In the structure represented by the formula [1], the ring formed by combining R ^{2 to} R ⁴ and the nitrogen atom bonded thereto may contain a nitrogen atom, a sulfur atom or an oxygen atom in the ring. For example, pyridine ring, pyrimidine ring, pyrazine ring, quinoline ring, bipyridyl ring and the like can be mentioned.
Examples of combinations of R ^{2 to} R ⁴ include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], [methyl group] Group, methyl group, n-hexyl group], [methyl group, methyl group, n-octyl group], [methyl group, methyl group, n-decyl group], [methyl group, methyl group, n-dodecyl group], [Methyl group, methyl group, n-tetradecyl group], [methyl group, methyl group, n-hexadecyl group], [methyl group, methyl group, n-octadecyl group], [ethyl group, ethyl group, ethyl group], [N-butyl group, n-butyl group, n-butyl group], [n-hexyl group, n-hexyl group, n-hexyl group], [n-octyl group, n-octyl group, n-octyl group] Among them, [methyl group, methyl group, - octyl], [n- octyl group, n- octyl group, a combination of n- octyl group] are preferable.
The X ^- is preferably a halogen atom _anion, ^PF 6 -, BF ₄ ^- or perfluoroalkane sulfonate and the like.

In the above formula [1], A ¹ represents a structure represented by the following formula [2].
In the above formula [2], A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
Y ^{1 to} Y ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group, or a cyano group. Represent.

Specific examples of the alkylene group of A ² include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, a methylethylene group, a butane-1,3-diyl group, 2 -Branched alkylene groups such as methylpropane-1,3-diyl group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic and bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms. For example, structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.

Examples of the alkyl group having 1 to 20 carbon atoms of Y ^{1 to} Y ^{4 in} the formula [2] include a methyl group, an ethyl group, an isopropyl group, an n-pentyl group, and a cyclohexyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, n-pentyloxy group, cyclohexyloxy group and the like. Y ^{1 to} Y ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

Preferably, the hyperbranched polymer used in the present invention includes a hyperbranched polymer represented by the following formula [3].
In the above formula ^{[3], R 1, R} 2 to ^{R 4} and n are as defined above.

The hyperbranched polymer having an ammonium group at the molecular end used in the present invention can be obtained, for example, by reacting an amine compound with a hyperbranched polymer having a halogen atom at the molecular end.
A hyperbranched polymer having a halogen atom at the molecular end can be produced from a hyperbranched polymer having a dithiocarbamate group at the molecular end in accordance with the description in WO 2008/029688. As the hyperbranched polymer having a dithiocarbamate group at the molecular end, a commercially available product can be used, and Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be suitably used.

  The amine compounds that can be used in this reaction include, as primary amines, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n -Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine , N-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosylamine and other aliphatic amines; cyclopentylamine, cyclohexylamine and other alicyclic amines; benzylamine, phenethylamine and the like The Alla Killamine: Anilines such as aniline, pn-butylaniline, p-tert-butylaniline, pn-octylaniline, pn-decylaniline, pn-dodecylaniline, pn-tetradecylaniline , Naphthylamines such as 1-naphthylamine and 2-naphthylamine, aminoanthracenes such as 1-aminoanthracene and 2-aminoanthracene, aminoanthraquinones such as 1-aminoanthraquinone, amino such as 4-aminobiphenyl and 2-aminobiphenyl Aminophenyls such as biphenyls, 2-aminofluorene, 1-amino-9-fluorenone, 4-amino-9-fluorenone, aminoindanes such as 5-aminoindane, aminoisoquinolines such as 5-aminoisoquinoline, 9 -Amino Aromatic amines such as amino-phenanthrene such as phenanthrene and the like. Furthermore, N- (tert-butoxycarbonyl) -1,2-ethylenediamine, N- (tert-butoxycarbonyl) -1,3-propylenediamine, N- (tert-butoxycarbonyl) -1,4-butylenediamine, N -(Tert-butoxycarbonyl) -1,5-pentamethylenediamine, N- (tert-butoxycarbonyl) -1,6-hexamethylenediamine, N- (2-hydroxyethyl) amine, N- (3-hydroxypropyl) ) Amine compounds such as amine, N- (2-methoxyethyl) amine, N- (2-ethoxyethyl) amine.

  Secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-pentylamine, ethylmethylamine, methyl- n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl- n-dodecylamine, methyl-n-tetradecylamine, methyl-n-hexadecylamine, methyl-n-octadecylamine, ethylisopropylamine, ethyl-n-octylamine, di-n-hexylamine, di-n- Octylamine, di-n-dode Aliphatic amines such as diamine, aralkyl amines such as dibenzylamine, aromatic amines such as diphenylamine, phthalimide, pyrrole, Examples thereof include nitrogen-containing heterocyclic compounds such as piperidine, piperazine, and imidazole. Furthermore, bis (2-hydroxyethyl) amine, bis (3-hydroxypropyl) amine, bis (2-ethoxyethyl) amine, bis (2-propoxyethyl) amine and the like can be mentioned.

  Tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-n-dodecyl. Amine, dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecyl Aliphatic amines such as amine, dimethyl-n-hexadecylamine, dimethyl-n-octadecylamine, dimethyl-n-eicosylamine; pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4′-bipyridyl, 4-methyl-4,4 ' Nitrogen-containing heterocyclic compound of bipyridyl, and the like.

  The amount of the amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, based on 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular end. Preferably, it may be 1 to 5 molar equivalents.

The reaction between the hyperbranched polymer having a halogen atom at the molecular end and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base. The solvent to be used is preferably a solvent capable of dissolving a hyperbranched polymer having a halogen atom at the molecular end and an amine compound. Furthermore, a hyperbranched polymer having a halogen atom at the molecular end and an amine compound can be dissolved, but a solvent that does not dissolve the hyperbranched polymer having an ammonium group at the molecular end is more preferable because it can be easily isolated.
The solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. Water; alcohols such as isopropanol; organic acids such as acetic acid; benzene, toluene, xylene, ethylbenzene, 1,2-di- Aromatic hydrocarbons such as chlorobenzene; Ethers such as tetrahydrofuran (THF) and diethyl ether; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone; Chloroform, dichloromethane, 1,2-dichloroethane Halides such as n-hexane, n-heptane, cyclohexane, etc .; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), etc. The amides can be used. These solvents may be used alone or in combination of two or more. The amount used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably the mass of the hyperbranched polymer having a halogen atom at the molecular end. Is preferably 5 to 50 times the mass of the solvent.

  Suitable bases generally include alkali metal hydroxides and alkaline earth metal hydroxides (eg sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg lithium oxide). Calcium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg sodium hydride, potassium hydride, calcium hydride), alkali metal amides (eg sodium amide), alkali metal carbonates and alkaline earth metal carbonates Inorganic compounds such as salts (eg lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), and alkali metal alkyls, alkylmagnesium halides, alkali metal alkoxides, alkaline earth metals Alkoxy Organometallic compounds such as dimethoxy magnesium was used. Particularly preferred are potassium carbonate and sodium carbonate. The amount used is 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, most preferably 1 to 5 molar equivalents per mole of halogen atoms of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use the base.

  In this reaction, it is preferable to sufficiently remove oxygen in the reaction system before starting the reaction, and the system may be replaced with an inert gas such as nitrogen or argon. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C. The reaction time is preferably 0.1 to 72 hours, and the reaction temperature is 20 to 150 ° C.

When a tertiary amine is used, a hyperbranched polymer represented by the formula [1] can be obtained regardless of the presence / absence of a base.
When a hyperbranched polymer having a halogen atom at the molecular end is reacted with a primary amine or secondary amine compound in the absence of a base, the terminal secondary amine and tertiary tertiary of the corresponding hyperbranched polymer are respectively reacted. A hyperbranched polymer having ammonium groups terminated with protonated primary amines is obtained. In addition, even when the reaction is performed using a base, the terminal secondary amine of the corresponding hyperbranched polymer can be obtained by mixing with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. And a hyperbranched polymer having an ammonium group terminated with a tertiary amine protonated.

  The hyperbranched polymer has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 1,000 to 5,000,000, more preferably 2,000 to 200,000, most preferably 3,000 to 100,000. Further, the dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and more preferably 1.2 to 5. 0.

<(B) Metal fine particles>
(B) The metal fine particles used in the photosensitive base material of the present invention are not particularly limited, and the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd). Silver (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof may be used, and one kind of these metals may be used or two or more kinds may be used in combination. Among these, preferable metal fine particles include palladium fine particles. The metal oxide may be used as the metal fine particles.

  The metal fine particles can be obtained by reducing metal ions by, for example, a method of irradiating an aqueous solution of a metal salt with a high-pressure mercury lamp or a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution. For example, by adding an aqueous solution of a metal salt to the solution in which the hyperbranched polymer is dissolved and irradiating it with ultraviolet light, or adding an aqueous solution of a metal salt and a reducing agent to the hyperbranched polymer solution, etc. The base agent containing the hyperbranched polymer and the metal fine particles can be prepared while forming a complex of the hyperbranched polymer and the metal fine particles.

Examples of the metal salt include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, copper acetate, tin chloride, platinum chloride, chloroplatinic acid, Pt (dba) ₂ [dba = dibenzylideneacetone], Pt (cod) ₂ [cod = 1,5-cyclooctadiene], Pt (CH ₃ ) ₂ (cod), palladium chloride, palladium acetate (Pd (OC (═O) CH ₃ ) ₂ ), palladium nitrate, Pd ₂ (dba) _{3 · CHCl 3, Pd (dba} ) 2, rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni _{(cod) 2,} etc. Is mentioned.
The reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species to be contained in the obtained base material. Examples of the reducing agent that can be used include metal borohydrides such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, hydrogenation Aluminum hydride salts such as aluminum magnesium and calcium aluminum hydride; hydrazine compounds; citric acid and salts thereof; succinic acid and salts thereof; ascorbic acid and salts thereof; primary or secondary such as methanol, ethanol, isopropanol and polyol Tertiary alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine (TMEDA), ethylenediaminetetraacetic acid (EDTA); Roxylamine; tri-n-propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis (diphenylphosphino) ethane (DPPE), 1,3 -Bis (diphenylphosphino) propane (DPPP), 1,1'-bis (diphenylphosphino) ferrocene (DPPF), 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP), etc. And phosphines.

  The average particle size of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the metal fine particles to 100 nm or less, a sufficient catalytic activity can be obtained with little reduction in surface area. As an average particle diameter, 75 nm or less is further more preferable, and 1-30 nm is especially preferable.

  The addition amount of the (a) hyperbranched polymer in the photosensitive base material of the present invention is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of the (b) metal fine particles. By setting it to 50 parts by mass or more, the metal fine particles can be sufficiently dispersed, and by setting it to 2,000 parts by mass or less, problems such as physical properties due to an increase in organic content can be suppressed. it can. More preferably, it is 100-1,000 mass parts.

<(C) Polymerizable compound having one or more (meth) acryloyl groups in the molecule>
As the polymerizable compound (c) having at least one (meth) acryloyl group in the molecule (hereinafter also simply referred to as a polymerizable compound) used in the photosensitive base agent of the present invention, preferably three in the molecule. The compound which has the above (meth) acryloyl group is mentioned, Especially, the compound which has three or more (meth) acryloyl groups in a molecule | numerator, and has an oxyalkylene group is mentioned.
As the oxyalkylene group, an oxyalkylene group having 2 to 4 carbon atoms is preferable, and among them, an oxyethylene group [—OCH ₂ CH ₂ —] or an oxypropylene group [—OCH ₂ C (CH ₃ ) H—] is preferable. . The oxyalkylene group may be a poly (oxyalkylene) group in which a plurality of oxyalkylene groups are connected. In that case, the oxyalkylene group may have a single oxyalkylene group or a combination of two or more. Also good. In the case of having a plurality of types of oxyalkylene groups, these bonds may be block bonds or random bonds.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of the polymerizable compound include monomers containing one or more (meth) acryloyl groups such as urethane acrylic, epoxy acrylic, and various (meth) acrylates, particularly those containing three or more (meth) acryloyl groups. A functional monomer etc. are mentioned.
Among these polymerizable compounds, a compound having 3 or more (meth) acryloyl groups and an oxyalkylene group and a polyfunctional urethane (meth) acrylate compound having 3 or more (meth) acryloyl groups are preferable.
Hereinafter, although an example of a compound suitable as (c) polymeric compound of this invention is given, (c) polymeric compound is not limited to these illustrations.

[Compound having 3 or more (meth) acryloyl groups and an oxyalkylene structure]
(1) Trifunctional compound (having three (meth) acryloyl groups) As a compound having three (meth) acryloyl groups and having an oxyalkylene structure (trifunctional compound), for example, ethylene oxide modified 1,1, 1-trimethylolethane tri (meth) acrylate [ethylene oxide addition mole number 3 to 30], ethylene oxide modified trimethylolpropane tri (meth) acrylate [ethylene oxide addition mole number 3 to 30], propylene oxide modified trimethylolpropane tri (meth) Acrylate [propylene oxide addition mole number 3-30], ethylene oxide modified glycerol tri (meth) acrylate [ethylene oxide addition mole number 3-30], propylene oxide modified glycerol tri (meth) acrylate [propylene oxide addition] Mole number 3 to 30], tris (2- (acryloyloxy) ethyl) isocyanurate, ε-caprolactone-modified tris (2- (acryloyloxy) ethyl) isocyanurate [ε-caprolactone addition mole number 1 to 30] and the like. It is done.

  Commercially available products can be suitably used as the trifunctional compound, for example, Biscote # 360 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); NK ester A-GLY-9E, A-GLY-20E, AT-20E [above or more] , All manufactured by Shin-Nakamura Chemical Co., Ltd.]; TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [all manufactured by Daicel Ornex Co., Ltd.] and the like.

(2) Tetrafunctional compound (having four (meth) acryloyl groups) As the compound (tetrafunctional compound) having four (meth) acryloyl groups and having an oxyalkylene structure, for example, ethylene oxide-modified ditrimethylolpropanetetra (Meth) acrylate [ethylene oxide addition mole number 4 to 40], ethylene oxide modified pentaerythritol tetra (meth) acrylate [ethylene oxide addition mole number 4 to 40] and the like.

  Commercially available products can be suitably used as the tetrafunctional compound, for example, NK ester ATM-4E, ATM-35E [all are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 40 [Daicel Ornex] Etc.].

(3) A compound having 5 or more functional groups (having 5 or more (meth) acryloyl groups) As a compound having 5 or more (meth) acryloyl groups and having an oxyalkylene structure (a compound having 5 or more functional groups), for example, Examples include ethylene oxide-modified dipentaerythritol hexa (meth) acrylate [ethylene oxide addition mole number 6 to 60], ethylene oxide-modified tripentaerythritol octa (meth) acrylate [ethylene oxide addition mole number 6 to 60], and the like.

  Commercially available products can be suitably used as the pentafunctional or higher compound, and examples thereof include NK ester A-DPH-12E [manufactured by Shin-Nakamura Chemical Co., Ltd.].

[Polyfunctional urethane (meth) acrylate compound having 3 or more (meth) acryloyl groups]
By using a urethane compound in combination as the polymerizable compound (c) of the present invention, it is preferable because the back surface of the coating can be blackened after the metal plating coating described below is formed.

(1) Trifunctional (having three (meth) acryloyl groups) urethane (meth) acrylate As a specific example of a commercially available polyfunctional urethane (meth) acrylate compound having three (meth) acryloyl groups, NK Oligo UA -7100 [manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 204, 205, 264, 265, 294 / 25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 [above, all manufactured by Daicel Ornex Co., Ltd.]; Muriko (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B [above, all Nippon Synthetic Chemical Industry Co., Ltd.].

(2) Tetrafunctional (having four (meth) acryloyl groups) urethane (meth) acrylate As a specific example of a commercially available polyfunctional urethane (meth) acrylate compound having four (meth) acryloyl groups, EBECRYL (registered) Trademarks) 8210, 8405, KRM (registered trademark) 8528 [all of which are manufactured by Daicel Ornex Co., Ltd.];

(3) Polyfunctional urethane (meth) acrylate compound having 5 or more functional groups (having 5 or more (meth) acryloyl groups) (functional) urethane (meth) acrylate compound having 5 or more (meth) acryloyl groups ) Acrylate), for example, urethanized product of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, urethanized product of pentaerythritol tri (meth) acrylate and toluene diisocyanate, pentaerythritol tri (meth) acrylate and isophorone diisocyanate And urethanized products of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate.

Commercially available urethane (meth) acrylate having 5 or more functional groups can be suitably used. For example, UA-306H, UA-306T, UA-306I, UA-510H [above, all are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [above, all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (Registered Trademark) 220, 1290, 5129, 8254, 8301R, KRM (Registered Trademark) 8200, 8200AE, 8904, 8452 [all are manufactured by Daicel Ornex Co., Ltd.]; Trademarks) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [above, both Nippon Synthetic Chemical Industry Co., Ltd.], and the like.

[Other compounds having three or more (meth) acryloyl groups]
(C) Polymerizability of the present invention other than a compound having three or more (meth) acryloyl groups and an oxyalkylene structure and a polyfunctional urethane (meth) acrylate compound having three or more (meth) acryloyl groups Examples of suitable compounds are shown below.

(1) Trifunctional (having three (meth) acryloyl groups) compounds As compounds having three (meth) acryloyl groups, 1,1,1-trimethylolethane tri (meth) acrylate, trimethylolpropane tri ( Examples include meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerin tri (meth) acrylate.

  As the compound having three (meth) acryloyl groups, a commercially available product can be suitably used. For example, Biscote # 295, # 300 [all are manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light acrylate TMP-A, PE-3A, light ester TMP [above, all manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester A-9300, same A-9300-1CL, same A-TMM-3, same A-TMM-3L, same A -TMM-3LM-N, A-TMPT, TMPT [above, all manufactured by Shin-Nakamura Chemical Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [above, all of which are Daicel Ornex ( Etc.].

(2) Tetrafunctional (having four (meth) acryloyl groups) compounds Examples of the compound having four (meth) acryloyl groups include ditrimethylolpropane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate. .

  As the compound having four (meth) acryloyl groups, a commercially available product can be suitably used. For example, Biscoat # 300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light acrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester AD-TMP, A-TMMT [above, all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 140, 1142, 180 [above, both manufactured by Daicel Ornex Co., Ltd.] Etc.

(3) A compound having 5 or more functional groups (having 5 or more (meth) acryloyl groups) As a compound having 5 or more (meth) acryloyl groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) An acrylate, tripentaerythritol octa (meth) acrylate, etc. are mentioned.

  As the compound having 5 or more (meth) acryloyl groups, a commercially available product can be suitably used. For example, Biscoat # 802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.] NK ester A-9550, A-DPH [all above, manufactured by Shin-Nakamura Chemical Co., Ltd.]; DPHA [manufactured by Daicel Ornex Co., Ltd.].

[(Meth) acrylate compound having one or two (meth) acryloyl groups in the molecule]
As the compound (c) polymerizable compound used in the photosensitive base material of the present invention, various compounds including commercially available products may be used as the compound having one or two (meth) acryloyl groups in the molecule. it can.
For example, as described above, a urethane (meth) acrylate compound having one or two (meth) acryloyl groups in the molecule contributes to achieving blackening of the back surface of the coating after forming a metal plating coating described later. Can be suitably used together.

[Urethane (meth) acrylate compounds having one or two (meth) acryloyl groups in the molecule]
(1) Monofunctional urethane (meth) acrylate The monofunctional urethane (meth) acrylate compound is not particularly limited. For example, polyisocyanate (isocyanate component) and monool (active hydrogen component) are reacted to obtain an isocyanate-terminated prepolymer. This can be reacted with a compound having a (meth) acryloyl group and an isocyanate-reactive group to obtain a urethane (meth) acrylate having an average of one (meth) acryloyl group per molecule. A polyol may be used in place of the monool, but in this case, it is necessary to operate so as not to introduce a (meth) acryloyloxy group into a part of the terminal hydroxy group of the polyol.

(2) Bifunctional urethane (meth) acrylate Examples of the bifunctional urethane (meth) acrylate include urethanized products of phenylglycidyl ether (meth) acrylic acid adduct and hexamethylene diisocyanate, phenyl glycidyl ether (meth) acrylic. Examples include urethanates of acid adducts and toluene diisocyanate.

  Commercially available products can be suitably used as the bifunctional urethane (meth) acrylate, for example, AH-600, AT-600 [all are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 210 215, 230, 244, 245, 270, 280 / 15IB, 284, 285, 4858, 8307, 8402, 8411, 8804, 8807, 9227EA, 9270 , KRM (registered trademark) 7735 [above, both manufactured by Daicel Ornex Co., Ltd.]; Murasaki (registered trademark) UV-6630B, 7000B 7461TE, 2000B, 2750B, 3000, 3200B, 3210EA, 3300B, 3310B, 3500BA, 3520TL, 3700B, 6640B [all are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc. Is mentioned.

  In addition, in the photosensitive base agent of the present invention, the intramolecular molecules mentioned as examples of the preferred (c) polymerizable compounds mentioned above are urethane (meth) acrylate compounds having one or two (meth) acryloyl groups in the molecule. When using together with a compound having 3 or more (meth) acryloyl groups, the addition amount is 200 parts by mass or less with respect to 100 parts by mass of the compound having 3 or more (meth) acryloyl groups in the molecule. Preferably, it is 10-200 mass parts, More preferably, it is 20-100 mass parts. Even if the urethane (meth) acrylate compound having one or two (meth) acryloyl groups is added in less than 10 parts by mass, it does not contribute to the realization of blackening of the back surface of the metal plating film, and 200 masses. If it is added beyond the part, it is necessary to be careful because it may be difficult to form a pattern of the plating base layer by photolithography.

[(Meth) acrylate compound having one or two (meth) acryloyl groups in other molecule]
(1) Monofunctional (having one (meth) acryloyl group) compound As the compound having one (meth) acryloyl group, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, lauryl (meth) methacrylate, pentadecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate , Naphthyl (meth) acrylate, anthryl (meth) acrylate, anthryl (meth) methyl acrylate, phenyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2-ethylhexyl diglycol (meth) Acrylate methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) Acrylate, ethoxyethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-methoxybutyl (Meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-propyl-2-adamantyl (meth) acrylate, γ-butyrolactone (meth) acrylate, dicyclopentanyl (meth) acrylate, 8-methyl-8 -Tricyclodecyl (meth) acrylate, 8-ethyl-8-tricyclodecyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (Meth) acrylate, nonylphenol ethoxylated (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N -Dimethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-diacetone (meth) acrylamide, N, N'-methylenepis (meth) acrylamide, (meth) acrylonitrile, glycidyl (Meth) acrylate, (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl-succinic acid 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl Examples include phthalic acid and 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

  As the compound having one or more (meth) acryloyl groups, commercially available products can be suitably used. For example, light acrylate IAA, light acrylate LA, light acrylate SA, light acrylate EC-A, light acrylate MTG- A, Light acrylate EHDG-AT, Light acrylate 130A, Light acrylate DPM-A, Light acrylate PO-A, Light acrylate P2H-A, Light acrylate P-200A, Light acrylate NP-4EA, Light acrylate THF-A, Light acrylate IB-XA, light ester HOA (N), light ester HOP-A (N), light acrylate HOB-A, epoxy ester M-600A, HOA-MS (N), light acrylate HOA-HH ( ), HOA-MPL (N), HOA-MPE (N), light acrylate BA-104, light acrylate P-1A (N), light ester E, light ester NB, light ester IB, light ester TB, light ester EH , Light ester ID, light ester L, light ester L-7, light ester S, light ester BC, light ester 130MA, light ester 041MA, light ester CH, light ester THF (1000), light ester BZ, light ester PO, Light ester IB-X, Light ester HO-250 (N), Light ester HOP (N), Light ester HOB (N), Light ester DM, Light ester DE, Light ester DQ-100, Light ester HO-MS ( ), Light ester HO-HH (N), light ester G, light ester P-1M, light ester M-3F [all are manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester A-LEN-10, same AM- 90G, AM-130G, AMP-20GY, A-SA, S-800A, CB-1, M-90G, M-230G, PHE-1G, S, SA All manufactured by Shin-Nakamura Chemical Co., Ltd.]; FANCYL (registered trademark) FA-511AS, FA-512AS, FA-513AS, FA-BZA, FA-310A, FA-314A, FA-318A FA-THFA, FA-512M, FA-512MT, FA-513M, FA-711MM, FA-712HM, FA-BZM, FA-310M, FA -400M (100), same FA-THFM [above, all manufactured by Hitachi Chemical Co., Ltd.]; β-CEA, IBOA-B, ODA-N, EBECRYL (registered trademark) 110, 114 [Daicel Ornex Co., Ltd. HEA, HPA, 4-HBA, AIB, TBA, NOAA, IOAA, INAA, LA, STA, ISTA, IBXA, Biscote # 150, # 155, # 160, # 192, # 190, #MTG, # 200, 2-MTA, MPE400A, MPE550A, MEDOL-10, OXE-10, OXE-30 [all of which are manufactured by Osaka Organic Chemical Co., Ltd.].

(2) Bifunctional compound (having two (meth) acryloyl groups) Examples of the compound having two (meth) acryloyl groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol. Di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) a Chryrate, 1,10-decanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, tricyclo [5.2.1.02,6] decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, trishydroxyethyl isocyanurate di (meth) acrylate, 9,9-bis [4 -(2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxyethylene glycol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantanedimethanol di (meth) Accel Relay , And ethoxylated bisphenol A di (meth) acrylate.

  As the compound having two or more (meth) acryloyl groups, commercially available products can be suitably used. For example, Light acrylate 3EG-A, Light acrylate 4EG-A, Light acrylate 9EG-A, Light acrylate 14EG-A, Light acrylate PTMGA-250, light acrylate NP-A, light acrylate MPD-A, light acrylate 1.6HX-A, light acrylate 1.9ND-A, light acrylate MOD-A, light acrylate DCP-A, light acrylate BP-4EAL, Light acrylate BP-4PA, Light acrylate HPP-A, Light ester G-201P, Light ester P-2M, Light ester EG, Light ester 2EG, Light ester 3EG, Light ester 4EG, La Toester 9EG, light ester 14EG, light ester 1.4BG, light ester NP, light ester 1.6HX, light ester 1.9ND, light ester G-101P, light ester G-201P, light ester BP-2EMK [or more, any NK Ester 701A, A-200, A-400, A-600, A-1000, A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD- N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, 1G, 2 3G, 4G, 9G, 14G, 23G, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, DCP, DCP-N, HD-N, NOD-N, NPG, 1206PE, 701, 9PG [all are manufactured by Shin-Nakamura Chemical Co., Ltd.]; FANCYL FA-124AS, FA-129AS, FA-222A, FA-240A, FA-P240A, FA-P270A, FA-321A, FA-324A, FA-PTG9A, FA-121M, FA-124M, FA-125M, FA-220M, FA-240M, FA-320M, FA-321M, FA-3218M, FA-PTG9M [All above, Hitachi Chemical ( DPGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [manufactured by Daicel Ornex Co., Ltd.]; Biscote # 195, The same # 230, the same # 260, the same # 310HP, the same # 335HP, the same # 700HV, the same # 540, the same # 802, the same # 295 [all are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

<(C) Polymer compound having a side chain whose terminal is a polymerizable unsaturated bond>
The component (c) used in the photosensitive base material of the present invention has a side chain in which one or more terminals are polymerizable unsaturated bonds in the molecule, and the oxyalkylene group is 15 per 100 moles of all repeating units. It may be a polymerizable polymer compound having ˜50 mol and having a weight average molecular weight of 5,000 to 100,000.
As such a polymer compound having a side chain whose terminal is a polymerizable unsaturated bond, a polymer compound having a (meth) acryloyl group in two or more side chains in the molecule is preferable. Includes a polymer compound having a (meth) acryloyl group and having an oxyalkylene group in three or more side chains in the molecule.
As the oxyalkylene group, an oxyalkylene group having 2 to 4 carbon atoms is preferable, and among them, an oxyethylene group [—OCH ₂ CH ₂ —] or an oxypropylene group [—OCH ₂ C (CH ₃ ) H—] is preferable. . The oxyalkylene group may be a poly (oxyalkylene) group in which a plurality of oxyalkylene groups are connected. In that case, the oxyalkylene group may have a single oxyalkylene group or a combination of two or more. Also good. In the case of having a plurality of types of oxyalkylene groups, these bonds may be block bonds or random bonds.
In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

As the above-mentioned polymer compound, a polymer compound containing at least one (meth) acryloyl group such as urethane acrylic, epoxy acrylic, various (meth) acrylates, etc., particularly containing at least three (meth) acryloyl groups. And a polyfunctional polymer compound.
Among these polymerizable polymer compounds, compounds having three or more (meth) acryloyl groups and an oxyalkylene group in the side chain are preferable.

  The weight average molecular weight of the polymer compound (c) is preferably 5,000 to 100,000, more preferably 20,000 to 50,000. If the molecular weight is less than 10,000, the effect of the present invention is not achieved. On the other hand, if the molecular weight exceeds 100,000, it may not dissolve in the composition.

The polymer compound (c) is preferably a polyethylene oxide-modified polymer having a polymerizable unsaturated double bond in two or more side chains. In this case, the modification rate is preferably 15% to 50%, more preferably 20% to 40%. When the modification rate is less than 15%, the solubility in the developer is lowered, so that the developability may be lowered. If the modification rate is over 50%, the pattern may flow during development.
Examples of the compound as the component (c) include EO-modified acrylic polymers such as 8KX-078H and 8KX-128 manufactured by Taisei Fine Chemical Co., Ltd.

The addition amount of the polymerizable compound (c) in the photosensitive base material of the present invention is 100 parts by mass of a composite formed from the hyperbranched polymer and metal fine particles described later (or the total mass of the hyperbranched polymer and metal fine particles). The amount is preferably 10 to 10,000 parts by mass. More preferably, they are 100-2,000 mass parts, for example, 500-2,000 mass parts, 800-2,000 mass parts. (C) When the addition amount of the polymerizable compound is less than 10 parts by mass, it becomes difficult to form a pattern of a plating base layer by photolithography described later, and when the amount exceeds 10,000 parts by mass, the base There is a possibility that the metal plating film is not formed on the base layer formed by the agent.
In addition, in order to make the pattern formation property of the plating underlayer and the formation property of the plating film on the underlayer suitable, the amount of (c) the polymerizable compound is relative to the total mass of the (c) polymerizable compound. The blending ratio of the compound having three or more (meth) acryloyl groups in the molecule mentioned as a preferred example is, for example, 30% by mass or more, preferably 50% by mass or more, and further 75% by mass to 100% by mass. Can do.

<(D) Photopolymerization initiator>
As the photopolymerization initiator (d) used in the photosensitive base material of the present invention, known ones can be used. For example, alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoate , Oxime esters, tetramethylthiuram monosulfides, thioxanthones and the like.
In particular, photocleavable photoradical polymerization initiators are preferred. Examples of the photocleavable photoradical polymerization initiator include those described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, published in 1991). .
Examples of commercially available radical photopolymerization initiators include IRGACURE (registered trademark) 184, 369, 500, 651, 784, 819, 907, 1000, 1300, 1700, and 1800. 1850, 2959, CGI1700, CGI1750, CGI1850, CGI1850, CG24-61, TPO, Darocur (registered trademark) 1116, 1173 (above, manufactured by BASF Japan Ltd.), ESACURE KIP150, KIP65LT, The same KIP100F, the same KT37, the same KT55, the same KTO46, the same KIP75 [above, manufactured by Lamberti Co., Ltd.] and the like are exemplified, but not limited thereto. These polymerization initiators can be used in combination of two or more.

  The addition amount of the (d) polymerization initiator in the photosensitive base agent of the present invention is, for example, 0.1 to 100% by mass, preferably 1 to 50% by mass with respect to the (c) polymerizable compound. Preferably it is 10-30 mass%.

<(E) Surfactant>
Examples of the surfactant include the following (A), (B), (C), (D), and (E).
(A) Nonionic surfactant:
(A-1) Polyethylene glycol type surfactant: for example, polyoxyethylene alkyl (C8-18) ether, ethylene oxide adduct of alkyl naphthol, polyoxyethylene (mono or di) alkyl (C8-12) phenyl ether, Formalin condensate of polyoxyethylene (mono or di) alkyl (C8-12) phenyl ether, polyoxyethylene (mono, di or tri) phenyl phenyl ether, polyoxyethylene (mono, di or tri) benzyl phenyl ether, poly Oxypropylene (mono, di or tri) benzyl phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxypropylene (mono, di or tri) styryl phenyl ether, polyoxyethylene ( , Di or tri) styryl phenyl ether polymer, alkyl (C8-18) polyoxyethylene polyoxypropylene block polymer ether, alkyl (C8-12) phenyl polyoxyethylene polyoxypropylene block polymer ether, polyoxyethylene bisphenyl Ether, polyoxyethylene resin acid ester, polyoxyethylene fatty acid (C8-18) monoester, polyoxyethylene fatty acid (C8-18) diester, polyoxyethylene sorbitan fatty acid (C8-18) ester, glycerol fatty acid ester ethylene oxide addition , Castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide adduct, alkyl (C8-18) amine ethylene oxide adduct and fatty acid (C8- 8) amide ethylene oxide adducts.
(A-2) Polyhydric alcohol type surfactant: for example, glycerol fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid (C8-18) ester, sorbitan fatty acid (C8-18) ester, sucrose fatty acid Examples thereof include esters, polyhydric alcohol alkyl ethers and fatty acid alkanolamides.
(A-3) Acetylene-based surfactant: Examples thereof include acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol, and the like.
(A-4) Other surfactants: Examples include alkyl glycosides.
(B) Anionic surfactant:
(B-1) Carboxylic acid type surfactant: For example, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid or maleic anhydride and olefin (for example, isobutylene and diisobutylene) Polymer, Copolymer of acrylic acid and itaconic acid, Copolymer of methacrylic acid and itaconic acid, Copolymer of maleic acid or maleic anhydride and styrene, Copolymer of acrylic acid and methacrylic acid, Acrylic acid Copolymer of acrylic acid and methyl ester, copolymer of acrylic acid and vinyl acetate, copolymer of acrylic acid and maleic acid or maleic anhydride, N-methyl-fatty acid (C8-18) sarcosinate, resin acid And carboxylic acids such as fatty acids (C8-18), and salts of these carboxylic acids.
(B-2) Sulfate ester type surfactant: For example, alkyl (C8-18) sulfate ester, polyoxyethylene alkyl (C8-18) ether sulfate ester, polyoxyethylene (mono or di) alkyl (C8-12) Phenyl ether sulfate, polyoxyethylene (mono or di) alkyl (C8-12) phenyl ether polymer sulfate, polyoxyethylene (mono, di or tri) phenyl phenyl ether sulfate, polyoxyethylene (mono, di) Or tri) benzyl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer sulfate, polyoxyethylene poly Sulfate esters of polyoxypropylene block polymers, sulfated oils, sulfated fatty acid esters, salts of sulfuric esters, and their sulfates, such as sulfated fatty acids and sulfated olefins.
(B-3) Sulfonic acid type surfactant: For example, paraffin (C8-22) sulfonic acid, alkyl (C8-12) benzenesulfonic acid, formalin condensate of alkyl (C8-12) benzenesulfonic acid, cresol sulfonic acid Formalin condensate, α-olefin (C8-16) sulfonic acid, dialkyl (C8-12) sulfosuccinic acid, polyoxyethylene (mono or di) alkyl (C8-12) phenyl ether sulfonic acid, polyoxyethylene alkyl (C8) -18) ether sulfosuccinic acid half ester, naphthalene sulfonic acid, (mono or di) alkyl (C1-6) naphthalene sulfonic acid, formalin condensate of naphthalene sulfonic acid, (mono or di) alkyl (C1-6) naphthalene sulfonic acid Formalin condensate, creosote Formalin condensate of sulfonic acid, alkyl (C8-12) diphenyl ether disulfonic acid, Igepon T (trade name), sulfonic acid such as polystyrene sulfonic acid and copolymer of styrene sulfonic acid and methacrylic acid, and salts of these sulfonic acids Is mentioned.
(B-4) Phosphate ester type surfactant: For example, alkyl (C8-12) phosphate ester, polyoxyethylene alkyl (C8-18) ether phosphate ester, polyoxyethylene (mono or di) alkyl (C8-12) Phenyl ether phosphate, polyoxyethylene (mono, di or tri) alkyl (C8-12) phenyl ether polymer phosphate ester, polyoxyethylene (mono, di or tri) phenyl phenyl ether phosphate, polyoxyethylene (mono , Di or tri) benzyl phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) styryl phenyl ether phosphate ester, polyoxyethylene (mono, di or tri) styryl phenyl ether polymer phosphate ester, polyoxyethylene Polyoxypropylene block phosphate ester of the polymer, phosphatidylcholine, phosphoric acid esters, such as phosphatidylethanolamine imine and condensation phosphoric acid (e.g., tripolyphosphate, etc.), and salts of these phosphate esters.
Examples of the salt in the above (B-1) to (B-4) include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium and various amines (for example, alkylamine, cyclohexane). Alkylamine and alkanolamine).
(C) Cationic surfactant:
Examples thereof include alkylamines, alkyl quaternary ammonium salts, alkylamine ethylene oxide adducts, and alkyl quaternary ammonium salt ethylene oxide adducts.
(D) Amphoteric surfactant:
Examples thereof include betaine type surfactants and amino acid type surfactants.
(E) Other surfactants:
For example, silicone surfactants and fluorine surfactants can be used.
These surfactants can be used alone or in combination of two or more, and the ratio in the case of mixing can be freely selected.
The addition amount of the (e) surfactant in the photosensitive base material of the present invention is, for example, 0.1 to 100 parts by mass, preferably 0.1 to 100 parts by mass of the polymerizable compound (c) of the present invention. 5 to 20 parts by mass.

<(F) Amine compound>
As the (f) amine compound used in the photosensitive base material of the present invention, known compounds can be used, and examples thereof include aliphatic amines such as alkylamines and hydroxyalkylamines, and cyclic substituents. Amines having an aromatic group, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group. Of these amine compounds, amine compounds having an alkoxysilyl group are preferred.
In addition, from the viewpoint of improving the storage stability of the plating base agent, the amino group of the amine compound is preferably protected by a ketone (protected by an alkylidene group). In the present invention, the amino group is protected by an alkylidene group. Both the amine compound and the amine compound thus formed are included in the component (c). In the case of using an amine compound protected by this alkylidene group as the component (f), the solvent for the base agent to be described later is not an alcohol solvent from which protection by the alkylidene group is removed, but ketones, ethers, It is preferable to use an ester solvent.
In the present invention, (f) dispersion stability in a base material of a composite composed of a metal fine particle, specifically, a metal fine particle described later and a hyperbranched polymer having an ammonium group, by blending an amine compound with the photosensitive base material. The improvement effect is obtained, and it contributes to the formation of a fine plating pattern.

Examples of the alkylamines include ethylamine (CH ₃ CH ₂ NH ₂ ), propylamine (CH ₃ (CH ₂ ) ₂ NH ₂ ), butylamine (CH ₃ (CH ₂ ) ₃ NH ₂ ), pentylamine (CH ₃ ( CH _{2) 4} NH _2), hexylamine _{(CH 3 (CH 2) 5} NH 2), heptyl amine _{(CH 3 (CH 2) 6} NH 2), octylamine _{(CH 3 (CH 2) 7} NH 2), Nonylamine (CH ₃ (CH ₂ ) ₈ NH ₂ ), decylamine (CH ₃ (CH ₂ ) ₉ NH ₂ ), undecylamine (CH ₃ (CH ₂ ) ₁₀ NH ₂ ), dodecylamine (CH ₃ (CH ₂ )) ₁₁ NH _2), tridecyl amine _{(CH 3 (CH 2) 12} NH 2), tetradecyl amine _{(CH 3 (CH 2) 13} NH ), Pentadecyl amine _{(CH 3 (CH 2) 14} NH 2), hexadecylamine _{(CH 3 (CH 2) 15} NH 2), heptadecyl amine _{(CH 3 (CH 2) 16} NH 2), octadecylamine ( Primary amines such as CH ₃ (CH ₂ ) ₁₇ NH ₂ ), nonadecylamine (CH ₃ (CH ₂ ) ₁₈ NH ₂ ), icosylamine (CH ₃ (CH ₂ ) ₁₉ NH ₂ ), and structural isomers thereof Secondary amines such as N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine and N, N-dibutylamine; thirds such as trimethylamine, triethylamine, tripropylamine and tributylamine; Secondary amines.

Examples of the hydroxyalkylamines (alkanolamines) include methanolamine (OHCH ₂ NH ₂ ), ethanolamine (OH (CH ₂ ) ₂ NH ₂ ), propanolamine (OH (CH ₂ ) ₃ NH ₂ ), butanolamine. (OH (CH ₂ ) ₄ NH ₂ ), pentanolamine (OH (CH ₂ ) ₅ NH ₂ ), hexanolamine (OH (CH ₂ ) ₆ NH ₂ ), heptanolamine (OH (CH ₂ ) ₇ NH ₂ ), Octanolamine (OH (CH ₂ ) ₈ NH ₂ ), nonanolamine (OH (CH ₂ ) ₉ NH ₂ ), decanolamine (OH (CH ₂ ) ₁₀ NH ₂ ), undecanolamine (OH ( CH _{2) 11} NH _2), dodecanol amine _{(OH (CH 2) 12 NH} 2), Toridekano Ruamine (OH (CH ₂ ) ₁₃ NH ₂ ), Tetradecanolamine (OH (CH ₂ ) ₁₄ NH ₂ ), Pentadecanolamine (OH (CH ₂ ) ₁₅ NH ₂ ), Hexadecanolamine (OH (CH (CH _{2) 16} NH _2), heptadecanol amine _{(OH (CH 2) 17 NH} 2), octadecanol amine _{(OH (CH 2) 18 NH} 2), nonadecamethylene alkanolamine _{(OH (CH 2) 19 NH} 2 ), Primary amines such as eicosadecanolamine (OH (CH ₂ ) ₂₀ NH ₂ ); N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N -Methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanol Amine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, etc. Secondary amines and the like.

  Other aliphatic amines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxy Examples thereof include alkoxyalkylamines such as butylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, and butoxybutylamine.

As an example of amines having a cyclic substituent, amine compounds represented by the formula R ¹¹ —R ¹² —NH ₂ are preferable.
In the above formula, R ¹¹ is a monovalent cyclic group having 3 to 10 carbon atoms, preferably 3 to 12 carbon atoms, and may be any of alicyclic groups, aromatic groups, and combinations thereof. Good. These cyclic groups may be substituted with any substituent, for example, an alkyl group having 1 to 10 carbon atoms. R ¹² represents a single bond or an alkylene group having 1 to 17 carbon atoms, preferably 1 to 3 carbon atoms.

In the present invention, preferred specific examples of the amine compound represented by the formula R ¹¹ —R ¹² —NH ₂ include compounds represented by the following formulas (A-1) to (A-10).

  Specific examples of aromatic amines (arylamines) include aniline, N-methylaniline, o-, m-, or p-anisidine, o-, m-, or p-toluidine, o-, m-, or Examples thereof include p-chloroaniline, o-, m-, or p-bromoaniline, o-, m-, or p-iodoaniline.

  Specific examples of the amine compound having an alkoxysilyl group include N, N′-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine and N, N′-bis [3- (triethoxysilyl). Propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2-ethanediamine, Bis- [3- (trimethoxysilyl) propyl] amine, bis- [3- (triethoxysilyl) propyl] amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxy Silane, 3-aminopropylmethyldiethoxysilane, trimethoxy [3- (methylamino)] propylsilane, 3- N-allylamino) propyltrimethoxysilane, 3- (N-allylamino) propyltriethoxysilane, 3- (diethylamino) propyltrimethoxysilane, 3- (diethylamino) propyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane Examples of the compound include silane and 3- (phenylamino) propyltriethoxysilane.

In addition, alkylamines, hydroxyalkylamines, other aliphatic amines, amines having a cyclic substituent, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group, which are specific examples above. Examples include amino compounds in which an amino group is protected by an alkylidene group with ketones such as methyl ethyl ketone and methyl isobutyl ketone.
The content of the (f) amine compound in the photosensitive base material of the present invention is 100 parts by mass of a composite formed from the hyperbranched polymer and metal fine particles described later (or the total mass of the hyperbranched polymer and metal fine particles). On the other hand, it is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly 10 to 15 parts by mass.
(F) When the content of the amine compound is less than the above numerical range, a complex formed from the hyperbranched polymer and metal fine particles to be described later, and further (g) dispersibility / solubility of the polyfunctional thiol to be described later If the stabilizing effect is not obtained, and if the addition is carried out greatly exceeding the above range (for example, 10 mass times the amount of the composite), the appearance of the plating film may be deteriorated.

<(G) Multifunctional thiol>
The polyfunctional thiol that is the component (g) used in the photosensitive base agent of the present invention is not particularly limited as long as it is a compound having two or more mercapto groups. Hydrocarbons having the above mercapto groups and other polyfunctional compounds include polyhydric alcohol mercaptocarboxylic acid esters such as polyhydric alcohol poly (mercaptoacetates), polyhydric alcohol poly (3-mercaptopro). Pionate), poly (2-mercaptopropionate) polyhydric alcohol, poly (3-mercaptobutyrate) polyhydric alcohol, poly (3-mercaptoisobutyrate) polyhydric alcohol, etc. Can be mentioned.
In the photosensitive base material of the present invention, the polyfunctional thiol plays a role not only as a crosslinking agent but also as a chain transfer agent, and contributes to realization of high sensitivity and excellent developability during photolithography.

  Specific examples of hydrocarbons having two or more mercapto groups as the substituent include hexane-1,6-dithiol, decane-1,10-dithiol, 1,4-benzenedithiol, 1,4-bis ( And mercaptomethyl) benzene.

  Other bifunctional compounds include ethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), Ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate) ), Trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate) ), Diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), and the like.

  Trifunctional compounds include glycerin tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), glycerin tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane. Tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptoisobutyrate) and the like can be mentioned.

  As tetrafunctional compounds, pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoisobutyrate) Etc.

  Examples of hexafunctional compounds include dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), and dipentaerythritol hexakis. (3-mercaptoisobutyrate), octanediol bis (3-mercaptobutyrate) and the like.

Among these polyfunctional thiols, it is preferable to use a tetrafunctional thiol compound from the viewpoint of improving the developability of the photosensitive base agent.
In this invention, (g) polyfunctional thiol can be used individually or in mixture of 2 or more types.

  The blending amount of (g) polyfunctional thiol in the photosensitive base material of the present invention is the total mass of a composite formed from the hyperbranched polymer and metal fine particles (or the total mass of the hyperbranched polymer and metal fine particles) described later. The content is preferably 0.01% by mass to 200% by mass, and more preferably 0.05% by mass to 50% by mass. If the blending ratio is less than the above range, the desired effect cannot be obtained. On the other hand, if it exceeds the above range, the stability, odor, sensitivity, resolution, developability, adhesion, plating of the photosensitive base agent There is a possibility that the precipitation of the material will deteriorate.

<Photosensitive base material>
The photosensitive base agent of the present invention comprises (a) a hyperbranched polymer having an ammonium group at the molecular end, (b) metal fine particles, (c) a polymerizable compound, (d) a photopolymerization initiator, and (e) a surface activity. An agent, optionally (f) an amine compound, and (g) a polyfunctional thiol, and optionally further other components. At this time, the hyperbranched polymer and the metal fine particles form a complex. It is preferable.
Here, the composite is a particle that is in contact with or close to the metal fine particles due to the action of the ammonium group at the end of the hyperbranched polymer to form a particulate form. It is expressed as a composite having a structure in which the ammonium group of the polymer is attached or coordinated to the metal fine particles.
Therefore, in the “composite” in the present invention, not only the metal fine particles and the hyperbranched polymer are combined to form one composite as described above, but also the metal fine particles and the hyperbranched polymer have bonding portions. Those that are present independently without being formed may also be included.

  Formation of a complex of a hyperbranched polymer having an ammonium group and metal fine particles is performed simultaneously with the preparation of a base material containing the hyperbranched polymer and metal fine particles, and the method includes a metal stabilized to some extent by a lower ammonium ligand. There are a method of exchanging a ligand with a hyperbranched polymer after producing fine particles, and a method of forming a complex by directly reducing metal ions in a solution of a hyperbranched polymer having an ammonium group. For example, by adding an aqueous solution of a metal salt to the solution in which the hyperbranched polymer is dissolved and irradiating it with ultraviolet light, or adding an aqueous solution of a metal salt and a reducing agent to the hyperbranched polymer solution, etc. A complex can also be formed by reducing.

In the ligand exchange method, the metal fine particles stabilized to some extent by the lower ammonium ligand as a raw material can be produced by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162 and the like. The target metal fine particle composite can be obtained by dissolving the hyperbranched polymer having an ammonium group in the obtained reaction mixture solution of metal fine particles and stirring at room temperature (approximately 25 ° C.) or with heating.
The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the hyperbranched polymer having an ammonium group at a required concentration or more. Specifically, alcohols such as ethanol, n-propanol, and isopropanol are used. Halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; and mixtures of these solvents. Preferably, tetrahydrofuran is used.
The temperature at which the reaction mixture of the metal fine particles and the hyperbranched polymer having an ammonium group are mixed usually ranges from 0 ° C. to the boiling point of the solvent, preferably from room temperature (approximately 25 ° C.) to 60 ° C. It is a range.
In the ligand exchange method, the metal fine particles can be stabilized to some extent in advance by using a phosphine dispersant (phosphine ligand) in addition to the amine dispersant (lower ammonium ligand).

The direct reduction method involves dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reducing it with a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc. A fine particle composite can be obtained.
As the metal ion source used here, the above-mentioned metal salts can be used.
The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the hyperbranched polymer having a metal ion and an ammonium group at a required concentration or more, and specifically, alcohols such as methanol, ethanol, propanol, isopropanol; Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF), N- Amides such as methyl-2-pyrrolidone (NMP); Sulfoxides such as dimethyl sulfoxide and the like, and a mixed solution thereof. Preferred examples include alcohols, halogenated hydrocarbons, and cyclic ethers. Than Mashiku are ethanol, isopropanol, chloroform, tetrahydrofuran, and the like.
The temperature of the reduction reaction can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.

As another direct reduction method, a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reacting them in a hydrogen gas atmosphere.
As a metal ion source used here, the above-mentioned metal salt, hexacarbonyl chromium [Cr (CO) ₆ ], pentacarbonyl iron [Fe (CO) ₅ ], octacarbonyl dicobalt [Co ₂ (CO) ₈ ]. A metal carbonyl complex such as tetracarbonyl nickel [Ni (CO) ₄ ] can be used. In addition, zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
The solvent to be used is not particularly limited as long as it can dissolve a hyperbranched polymer having a metal ion and an ammonium group at a required concentration or higher. Specifically, alcohols such as ethanol and propanol; methylene chloride, chloroform Halogenated hydrocarbons such as: cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; and a mixture of these solvents, preferably tetrahydrofuran.
As the temperature for mixing the metal ion and the hyperbranched polymer having an ammonium group, a range of usually 0 ° C. to the boiling point of the solvent can be used.

Further, as a direct reduction method, a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and causing a thermal decomposition reaction.
As the metal ion source used here, the above metal salts, metal carbonyl complexes, other zero-valent metal complexes, and metal oxides such as silver oxide can be used.
The solvent to be used is not particularly limited as long as it can dissolve a hyperbranched polymer having a metal ion and an ammonium group to a concentration higher than the required concentration. Specifically, methanol, ethanol, n-propanol, isopropanol, ethylene glycol Alcohols such as: Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Aromatics such as benzene and toluene Examples thereof include hydrocarbons and a mixture of these solvents, and preferably toluene.
The temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed is usually 0 ° C. to the boiling point of the solvent, preferably around the boiling point of the solvent, for example, 110 ° C. (heating reflux) in the case of toluene. It is.

  The complex of the hyperbranched polymer having an ammonium group and the metal fine particles obtained in this way can be made into a solid form such as a powder through a purification treatment such as reprecipitation.

  The photosensitive base agent of the present invention comprises (a) a hyperbranched polymer having an ammonium group, (b) metal fine particles (preferably a composite comprising them), (c) a polymerizable compound, and (d) photopolymerization. It contains an initiator, (e) a surfactant, optionally (f) an amine compound, and (g) a polyfunctional thiol, and optionally other components. The form of the varnish used at the time of formation of an electroplating base layer] may be sufficient.

<Other additives>
As long as the effects of the present invention are not impaired, the photosensitive base material of the present invention may further contain additives such as various surface conditioners, sensitizers, polymerization inhibitors, polymerization initiators and the like as appropriate. Also good.

  Further, as the surface conditioner, silicone leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; BYK (registered trademark) -302, 307, 322, 323 , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.

  These additives may be used individually by 1 type, and may use 2 or more types together. The amount of the additive used is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the composite formed from the hyperbranched polymer and the metal fine particles. 01-5 mass parts is still more preferable.

[Electroless plating underlayer]
The above-described photosensitive base material of the present invention can be applied to a base material to form a thin film, and a photolithography process is performed to form a patterned electroless plating base layer. The underlayer is also an object of the present invention.

Although it does not specifically limit as said base material, A nonelectroconductive base material or a conductive base material can be used preferably.
Examples of the non-conductive substrate include glass, ceramic, etc .; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene) Terephthalate) resin, PEEK (polyetheretherketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, etc .; and paper. These are suitably used in the form of a sheet or a film, and the thickness in this case is not particularly limited.
Examples of the conductive substrate include ITO (tin doped indium oxide), ATO (antimony doped tin oxide), FTO (fluorine doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), and Various stainless steels, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and copper alloys such as brass, phosphor bronze, white copper and beryllium copper, metals such as nickel and nickel alloys, and silver alloys such as silver and western silver Etc.
Furthermore, the base material in which the thin film was formed with these electroconductive base materials on the said nonelectroconductive base material can also be used.
Further, the base material may be a three-dimensional molded body.

A specific method of forming an electroless plating base layer from the above-described hyperbranched polymer having an ammonium group and metal fine particles, a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a photosensitive base agent containing a polyfunctional thiol First, the hyperbranched polymer having an ammonium group and metal fine particles (preferably a composite comprising these), a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a polyfunctional thiol are used in an appropriate solvent. Dissolve or disperse to form a varnish, and apply the varnish onto a substrate on which a metal plating film is to be formed; a blade coating method; a dip coating method; a roll coating method; a bar coating method; a die coating method; ; Inkjet method; fountain pen nanolithography (FPN), dip pen Pen lithography such as nolithography (DPN); letterpress printing, flexographic printing, resin letterpress printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), nanotransfer printing (nTP) and other relief printing methods; Intaglio printing methods such as gravure printing and engraving; lithographic printing methods; stencil printing methods such as screen printing and stencil printing; coating by offset printing methods, etc., and then evaporating and drying the solvent to form a thin layer .
Among these coating methods, spin coating method, bar coating method, spray coating method, ink jet method, pen lithography, contact printing, μCP, NIL and nTP are preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed. When the spray coating method is used, highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous. When an ink jet method, pen lithography, contact printing, μCP, NIL, or nTP is used, a fine pattern such as a wiring can be efficiently formed (drawn), which is very advantageous industrially.

The solvent used here is one that dissolves or disperses the complex (hyperbranched polymer and metal fine particles having an ammonium group), a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a polyfunctional thiol. Although not particularly limited, for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n -Alcohols such as hexanol, n-octanol, 2-octanol, 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve; propylene glycol monomethyl ether (PGME) Propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol Glycol ethers such as dimethyl ether and tripropylene glycol dimethyl ether; glycol esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate (PGMEA); tetrahydrofuran (THF), methyltetrahydrofuran, 1,4-dioxane, diethyl ether Ethers such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone and cyclohexanone; n-heptane, n-hexane, cyclohexane and the like Aliphatic hydrocarbons; Halogenated aliphatic hydrocarbons such as 1,2-dichloroethane and chloroform; N-methyl-2-pyrrolidone (NMP), N , N-dimethylformamide (DMF), amides such as N, N-dimethylacetamide; dimethyl sulfoxide and the like can be used. These solvents may be used alone, or two or more kinds of solvents may be mixed. Furthermore, for the purpose of adjusting the viscosity of the varnish, glycols such as ethylene glycol, propylene glycol and butylene glycol may be added.
Moreover, although the density | concentration dissolved or disperse | distributed to the said solvent is arbitrary, the solid content density | concentration in a varnish is 0.005-90 mass%, Preferably it is 0.01-80 mass%. Here, solid content is a component except the solvent in varnish.

  The method for drying the solvent is not particularly limited. For example, the solvent may be evaporated in a suitable atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using a hot plate or an oven. Thereby, it is possible to obtain an underlayer having a uniform film formation surface. Although a calcination temperature will not be specifically limited if a solvent can be evaporated, It is preferable to carry out at 40-250 degreeC.

The thin film obtained as described above is then exposed through a mask having a predetermined pattern at an exposure amount of about 10 to 3,000 mJ / cm ² , and then developed using a developer, thereby exposing the exposed portion. By washing out, a patterned electroless plating base layer is obtained.

  For the exposure, for example, ultraviolet rays such as a mercury lamp, far ultraviolet rays, electron beams, or X-rays are used. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.

  Further, the developing method is not particularly limited, and can be performed by a known method such as a liquid filling method, a paddle method, a dipping method, a spray method, or a rocking dipping method. The development temperature is preferably 20 to 50 ° C., and the development time is, for example, 10 seconds to 10 minutes.

As the developer, an organic solvent or an alkaline aqueous solution can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, and isopropanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), 3-methoxy-3-methyl-1-butanol, and the like. Glycol ethers; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF) and 1,4-dioxane; ether esters such as propylene glycol monomethyl ether acetate (PGMEA); esters such as ethyl acetate and butyl acetate Ketones such as acetone and cyclohexanone; amides such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylacetamide (DMAc); Etc. sulfoxides such as Kishido like.
Examples of alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; ethanolamine. And aqueous amine solutions such as propylamine, ethylenediamine, and morpholine.
These developers may be used alone or in combination of two or more. As the mixed solution, for example, a PGME / PGMEA mixed solution (mass ratio 7: 3) can be preferably used.
In order to adjust developability, water; glycols such as ethylene glycol, propylene glycol and polyethylene glycol may be added to these developers. Further, a surfactant or the like may be added in order to improve the removability of the unexposed area.
Moreover, a commercial item can be used suitably for the said developing solution, for example, OK73 thinner [Tokyo Ohka Kogyo Co., Ltd.] etc. are mentioned.

  After the development, washing with water or a general organic solvent is preferably performed for about 20 to 90 seconds, for example. Then, the water | moisture content on a base material is removed by air drying by compressed air or compressed nitrogen, or by spinning. If necessary, it is heat-dried using a hot plate or an oven to obtain a patterned electroless plating base layer.

[Electroless plating treatment, metal plating film, metal coating substrate]
By electrolessly plating the electroless plating base layer formed on the substrate obtained as described above, a metal plating film is formed on the electroless plating base layer. The metal plating film thus obtained, and the metal-coated base material provided in the order of the electroless plating base layer and the metal plating film on the base material are also objects of the present invention.
The electroless plating treatment (process) is not particularly limited, and can be performed by any generally known electroless plating treatment. For example, the plating is performed using a conventionally known electroless plating solution. A method of immersing the electroless plating base layer formed on the substrate in a liquid (bath) is common.

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and a pH adjuster, a pH buffering agent, a reaction accelerator (second complexing agent) according to other uses. , Stabilizers, surfactants (use for imparting gloss to the plating film, use for improving wettability of the surface to be treated, etc.) and the like are appropriately included.
Examples of the metal used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and are appropriately selected according to the purpose. Is done.
The complexing agent and the reducing agent may be appropriately selected according to the metal ion.
The electroless plating solution may be a commercially available plating solution. For example, an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd., an electroless copper plating chemical (Melplate ( (Registered trademark) CU series); electroless nickel plating solution (ICP Nicolon (registered trademark) series, Top Piena 650) manufactured by Okuno Pharmaceutical Co., Ltd., electroless copper plating solution (OPC-700 electroless copper M-K, ATS Ad Copper IW, CT, OPC Copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (Flash Gold 330, Self Gold OTK) -IT), electroless silver plating solution (muden silver); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd. Electroless gold plating solution (dip G series, NC gold series); electroless silver plating solution (Esdia AG-40) manufactured by Sasaki Chemical Co., Ltd .; electroless nickel plating solution (Kanizen (made by Kanisen Co., Ltd.)) (Registered trademark) series, Schuma (registered trademark) series, Schumer (registered trademark) Crab Black (registered trademark) series), electroless palladium plating solution (S-KPD); (Registered trademark) Coppermix series, Circoposit (registered trademark) series, electroless palladium plating solution (Paramars (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating Solution (Aurolectroles (registered trademark) series), electroless tin plating solution ( Inposito (registered trademark) series, electroless copper plating solution manufactured by Uemura Kogyo Co., Ltd. (Sulcup (registered trademark) ELC-SP, PSY, PCY, PGT, PSR, PEA), Atotech Japan ) Electroless copper plating solution (Print Gantt (registered trademark) PVE) or the like can be suitably used.

  The electroless plating process adjusts the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring, stirring speed, presence / absence of supply of air / oxygen, supply speed, etc. And the film thickness can be controlled.

Thus, the metal film base material of the present invention in which a metal plating film is formed on the base layer obtained by using the photosensitive base material of the present invention is a plating film when a transparent base material is used as the base material. The surface seen when observing the transparent substrate from the surface opposite to the side on which the film is formed can be black.
Therefore, by applying a metal plating film on the base layer patterned by printing, a metal coating substrate having a black back surface of the patterned plating film forming portion can be obtained. It becomes possible to use as a transparent electrode with high.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by this. In the examples, the physical properties of the samples were measured using the following apparatus under the following conditions.

(1) GPC (gel permeation chromatography)
Device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC KF-804L + KF-803L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: UV (254 nm), RI
(2) ¹ H NMR spectrum device: JNM-L400 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Reference peak: Tetramethylsilane (0.00ppm)
(3) ¹³ C NMR spectrum device: JNM-ECA700 manufactured by JEOL Ltd.
Solvent: CDCl ₃
Relaxing reagent: trisacetylacetonatochrome (Cr (acac) ₃ )
Reference peak: CDCl ₃ (77.0 ppm)
(4) ICP emission analysis (inductively coupled plasma emission analysis)
Apparatus: ICPM-8500 manufactured by Shimadzu Corporation
(5) TEM (Transmission Electron Microscope) Image Device: H-8000 manufactured by Hitachi High-Technologies Corporation
(6) Pattern exposure (mask aligner)
Apparatus: MA6 manufactured by SUSS MICROTECH
(7) Developer: Actes Kyozo Co., Ltd. Small developer ADE-3000S
(8) Digital microscope image device: VHX-2000 manufactured by Keyence Corporation

The abbreviations used are as follows.
HPS: Hyperbranched polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd.]
P6A-12E: Ethylene oxide-modified dipentaerythritol hexaacrylate (ethylene oxide addition mole number 12) [Shin-Nakamura Chemical Co., Ltd. NK ester A-DPH-12E]
G3A-20E: ethylene oxide-modified glycerin triacrylate (number of moles of ethylene oxide added 20) [manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-GLY-20E]
P4A-35E: Ethylene oxide-modified pentaerythritol tetraacrylate (35 ethylene oxide addition moles) [Shin Nakamura Chemical Co., Ltd. NK ester ATM-35E]
T3A-20E: ethylene oxide-modified trimethylolpropane triacrylate (number of moles of ethylene oxide added 20) [NK Nakagawa Chemical Industries, Ltd. NK ester AT-20E]
UA-4200: Polyether skeleton bifunctional urethane acrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., NK Oligo UA-4200]
OXE-01: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] [IRGACURE (registered trademark) OXE-01] manufactured by BASF Japan Ltd.
IPA: isopropanol IPE: diisopropyl ether PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate PrOH: n-propanol KBM-903: 3-aminopropyltrimethoxysilane [Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (registered trademark) KBM -903]
Karenz MTPE1: pentaerythritol tetrakis (3-mercaptobutyrate) [Karenz MT (registered trademark) PE1 manufactured by Showa Denko KK]
8KX-078H: Acrylic modified polymer [Akrit (registered trademark) manufactured by Taisei Fine Chemical Co., Ltd.]
8KX-128: Acrylic modified polymer [Acryt (registered trademark) manufactured by Taisei Fine Chemical Co., Ltd.]
1SX1055: Quaternary ammonium salt type acrylic polymer [Acrit (registered trademark) 1SX-1055, manufactured by Taisei Fine Chemical Co., Ltd.]
L-34: Polyoxyethylene / polyoxypropylene block polymer [ADEKA (registered trademark) Pluronic L-34, manufactured by ADEKA Corporation]
PVP-30K: Polyvinylpyrrolidone [Tokyo Chemical Industry Co., Ltd.]
PNVAc: Poly-N-vinylacetamide [PVA (registered trademark) GE191-104 manufactured by Showa Denko KK]

[Production Example 1] Production of HPS-Cl
In a 500 mL reaction flask, 27 g of sulfuryl chloride [manufactured by Kishida Chemical Co., Ltd.] and 50 g of chloroform were charged and stirred to dissolve uniformly. The solution was cooled to 0 ° C. under a nitrogen stream.
In another 300 mL reaction flask, 15 g of hyperbranched polymer HPS having a dithiocarbamate group at the molecular end and 150 g of chloroform were charged and stirred under nitrogen flow until uniform.
From the 300 mL reaction flask charged with the HPS / chloroform solution in a sulfuryl chloride / chloroform solution cooled to 0 ° C. in a nitrogen stream, the solution was cooled to the temperature of the reaction solution. Was added over 60 minutes so that it might become -5-5 degreeC. After completion of the addition, the mixture was stirred for 6 hours while maintaining the temperature of the reaction solution at -5 to 5 ° C.
Furthermore, a solution prepared by dissolving 16 g of cyclohexene [manufactured by Tokyo Chemical Industry Co., Ltd.] in 50 g of chloroform was added to this reaction solution so that the temperature of the reaction solution became −5 to 5 ° C. After completion of the addition, this reaction solution was added to 1,200 g of IPA to precipitate a polymer. The white powder obtained by filtering this precipitate was dissolved in 100 g of chloroform and added to 500 g of IPA to reprecipitate the polymer. The precipitate was filtered under reduced pressure and vacuum dried to obtain 8.5 g of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end as a white powder (yield 99%).
The ¹ H NMR spectrum of the obtained HPS-Cl is shown in FIG. Since the peak derived from the dithiocarbamate group (4.0 ppm, 3.7 ppm) has disappeared, the obtained HPS-Cl has almost all of the dithiocarbamate groups at the HPS molecule terminals substituted by chlorine atoms. It became clear. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained HPS-Cl was 14,000, and dispersion degree Mw / Mn was 2.9.

[Production Example 2] Production of HPS-N (Me) ₂ OctCl
A 100 mL reaction flask equipped with a condenser was charged with 4.6 g (30 mmol) of HPS-Cl produced in Production Example 1 and 15 g of chloroform, and stirred until uniform. To this solution, a solution of 5.0 g (31.5 mmol) of dimethyloctylamine [Farmin (registered trademark) DM0898 manufactured by Kao Corporation] dissolved in 7.5 g of chloroform was added, and 7.5 g of IPA was further added. The mixture was stirred at 65 ° C. for 40 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., the solvent was distilled off. The obtained residue was dissolved in 60 g of chloroform, and this solution was added to 290 g of IPE for purification by reprecipitation. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C. to obtain 9.3 g of a hyperbranched polymer (HPS-N (Me) ₂ OctCl) having a dimethyloctylammonium group at the molecular end as a white powder.
The ¹³ C NMR spectrum of the obtained HPS-N (Me) ₂ OctCl is shown in FIG. The HPS-N (Me) ₂ OctCl obtained from the peak of the benzene ring and the peak of the methyl group at the end of the octyl group has the chlorine atom at the end of the HPS-Cl molecule substituted with an ammonium group almost quantitatively. Became clear. The weight average molecular weight Mw of HPS-N (Me) ₂ OctCl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (100%) was 28,000.

[Production Example 3] Production of HBP-Pd A 100 mL reaction flask equipped with a condenser was charged with 4.2 g of palladium acetate [manufactured by Kawaken Fine Chemicals Co., Ltd.] and 40 g of chloroform and stirred until uniform. A solution obtained by dissolving 8.0 g of HPS-N (Me) ₂ OctCl prepared in Production Example 2 in 100 g of chloroform was added to this solution using a dropping funnel. The dropping funnel was washed into the reaction flask using 20 g of chloroform and 40 g of ethanol. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere.
After cooling to a liquid temperature of 30 ° C., this solution was added to 2,000 g of an IPE / hexane solution (mass ratio 10: 1) and purified by reprecipitation. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50 ° C., and 8.9 g of a complex of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles (Pd [HPS-N (Me) ₂ OctCl]) was blackened. Obtained as a powder (HBP-Pd-1).
From the results of ICP emission analysis, the Pd content of the obtained Pd [HPS-N (Me) ₂ OctCl] (HBP-Pd-1) was 20% by mass. Moreover, the Pd particle diameter was about 2-4 nm from the TEM (transmission electron microscope) image.

Reference Example 1 Preparation of Electroless Nickel Plating Solution 40 mL of Kanisen (registered trademark) Blue Schumer [manufactured by Nippon Kanisen Co., Ltd.] was charged into a 2 L beaker, and pure water was added to make the total amount of the solution 200 mL. This solution was stirred to obtain an electroless nickel plating solution.

[Example 1]
[Preparation of photosensitive base material]
22.1 parts by mass of HBP-Pd-1 produced in Production Example 3 as a Pd catalyst, 2.8 parts by mass of KBM-903, 8KX-078H, 8KX-128, A-DPH-48E, UA-4200 as polymerizable compounds 80 parts by weight, 1.4 parts by weight of PE1 as a polyfunctional thiol (also referred to as RSH), 7.5 parts by weight of a surfactant, 13.8 parts by weight of OXE-01 as a polymerization initiator, and PrOH: MIBK = 8 as a solvent 1 was mixed to prepare a photosensitive base agent for electroless plating having a concentration of 5% by mass of non-solvent components (all components excluding the solvent in the mixture). In addition, in order to easily mix each component, a solution in which each component was previously dissolved in a part of the usage amount of PrOH: MIBK = 8: 1 was mixed.

[Application]
The photosensitive base agent 2.4 mL was bar-coated on an untreated surface of a PET film (Cosmo Shine A-4100, manufactured by Toyobo Co., Ltd.). This substrate was dried in an oven at 80 ° C. for 5 minutes to obtain a substrate having a base layer on the entire surface of the substrate.

[Patterning (exposure and development)]
The resulting underlayer is a mask aligner provided with a photomask on which patterns of various line widths are drawn so that i-line with an illuminance of 10.5 mW / cm ² is exposed to 600 mJ / cm ² in an air atmosphere. Irradiated and exposed.
The exposed substrate was developed using a developing device equipped with a shower nozzle. The development was carried out with an electroless plating base layer patterned on the substrate by rotating the substrate at 300 rpm for 60 seconds with ion-exchanged water, then raising the rotation speed to 2,000 rpm and shaking off the water. A substrate was obtained.

[Electroless plating]
The obtained base material was immersed in the electroless nickel plating solution prepared in Reference Example 1 heated to 80 ° C. for 3 minutes. Thereafter, the removed substrate was washed with water to obtain a plating substrate.

<Plating formation evaluation criteria>
○: Plating is deposited △: Plating is partially deposited ×: Plating is not deposited

[Examples 2 to 4]
Operations were evaluated in the same manner as in Example 1 except that the components of the surfactant were changed to those described in Table 1. The results are shown in Table 2. In Table 1, the numerical value [n-PrOH: MIBK = 8: 1] written in the [Solvent] column in Examples 1 to 4 is 8: 1 of the two solvents n-PrOH and MIBK used. It shows that it was used at a mass ratio.

As shown in Table 2, on the patterned electroless plating base layer obtained by forming a base layer using the photosensitive base material of the present invention, exposing it through a mask and developing it. When the plating film was formed (Examples 1 to 4), the plating film was formed almost according to the mask pattern.
On the other hand, in Comparative Example 1 in which no surfactant was added, the pattern forming property was inferior in a line width of 40 μm or less.
From the above results, it is clear that the photosensitive base material of the present invention can form a plating base layer patterned by photolithography, and is advantageous in obtaining a fine metal plating film having a width of 40 μm or less. It became.

Claims (17)

A base agent for forming a metal plating film by electroless plating on a substrate,
(A) a hyperbranched polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000,
(B) metal fine particles,
(C) a polymerizable compound having one or more (meth) acryloyl groups in the molecule;
(D) A photosensitive base agent comprising a photopolymerization initiator and (e) a surfactant. The photosensitive base agent of Claim 1 whose said (c) polymeric compound is a compound which has a 3 or more (meth) acryloyl group in a molecule | numerator. The photosensitive base agent of Claim 1 or Claim 2 whose said (c) polymeric compound is a compound which has a 3 or more (meth) acryloyl group in a molecule | numerator, and has an oxyalkylene group. The photosensitive base agent according to claim 1, further comprising (f) a compound having an amino group. Furthermore, the photosensitive base agent as described in any one of Claims 1 thru | or 4 containing (g) polyfunctional thiol. The photosensitive base agent according to claim 4 or 5, wherein the compound (f) having an amino group is an alkoxysilane compound having an amino group. The photosensitive base agent of Claim 5 or Claim 6 whose said (g) polyfunctional thiol is a tetrafunctional thiol. The photosensitive base agent as described in any one of Claim 1 thru | or 7 whose said (a) hyperbranched polymer is a hyperbranched polymer represented by Formula [1].
(In the formula, each R ¹ independently represents a hydrogen atom or a methyl group, and R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. , An arylalkyl group having 7 to 20 carbon atoms or — (CH ₂ CH ₂ O) _m R ⁵ (wherein R ⁵ represents a hydrogen atom or a methyl group, and m represents an integer of 2 to 100). (The alkyl group and the arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group), or ^two of R ^{2 to} R ⁴ may be bonded together. Represents a linear, branched or cyclic alkylene group, or R ^{2 to} R ⁴ may form a ring together with the nitrogen atom to which they are bonded, and X ⁻ represents an anion. N is repeated A number of unit structures represents an integer of 5 to 100,000, ^{A 1} represents a structure represented by the formula [2].)
(In the formula, A ² represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, and Y ^{1 to} Y ⁴ are each independently hydrogen. And represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group, or a cyano group. The photosensitive base agent of Claim 8 whose said (a) hyperbranched polymer is a hyperbranched polymer represented by Formula [3].
(In the formula, R ^{1 to} R ⁴ and n represent the same meaning as described above.) The metal fine particles (b) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt) and gold ( The photosensitive base agent according to claim 1, wherein the photosensitive base material is at least one metal fine particle selected from the group consisting of Au). The photosensitive base agent of Claim 10 whose said (b) metal microparticles are palladium microparticles | fine-particles. The photosensitive base agent according to any one of claims 1 to 11, wherein the (b) metal fine particles are fine particles having an average particle diameter of 1 to 100 nm. The photosensitive base agent as described in any one of Claims 1 thru | or 12 for forming the layer in which pattern formation is possible by photolithography. An electroless plating base layer obtained by using the photosensitive base agent according to any one of claims 1 to 13. A metal plating film formed on the electroless plating base layer according to claim 14. A base material, the electroless plating base layer according to claim 14 formed on the base material, and the metal plating film according to claim 15 formed on the electroless plating base layer. Metal coating substrate. The manufacturing method of a metal film base material including the following A process thru | or C process.
Step A: Step of coating the photosensitive base agent according to any one of claims 1 to 13 on a substrate and providing a base layer Step B: Under a desired pattern by printing or photolithography Step C for forming a base layer: a step of immersing a base material provided with a patterned underlayer in an electroless plating bath to form a metal plating film.