JP2016033641A - Photosensitive film, method for forming metal pattern, and pattern substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive film that gives a metal pattern by plating without depending on types of substrates.SOLUTION: A photosensitive film 10 comprises a support film 1, a photosensitive resin layer 2 disposed on the support film 1, and a plate seed layer 3 disposed on the photosensitive resin layer 2.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive film, a metal pattern forming method, and a pattern substrate.

In an electronic component such as a touch panel, a liquid crystal display, an organic electroluminescence display, a solar cell module, a printed wiring board, and electronic paper, wiring for transmitting a signal is disposed on a base material.
In order to obtain the electronic component, a metal pattern substrate having a metal pattern is used, and attempts have been made to obtain a metal pattern by selectively depositing plating.

  As a method for obtaining a metal pattern by plating, a composition for forming a layer to be plated containing a copolymer having a non-dissociative functional group, radical polymerizable group or ionic polar group that interacts with a plating catalyst or its precursor A method of plating the pattern is known (for example, see Patent Document 1 below).

JP 2010-248464 A

  However, in Patent Document 1, the concentration of the plating precursor solution is adjusted in order to obtain the selectivity of plating, but since the influence of plating deposition on the substrate is not taken into consideration, the substrate on which plating is likely to precipitate. When (for example, easy-adhesion-treated polyethylene terephthalate (PET) having an ionic polar group on the surface) is used, the plating is likely to be deposited at a position where it is not desired to deposit the plating. In this case, it is difficult to selectively deposit plating, and a metal pattern may not be formed.

  Then, an object of this invention is to provide the photosensitive film which can obtain a metal pattern selectively by plating, without depending on the kind of base material. Another object of the present invention is to provide a method for forming a metal pattern using the photosensitive film, and a pattern substrate obtained using the photosensitive film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a photosensitive film having a photosensitive resin layer and a plating seed layer provided on the photosensitive resin layer. It has been found that a metal pattern can be selectively obtained by plating without depending on the type of material.

  That is, the first aspect of the present invention relates to a photosensitive film having a support film, a photosensitive resin layer provided on the support film, and a plating seed layer provided on the photosensitive resin layer. .

  According to the photosensitive film which concerns on the 1st aspect of this invention, a metal pattern can be selectively obtained by plating, without depending on the kind of base material. Thereby, a metal pattern can be selectively formed on any substrate by plating without being affected by plating deposition on the substrate.

  The plating seed layer may contain a compound including at least one atom selected from the group consisting of P, O, and N. In this case, the interaction between the plating seed layer and the plating catalyst or precursor thereof used in the plating step is increased, and the plating precipitation of the plating seed layer can be improved.

  The photosensitive resin layer can contain a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. When the photosensitive resin layer contains the above components, the patterning property can be further improved.

  The photopolymerization initiator of the photosensitive resin layer preferably contains an oxime ester compound. By using an oxime ester compound, the sensitivity and patterning property of the photosensitive resin layer can be improved.

  The photosensitive resin layer may contain a compound containing at least one atom selected from the group consisting of S and I. In this case, since it is easy to suppress plating deposition on the photosensitive resin layer, further selective plating is possible, and a metal pattern can be easily formed.

  The second aspect of the present invention includes a step of laminating the photosensitive film on a base material such that the plating seed layer is positioned on the base material side of the photosensitive resin layer, and the photosensitive resin. An exposure step of irradiating a predetermined portion of the layer with an actinic ray to form an exposed portion, and after the exposure step, developing the photosensitive resin layer to remove an unexposed portion of the photosensitive resin layer, The present invention relates to a method for forming a metal pattern, including a step of forming an exposed portion on a plating seed layer and a step of forming a metal layer covering the exposed portion of the plating seed layer by electroless plating.

  A 3rd aspect of this invention is related with the pattern board | substrate provided with the board | substrate and the metal pattern provided on the said board | substrate, and the said metal pattern was formed by the formation method of the said metal pattern.

  According to the present invention, it is possible to provide a photosensitive film capable of selectively obtaining a metal pattern by plating without depending on the type of substrate. Moreover, this invention can provide the formation method of the metal pattern which uses the said photosensitive film, and the pattern board | substrate obtained using the said photosensitive film.

  According to the present invention, an application to selective plating of a photosensitive film is provided. According to the present invention, application of a photosensitive film to the formation of a metal pattern is provided, for example, application of the photosensitive film to the formation of a wiring is provided. According to the present invention, application of a photosensitive film to the formation of a patterned substrate having a metal pattern is provided, and for example, application of the photosensitive film to the formation of a patterned substrate having wiring is provided. According to the present invention, application of a photosensitive film to the manufacture of electronic components is provided.

It is a schematic cross section showing one embodiment of a photosensitive film. It is a schematic cross section for demonstrating one Embodiment of the formation method of the exposed part of the plating seed layer using a photosensitive film. It is a schematic cross section for demonstrating one Embodiment of the formation method of the metal pattern using electroless plating. It is a photograph of the metal pattern obtained by electroless plating. It is a schematic diagram which shows an example of the state which plating has selectively deposited on the exposed part of a plating seed layer. It is a schematic diagram which shows an example of the state which plating has deposited on the exposure part of a plating seed layer, and its circumference | surroundings. It is a schematic diagram which shows an example of the state which plating has deposited on the sample whole surface.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  In the present specification, “(meth) acrylate” means acrylate or a corresponding methacrylate. The same applies to other similar expressions such as “(meth) acrylic acid”. “Acrylic resin” means a polymer mainly having monomer units derived from a polymerizable monomer having a (meth) acryloyl group. “EO” represents ethylene oxide, and “EO-modified” means a compound having an oxyethylene group. “PO” represents propylene oxide, and “PO-modified” compound means a compound having an oxypropylene group. Further, “A or B” only needs to include either A or B, and may include both. Further, the materials exemplified below may be used alone or in combination of two or more unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. means.

<Photosensitive film>
The photosensitive film which concerns on this embodiment has a photosensitive resin layer and the plating seed layer provided on the said photosensitive resin layer. For example, after removing a part of the photosensitive resin layer and forming a cured resin pattern (photosensitive resin layer pattern) in which the exposed portion of the plating seed layer is exposed between the remaining portions of the photosensitive resin layer, the plating seed layer By depositing plating on the exposed portion of the plating seed layer using as a seed layer, the plating can be selectively deposited. Such a photosensitive film is a photosensitive film for performing selective plating using a resin curing pattern obtained by patterning a photosensitive resin layer, and can also be referred to as a “photosensitive selective plating film”.

  FIG. 1 is a schematic cross-sectional view showing a photosensitive film according to this embodiment. As shown in FIG. 1, the photosensitive film 10 includes a support film 1 and a photosensitive layer 4 provided on the support film 1. The photosensitive layer 4 includes a photosensitive resin layer 2 provided on the support film 1 and a plating seed layer 3 provided on the photosensitive resin layer 2.

  Note that the boundary between the photosensitive resin layer 2 and the plating seed layer 3 is not necessarily clear. For example, the photosensitive resin layer 2 is difficult to deposit on the surface (exposed portion) of the resin cured pattern obtained after exposure and development, and the unexposed portion of the photosensitive resin layer 2 is removed after exposure and development. Any material can be used as long as the exposed portion of the plating seed layer 3 can be plated, and the photosensitive resin layer 2 and the plating seed layer 3 may be mixed. For example, the composition constituting the photosensitive resin layer 2 may be impregnated in the plating seed layer 3, or the composition constituting the photosensitive resin layer 2 may be present on the surface of the plating seed layer 3. .

  As the support film 1, a polymer film can be used, and a polymer film having heat resistance and solvent resistance is preferable. Examples of such a polymer film include a polyethylene terephthalate film (PET film), a polyethylene film, a polypropylene film, and a polycarbonate film. Among these, a polyethylene terephthalate film is preferable from the viewpoint of excellent transparency and heat resistance.

  From the viewpoint of excellent mechanical strength, the thickness of the support film 1 is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. When the thickness of the support film 1 is equal to or greater than the above numerical value, for example, a step of applying a photosensitive resin composition solution to form the photosensitive resin layer 2, a plating seed layer to form the plating seed layer 3 It is possible to prevent the support film 1 from being damaged in the step of applying the resin composition or the step of peeling the support film 1 from the photosensitive layer 4 during the development step described later. The thickness of the support film 1 is preferably 300 μm or less, more preferably 200 μm or less, and more preferably 100 μm or less from the viewpoint of sufficiently ensuring the resolution of the pattern when the photosensitive resin layer 2 is irradiated with actinic rays through the support film 1. Further preferred is 60 μm or less.

  From the viewpoint of highly achieving the above effects, the thickness of the support film 1 is preferably 5 to 300 μm, more preferably 10 to 200 μm, still more preferably 15 to 100 μm, and particularly preferably 15 to 60 μm.

  From the viewpoint of good sensitivity and resolution, the haze value of the support film 1 is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, and 0.01 to 2.0%. More preferred is 0.01 to 1.5%. The haze value can be measured according to JIS K 7105. For example, it can be measured with a commercially available turbidimeter such as NDH-5000 (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

  The photosensitive resin layer 2 comprises (A) a binder polymer (hereinafter sometimes referred to as “component (A)”), (B) a photopolymerizable compound having an ethylenically unsaturated bond (hereinafter sometimes referred to as “component (B)”. And (C) a photopolymerization initiator (hereinafter, sometimes referred to as “component (C)”). Patterning property can further be improved by the photosensitive resin layer 2 containing the said component.

  (A) As the binder polymer, for example, a reaction of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid. Examples thereof include an epoxy (meth) acrylate resin obtained and an acid-modified epoxy (meth) acrylate resin obtained by a reaction between an epoxy acrylate resin and an acid anhydride.

  As the component (A), an acrylic resin is preferable from the viewpoint of excellent alkali developability and film formability. As the component (A), an acrylic resin having a monomer unit derived from (meth) acrylic acid and a monomer unit derived from (meth) acrylic acid alkyl ester as a constituent unit is more preferable.

  The acrylic resin can be obtained, for example, by radical polymerization of a polymerizable monomer containing a (meth) acryloyl group.

  Examples of the polymerizable monomer having a (meth) acryloyl group include acrylamide (such as diacetone acrylamide), (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl, and (meth) acrylic acid dimethylamino. Ethyl, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) Examples include acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, and β-styryl (meth) acrylic acid.

  The acrylic resin may be a copolymer of a polymerizable monomer having a (meth) acryloyl group and another polymerizable monomer. Examples of the polymerizable monomer copolymerizable with the polymerizable monomer having a (meth) acryloyl group include styrene, acrylonitrile, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoester maleate. Examples include isopropyl, fumaric acid, and cinnamic acid.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , (Meth) acrylic acid pentyl, (meth) acrylic acid hexyl, (meth) acrylic acid heptyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid Examples include decyl, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

  The component (A) preferably has a carboxyl group from the viewpoint of obtaining better alkali developability. Examples of the polymerizable monomer that gives such a component (A) having a carboxyl group include (meth) acrylic acid as described above.

  From the viewpoint of excellent alkali developability, the proportion of the polymerizable monomer having a carboxyl group is preferably 10% by mass or more based on the total mass of the polymerizable monomer used to obtain the component (A). The mass% or more is more preferable. From the viewpoint of excellent alkali resistance, the proportion of the polymerizable monomer having a carboxyl group is preferably 50% by mass or less, based on the total mass of the polymerizable monomer used to obtain the component (A), and 40% by mass. % Or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less is particularly preferable.

  The acid value of the component (A) is preferably 50 to 150 mgKOH / g from the viewpoint of improving developability for various known developers in the development step. (A) The acid value of a component can be measured with reference to the measuring method of the Example mentioned later.

  The weight average molecular weight of the component (A) is preferably 5000 or more, more preferably 20000 or more, and still more preferably 30000 or more from the viewpoint of excellent developer resistance. The weight average molecular weight of the component (A) is preferably 300000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less, from the viewpoint of excellent development time. The weight average molecular weight of the component (A) is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, and still more preferably 30,000 to 100,000, from the viewpoint of balancing the mechanical strength and alkali developability. In addition, a weight average molecular weight can be measured with reference to the measuring method of the Example mentioned later.

  The content ratio of the component (A) is 30% by mass or more based on the total amount of the component (A) and the component (B), from the viewpoint of excellent photocurability and coatability on the support film 1. Preferably, 40 mass% or more is more preferable. The content ratio of the component (A) is preferably 80% by mass or less and 70% by mass based on the total amount of the component (A) and the component (B) from the viewpoint of excellent storage stability when wound as a film. The following is more preferable.

  (B) As a photopolymerizable compound having an ethylenically unsaturated bond, for example, a compound obtained by reacting a polyhydric alcohol and an α, β-unsaturated carboxylic acid; a glycidyl group-containing compound and an α, β-unsaturated compound Compound obtained by reacting with saturated carboxylic acid; Urethane monomer such as (meth) acrylate compound having urethane bond; γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β Phthalic acid compounds such as hydroxyethyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate; (meth) acrylic acid alkyl ester Is mentioned.

  Among the above, it is preferable to use a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. Specifically, for example, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, Bisphenol A (meth) acrylate compounds such as 2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol Polyalkylene glycol di (meth) acrylates such as di (meth) acrylate; trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethyl Trimethylolpropane (meta) such as propane propanediethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, etc. ) Acrylate compound; tetramethylolmethane tri (meth) acrylate, tetramethylolmethane (meth) acrylate compound such as tetramethylolmethanetetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples thereof include pentaerythritol (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate.

  The content ratio of the component (B) is 20% by mass or more based on the total amount of the component (A) and the component (B) from the viewpoint of excellent photocurability and coatability on the support film 1. Preferably, 30 mass% or more is more preferable. The content ratio of the component (B) is preferably 70% by mass or less, based on the total amount of the component (A) and the component (B), from the viewpoint of excellent storage stability when wound as a film, and 60% by mass. The following is more preferable.

  (C) The photopolymerization initiator is not particularly limited as long as it can cure the photosensitive resin layer 2 by irradiation with actinic rays, but a radical polymerization initiator is preferable from the viewpoint of excellent photocurability. . Examples of the component (C) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino- Aromatic ketone compounds such as 1- (4-morpholinophenyl) -1-butanone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 1- [4- (phenylthio) ) Phenyl] -1,2-octanedione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyl) Oxime ester compounds such as oxime); benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4, -Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- 2,4,5-triarylimidazole dimers such as (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; Examples include acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane; acylphosphine oxide compounds.

As the component (C), an aromatic ketone compound, an oxime ester compound, or an acyl phosphine oxide compound is preferable from the viewpoint of excellent sensitivity and patterning property of the photosensitive resin layer 2, and an oxime ester compound or an acyl phosphine oxide compound is preferable. Further preferred. By using these compounds, the sensitivity and patterning property of the photosensitive resin layer 2 can be improved.
As the aromatic ketone compound, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone is preferable. The oxime ester compound is preferably 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime). As the acylphosphine oxide compound, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferable.

  The content ratio of the component (C) is preferably 0.1% by mass or more and more preferably 1% by mass or more based on the total amount of the component (A) and the component (B) from the viewpoint of excellent photosensitivity. The content ratio of the component (C) is preferably 20% by mass or less, based on the total amount of the component (A) and the component (B), preferably 10% by mass, from the viewpoint of excellent photocurability inside the photosensitive resin layer 2. % Or less is more preferable, and 5 mass% or less is still more preferable.

  The photosensitive resin layer 2 contains (D) a compound containing at least one atom selected from the group consisting of S (sulfur atom) and I (iodine atom) (hereinafter sometimes referred to as “component (D)”). can do. Thereby, plating deposition on the photosensitive resin layer 2 can be suppressed, and further selective plating can be performed. In addition, the (A)-(C) component containing S or I shall belong to the (A)-(C) component.

  The sulfur compound containing S is preferably an organic sulfur compound from the viewpoint of effectively suppressing deposition of plating, and specific examples include 2-mercaptobenzothiazole, thiourea, and tetramethylthiuram monosulfide. The iodine compound containing I is preferably an organic iodo compound from the viewpoint of effectively suppressing plating deposition, and specific examples include o-iodobenzoic acid, o-iodoaniline, iodobenzene, and the like. A compound corresponding to both a sulfur compound and an iodine compound shall correspond to a sulfur compound.

  The content ratio of the component (D) is preferably 0.5% by mass or more, preferably 1% by mass or more, based on the total amount of the component (A) and the component (B), from the viewpoint of effectively suppressing plating deposition. Is more preferable. The content ratio of the component (A) is preferably 10% by mass or less, based on the total amount of the component (A) and the component (B), from the viewpoint of excellent photocurability and patterning property of the photosensitive resin layer 2. The mass% or less is more preferable.

  The photosensitive resin layer 2 can contain various additives as needed.

  The photosensitive resin layer 2 can be formed by applying a solution of a photosensitive resin composition having a solid content of about 10 to 60% by mass on the support film 1 and then drying. The amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.

  Coating can be performed by a known method. Examples of the coating method include a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. Drying for removing the organic solvent and the like can be performed at 70 to 150 ° C. for about 5 to 30 minutes with a hot air convection dryer or the like.

  Although the thickness (thickness after drying) of the photosensitive resin layer 2 varies depending on the application, it is preferably 0.5 μm or more from the viewpoint of easy layer formation by coating, and is excellent in photocurability of the photosensitive resin layer 2. From the viewpoint, it is preferably 100 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. The thickness of the photosensitive resin layer 2 can be measured with a scanning electron microscope.

  The plating seed layer 3 can contain at least one selected from the group consisting of a compound containing an electron-donating atom, a binder polymer, and a photopolymerizable compound having an ethylenically unsaturated bond.

  The plating seed layer 3 can contain a compound containing at least one electron donating atom selected from the group consisting of P (phosphorus atom), O (oxygen atom) and N (nitrogen atom). As a result, the interaction between the plating seed layer and the plating catalyst used in the plating step or its precursor can be increased, and the plating depositability of the plating seed layer can be improved. Examples of the compound containing an electron-donating atom include nitrogen compounds, phosphorus compounds (excluding compounds corresponding to the nitrogen compounds), and oxides (oxygen-containing compounds) not corresponding to nitrogen compounds and phosphorus compounds. . A compound containing an electron-donating atom, a binder polymer, or a compound in which the photopolymerizable compound having an ethylenically unsaturated bond contains P, O or N is a compound containing an electron-donating atom, a binder polymer, or And a photopolymerizable compound having an ethylenically unsaturated bond, respectively.

Examples of nitrogen compounds include amino compounds. Examples of the amino compound include a silane coupling agent containing an amino group (for example, a compound having no carbonyl group (CO) next to an amino group such as 3-aminopropyltriethoxysilane), an amino acid, an amino alcohol, 4-aminoquinoxaline, 8-aminoquinoline, 4-amino-5-aminomethylpyridine dihydrochloride, 8-azaquanin, 2-aminopyridine, 2-aminopyrimidine, 5-amino-1H-tetrazole, and 2,4 -Diamino-6-hydroxypyrimidine.
Examples of amino acids include glycine, α-alanine, valine, leucine, isoleucine, serine, threoline, lysine, arginine, aspartic acid, glutamic acid, asparagine, glutamine, phenylalanine, tyrosine, proline, hydroxyproline, tryptophan, histidine, β- Examples include alanine, ε-aminocaproic acid, sarcosine, and DL-pyroglutamic acid.
Examples of the amino alcohol include R-(−)-2-amino-1-butanol, 3-amino-2,2-dimethyl-1-propanol, 2- (2-aminoethylamyl) ethanol, 6-amino- Examples include 1-hexanol, 5-amino-1-pentanol, and 3-amino-1-propanol.

Examples of the phosphorus compound include a titanium-based coupling agent containing a phosphorus atom, ethyl diethylphosphonoacetate, isopropyl azido phosphate, ethyl azido phosphate, tris (2-butoxydiethyl) phosphate, dimethyl phosphate, and O- A phosphoryl ethanolamine is mentioned.
Examples of the titanium coupling agent containing a phosphorus atom include isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl (dioctyl phosphite) titanate, tetraoctyl bis (didodecyl phosphite) titanate, tetra (2,2 ′). -Diallyloxydimethyl-1-butyl) bis (ditridodecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, and isopropyltri (dioctylphosphate) ) Titanate.

  As an oxide which does not correspond to a nitrogen compound and a phosphorus compound, a carboxyl group-containing compound is mentioned, for example. Examples of the carboxyl group-containing compound include acetic acid, propionic acid, benzoic acid, isophthalic acid, terephthalic acid, cinnamic acid, malonic acid, and succinic acid.

  The content of the compound containing an electron-donating atom is preferably 0.5% by mass or more, preferably 1% by mass or more, based on the total amount of the plating seed layer 3, from the viewpoint of effectively improving the plating deposition property. More preferred. The content ratio of the compound containing an electron-donating atom is 10% by mass based on the total amount of the plating seed layer 3 from the viewpoint of excellent solubility of the plating seed layer resin composition in the solution and stability of the solution. The following is preferable, and 5 mass% or less is more preferable.

  The plating seed layer 3 can contain a binder polymer. Specifically, (A) binder polymer in the photosensitive resin layer 2 mentioned above is mentioned.

  The binder polymer of the plating seed layer 3 preferably has a carboxyl group from the viewpoint of obtaining sufficient adhesion with the plating metal. Examples of the polymerizable monomer that gives such a binder polymer having a carboxyl group include (meth) acrylic acid as described above.

  On the other hand, from the viewpoint of the formability of the exposed portion 3b of the plating seed layer 3 to be described later, since it is preferable to use a plating seed layer that is difficult to be removed in the development step, the ratio of the polymerizable monomer having a carboxyl group is 10 mass% or less is preferable and 5 mass% or less is more preferable on the basis of the total mass of the polymerizable monomer used in order to obtain a binder polymer. The minimum of the ratio of the polymerizable monomer which has a carboxyl group is 0 mass% on the basis of the total mass of the polymerizable monomer used in order to obtain a binder polymer, for example.

  The weight average molecular weight of the binder polymer of the plating seed layer 3 is preferably 5000 or more, more preferably 20000 or more, and further preferably 30000 or more, from the viewpoint of excellent developer resistance and plating solution resistance. From the viewpoint of excellent development time, the weight average molecular weight of the binder polymer of the plating seed layer 3 is preferably 300000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. In addition, a weight average molecular weight can be measured with reference to the measuring method of the Example mentioned later.

  The content of the binder polymer is preferably 30% by mass or more and more preferably 40% by mass or more based on the total amount of the plating seed layer 3 from the viewpoint of excellent coating properties on the photosensitive resin layer 2. The content of the binder polymer is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total amount of the plating seed layer 3, from the viewpoint of excellent storage stability when wound as a film.

  The plating seed layer 3 can contain a photopolymerizable compound having an ethylenically unsaturated bond. Specifically, (B) the photopolymerizable compound which has an ethylenically unsaturated bond in the photosensitive resin layer 2 mentioned above is mentioned.

  The content of the photopolymerizable compound having an ethylenically unsaturated bond is preferably 20% by mass or more based on the total amount of the plating seed layer 3 from the viewpoint of excellent storage stability when wound up as a film. The mass% or more is more preferable. The content of the photopolymerizable compound having an ethylenically unsaturated bond is preferably 80% by mass or less, based on the total amount of the plating seed layer 3, from the viewpoint of excellent coating properties on the photosensitive resin layer 2. 60 mass% or less is more preferable.

  The plating seed layer 3 can contain a photopolymerization initiator. The photopolymerization initiator may be a compound containing at least one atom selected from the group consisting of P, O and N (the compound belongs to the photopolymerization initiator), and the P, It may be a compound different from the compound containing at least one atom selected from the group consisting of O and N. When the compound containing at least one atom selected from the group consisting of P, O, and N is a photopolymerization initiator, the interaction between the plating seed layer and the plating catalyst used in the plating step or its precursor can be reduced. In addition, the plating deposition property of the plating seed layer can be improved.

  Known photopolymerization initiators can be used without particular limitation, but acylphosphine oxide compounds are preferred from the viewpoint of excellent plating deposition and availability. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the photopolymerization initiator, (C) the photopolymerization initiator in the photosensitive resin layer 2 described above may be used.

  The content of the photopolymerization initiator is preferably 0.1% by mass or more and more preferably 1% by mass or more based on the total amount of the plating seed layer 3 from the viewpoint of excellent photosensitivity. The content of the photopolymerization initiator is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the plating seed layer 3, from the viewpoint of excellent photocurability inside the plating seed layer 3.

  The plating seed layer 3 preferably contains a silane coupling agent containing an amino group or an acyl phosphine oxide compound.

  The plating seed layer 3 can contain various additives as required.

  The plating seed layer 3 can be formed by applying a solution of a plating seed layer resin composition having a solid content of about 10 to 60% by mass to the photosensitive resin layer 2 formed on the support film 1 and then drying. The amount of the remaining organic solvent in the plating seed layer after drying is preferably 2% by mass or less in order to prevent diffusion of the organic solvent in the subsequent process.

  Coating can be performed by a known method. Examples of the coating method include a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. Drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes with a hot air convection dryer or the like.

  Although the thickness (thickness after drying) of the plating seed layer 3 varies depending on the use of the metal pattern (wiring etc.) to be formed and the required plating precipitation, the following ranges are preferable. The thickness of the plating seed layer 3 is preferably 0.5 μm or more from the viewpoint of easy layer formation by coating. The thickness of the plating seed layer 3 is excellent in the photocurability of the plating seed layer 3 and suppresses the seepage (edge fusion) of the resin from the end of the winding roll when the photosensitive film 10 is wound up. In view of this, it is preferably 50 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. The thickness of the plating seed layer 3 can be measured with a scanning electron microscope.

  The photosensitive film 10 may be formed by laminating (laminating or the like) the photosensitive resin layer 2 formed on the support film 1 on the plating seed layer 3 provided on the base material (substrate or the like). .

  The photosensitive film 10 may further include a protective film so as to be in contact with the surface of the plating seed layer 3 opposite to the support film 1 side.

  As the protective film, a polymer film having heat resistance and solvent resistance can be used. Examples of the protective film include a polyethylene terephthalate film, a polypropylene film, and a polyethylene film. Moreover, you may use the polymer film similar to the support film 1 as a protective film.

  From the viewpoint of excellent mechanical strength, the thickness of the protective film is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 15 μm or more. The thickness of the protective film is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less, and particularly preferably 30 μm or less from the viewpoint of excellent handleability.

  The adhesive force between the protective film and the plating seed layer 3 is such that the support film 1 and the photosensitive layer 4 (the photosensitive resin layer 2 and the plating seed layer 3) can be easily separated from the plating seed layer 3. It is preferable that it is smaller than the adhesive force between.

  The photosensitive film 10 can be stored, for example, in the form of a flat plate as it is, or can be stored in the form of a roll wound around a cylindrical core. In addition, when storing with a roll form, it is preferable to wind up so that the support film 1 may be arrange | positioned on the outermost side. Moreover, when the photosensitive film 10 does not have a protective film, the photosensitive film 10 can be stored with the flat form as it is.

  The core is not particularly limited as long as it is conventionally used. Examples of the constituent material of the core include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). Moreover, it is preferable to install an end face separator on the end face of the photosensitive film wound up in a roll shape from the viewpoint of end face protection, and it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Moreover, when packing a photosensitive film, it is preferable to wrap and wrap in a black sheet with small moisture permeability.

<Metal pattern forming method and pattern substrate>
The method for forming a metal pattern (wiring or the like) according to this embodiment is a method for forming a metal pattern by plating. The metal pattern forming method according to the present embodiment includes a seed layer exposed pattern forming step and a plating step in this order. The seed layer exposed pattern forming step includes a photosensitive film laminating step, an exposing step, and a developing step in this order.

  In the photosensitive film laminating step, the photosensitive film according to this embodiment is laminated (for example, laminated) on a base material (substrate or the like) so that the plating seed layer is positioned on the base material side with respect to the photosensitive resin layer. . In the exposure step, an exposed portion is formed by irradiating a predetermined portion of the photosensitive resin layer with actinic rays. Moreover, actinic light can be irradiated also to the predetermined part of a plating seed layer with the photosensitive resin layer. In the development step, for example, after peeling the support film, the photosensitive resin layer is developed to remove the unexposed portion of the photosensitive resin layer, and the exposed portion (for example, the exposed portion of the photosensitive resin layer) is exposed to the plating seed layer. (Part exposed from between) is formed (a cured resin pattern in which the plating seed layer is exposed is formed). In the plating step, a metal layer that covers the exposed portion of the plating seed layer is formed by electroless plating to obtain a metal pattern.

  An example of a method for forming a cured resin pattern in which the plating seed layer is exposed will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view for explaining an example of a method for forming an exposed portion of a plating seed layer using a photosensitive film. The method for forming the exposed portion of the plating seed layer shown in FIG. 2 includes a laminating step (photosensitive film laminating step), an exposure step, and a developing step in this order. According to such a method for forming the exposed portion of the plating seed layer, on the base material (substrate etc.) composed of glass, plastic, metal, etc. without being affected by the plating deposition property of the base material in the plating process. A metal pattern (for example, a transparent metal pattern) can be easily formed as a plating deposition pattern.

  In the laminating step, for example, the photosensitive film 10 is laminated on the substrate 20 so that the plating seed layer 3 is in contact with the substrate 20 (FIG. 2A). In the exposure step, an actinic ray L is applied to a predetermined portion of the photosensitive layer 4 covered with the support film 1 (FIG. 2B). In the development step, after the support film 1 is peeled off, the photosensitive resin layer 2 is developed to remove the unexposed portion of the photosensitive resin layer 2 and form an exposed portion 3b in the plating seed layer 3 (FIG. 2C). )). Hereinafter, each step will be further described.

(Lamination process)
Although it can use without a restriction | limiting especially as the board | substrate 20, For example, plastic substrates, such as a glass substrate, a resin substrate with a copper foil, and a polycarbonate substrate, are mentioned. The thickness of the substrate 20 can be appropriately selected according to the purpose of use. As the substrate 20, a film-like substrate may be used. Examples of the material for the film-like substrate include a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film. For applications requiring transparency, the minimum light transmittance in the wavelength region of 450 to 650 nm in the substrate 20 is preferably 80% or more.

In the laminating step, for example, the photosensitive film 10 can be laminated by pressing the plating seed layer 3 side of the photosensitive film 10 to the substrate 20 while heating. When the photosensitive film 10 has a protective film, a lamination process is performed after removing a protective film. The laminating step is preferably performed under reduced pressure from the viewpoint of excellent adhesion and followability. The lamination of the photosensitive film 10 is preferably performed while heating the plating seed layer 3 or the substrate 20 to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). Although preferred, these conditions are not particularly limited. Further, if the plating seed layer 3 is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the substrate 20 in advance, but pre-heat treatment of the substrate 20 is performed in order to further improve the stackability. You can also.

  According to the present embodiment, by providing the photosensitive layer 4 by laminating the separately prepared photosensitive film 10 to the substrate 20, it is possible to more easily form the photosensitive layer 4 on the substrate 20, and productivity. Can be improved.

(Exposure process)
As an exposure method in the exposure step, for example, a method of irradiating an actinic ray L in an image form through a negative or positive mask pattern 5 called an artwork as shown in FIG. 2B (mask exposure method) Is mentioned.

  As the light source of actinic rays in the exposure step, a known light source can be mentioned. For example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp can be used. An Ar ion laser or a semiconductor laser can also be used. A light source that effectively emits visible light, such as a photographic flood bulb or a solar lamp, can also be used. You may employ | adopt the method of irradiating an actinic ray in an image form with the direct drawing method using a laser exposure method etc.

Although the exposure amount in an exposure process changes with the apparatuses to be used and the composition of the photosensitive resin composition, the following ranges are preferable. Exposure dose in the exposure step, from the viewpoint of excellent photocuring properties, preferably 5 mJ / cm ² or more, 10 mJ / cm ² or more is more preferable. Exposure dose in the exposure step, from the viewpoint of achieving excellent resolution, preferably 1000 mJ / cm ² or less, 200 mJ / cm ² or less being more preferred.

  By exposing the photosensitive layer 4 in the exposure step without peeling off the support film 1, the influence of oxygen inhibition is reduced and the photosensitive resin layer 2 is easily cured.

(Development process)
In the development step, the photosensitive resin layer 2 is developed to remove the unexposed portion of the photosensitive resin layer 2 and pattern it, thereby obtaining a resin cured pattern 2a in which a part of the plating seed layer 3 is exposed.

  In the development process, for example, uncured portions of the photosensitive resin layer 2 exposed in the exposure process are not cured. For example, the unexposed portion of the photosensitive resin layer 2 on the plating seed layer 3 that has not been cured is removed by wet development. Thereby, as shown in FIG. 2C, a cured resin pattern 2a made of a cured product of the photosensitive resin layer 2 cured in the exposure process is left on the cured product 3a of the plating seed layer. In the region where the resin cured pattern 2a does not exist, the exposed portion 3b of the plating seed layer 3 is exposed. According to this embodiment, the pattern substrate 30 having the exposed portion 3b of the plating seed layer 3 is obtained. The exposed portion 3b of the plating seed layer 3 can be formed by using a plating seed layer that is difficult to remove in the development process.

  The wet development is performed by a known method such as spraying, rocking immersion, brushing, or scraping, using, for example, an alkaline aqueous solution, an aqueous developer, an organic solvent developer, or the like.

  As the developer, an alkaline aqueous solution is preferable because it is safe and stable and has good operability. As alkaline aqueous solution, for example, 0.1-5 mass% sodium carbonate aqueous solution, 0.1-5 mass% potassium carbonate aqueous solution, 0.1-5 mass% sodium hydroxide aqueous solution, and 0.1-5 mass% A sodium tetraborate aqueous solution is preferred. The pH of the alkaline aqueous solution used for development is preferably in the range of 9-11. The temperature of the alkaline aqueous solution is adjusted according to the developability of the photosensitive resin layer 2. Further, the alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like.

  Also, an aqueous developer composed of water or an aqueous alkali solution and one or more organic solvents can be used. Here, as the base contained in the alkaline aqueous solution, in addition to the above-mentioned bases, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diamino-2-propanol, and morpholine.

  Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Is mentioned.

  The content ratio of the organic solvent in the aqueous developer is preferably 2 to 90% by mass. The temperature of the aqueous developer can be adjusted according to the developability. The pH of the aqueous developer is preferably as low as possible within a range where the photosensitive resin layer can be sufficiently developed. The pH of the aqueous developer is preferably 8 to 12, and more preferably 9 to 10. The aqueous developer can contain a small amount of a surfactant, an antifoaming agent and the like.

  Examples of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvent-based developers preferably contain water in the range of 1 to 20% by mass in order to prevent ignition.

  Examples of the development method include a dip method, a battle method, a spray method (such as a high-pressure spray method), brushing, and slapping. Among these, it is preferable to use a high-pressure spray system from the viewpoint of improving the resolution.

In the method of forming a cured resin pattern in which the plating seed layer is exposed, the plating seed layer is formed by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary after development. The resin cured pattern may be further cured.

(Plating process)
In the plating step, a metal pattern is obtained by forming a metal layer covering the exposed portion of the plating seed layer by electroless plating.

  An example of the electroless plating process will be described with reference to FIG. FIG. 3 is a schematic cross-sectional view for explaining an example of a method for forming a metal pattern using electroless plating. First, a pattern substrate 30 similar to that shown in FIG. 2C is prepared (FIG. 3A). Next, the plating catalyst 22 composed of a metal compound is brought into contact with the surface of the exposed portion 3b of the plating seed layer 3 in advance (FIG. 3B). Then, electroless plating is performed to form a metal layer 24 on the exposed portion 3b of the plating seed layer 3 (FIG. 3C). Thereby, a pattern substrate (selective plating pattern substrate) 40 having the metal pattern 26 composed of the metal layer 24 is obtained.

  As the metal element of the metal compound constituting the plating catalyst 22, at least one selected from the group consisting of palladium, silver, copper, gold and platinum can be used. As the metal compound, a compound of palladium, silver, copper, gold or platinum (for example, a water-soluble compound) or a combination of two or more of these metal elements is preferable. Examples of the metal compound include palladium compounds such as palladium chloride, palladium sulfate, palladium nitrate, and palladium acetate; copper compounds such as copper sulfate; silver compounds such as silver nitrate; tetrachlorogold (IV) acid salt, tetrachlorogold (III) acid Examples thereof include gold compounds such as salts; platinum compounds and the like. As these metal compounds, palladium compounds containing palladium are particularly preferable.

  The plating catalyst 22 containing a palladium compound can be formed by a palladium catalyst treatment. The palladium catalyst treatment can be performed by a known method. Although it does not specifically limit as a method of a palladium catalyst treatment, For example, the catalyst treatment method using the catalyst treatment liquid called an alkali seeder or an acidic seeder is mentioned.

  Examples of the catalyst treatment method using an alkali seeder include the following methods. First, a palladium ion solution coordinated with 2-aminopyridine is brought into contact with the exposed portion of the plating seed layer to adsorb the palladium ions on the surface of the exposed portion of the plating seed layer. After washing with water, the exposed portion of the plating seed layer to which the palladium ions have been adsorbed is brought into contact with a solution containing a reducing agent such as sodium hypophosphite, sodium borohydride, dimethylamine borane, hydrazine, formalin, and the like to perform a reduction treatment. Thus, palladium ions adsorbed on the exposed portion of the plating seed layer are reduced to metallic palladium.

  Examples of the catalyst treatment method using an acidic seeder include the following methods. First, a sensitization treatment is performed in which a stannous chloride solution is brought into contact with the exposed portion of the plating seed layer, and tin ions are adsorbed on the surface of the exposed portion of the plating seed layer. After washing with water, a solution containing palladium chloride is brought into contact, and an activation treatment for trapping palladium ions on the resin surface is performed, followed by washing with water. Further, reduction treatment is performed by contacting a solution containing a reducing agent such as sodium hypophosphite, sodium borohydride, dimethylamine borane, hydrazine, formalin and the like. Thus, palladium ions adsorbed on the exposed portion of the plating seed layer are reduced to metallic palladium.

  In these palladium-catalyzed treatment methods, palladium ions are adsorbed on the surface, washed with water, and further, palladium ions adsorbed on the surface are reduced using a solution containing a reducing agent to form palladium precipitation nuclei.

  As a method for bringing the surface of the exposed portion of the plating seed layer into contact with at least one metal element selected from the group consisting of palladium, silver, copper, gold and platinum, for example, as described above, these metal elements are contained. The method of immersing in the aqueous solution containing a metal compound and the method of spraying the aqueous solution of these metal compounds are mentioned.

  The concentration of the aqueous solution containing the metal compound is preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass. The contact time is preferably 30 seconds to 24 hours, more preferably 1 minute to 1 hour, further preferably 1 minute to 10 minutes.

  In order to improve the hydrophilicity by cleaning the surface of the exposed portion of the plating seed layer, if necessary, the exposed portion of the plating seed layer may be contacted with a degreasing solution before contacting with the aqueous solution of the metal compound serving as a catalyst. Good. As the degreasing liquid, for example, Z-200 (trade name, manufactured by World Metal Co., Ltd.) and S-135 (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.) can be used.

  From the viewpoint of improving the depositability of the electroless plating, a treatment for bringing into contact with a reducing agent solution can be performed as necessary before performing the electroless plating. Examples of the reducing agent include hypophosphites, alkali borohydrides, dimethylamine borane, diethylamine borane, and hydrazine. It can be reduced by dipping in a solution of these reducing agents or by spraying the solution.

  As electroless plating after contacting the exposed portion of the plating seed layer with an aqueous solution of a metal compound serving as a catalyst, general-purpose electroless copper plating, electroless nickel plating, or the like can be used, but is not limited thereto. As electroless nickel plating, electroless nickel-phosphorous plating and electroless nickel-boron plating are generally known, but both can be used. Moreover, if necessary, electroplating (electroplating) may be performed to further deposit a metal layer on the electroless plating film to increase the thickness.

  Examples of the metal layer 24 formed by electroless plating include copper; an alloy of copper and nickel; an alloy of nickel and phosphorus; and an alloy of nickel and boron. Copper and an alloy of copper and nickel are characterized by low resistance. Nickel and phosphorus alloys and nickel and boron alloys are characterized by relatively hard coatings. These can be properly used according to the application.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

<Preparation of binder polymer (component (A)) solution>
[Preparation of binder polymer solution (A1)]
Into a flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer, the component (1) shown in Table 1 was charged, and the temperature was raised to 80 ° C. in a nitrogen gas atmosphere. While maintaining the reaction temperature at 80 ° C. ± 2 ° C., the component (2) shown in Table 1 was uniformly added dropwise over 4 hours. After dropwise addition of component (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (solid content 50% by mass) (A1) having a weight average molecular weight (Mw) of 50000 and an acid value of 78 mgKOH / g. .

[Preparation of binder polymer solution (A2)]
A component (1) shown in Table 2 was charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, and heated to 80 ° C. in a nitrogen gas atmosphere. While keeping the reaction temperature at 80 ° C. ± 2 ° C., the component (2) shown in Table 2 was uniformly added dropwise over 4 hours. After dropwise addition of component (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (solid content 50% by mass) (A2) having a weight average molecular weight (Mw) of 47000 and an acid value of 78 mgKOH / g. .

[Preparation of binder polymer solution (A3)]
A component (1) shown in Table 3 was charged into a flask equipped with a stirrer, a reflux condenser, an inert gas inlet, and a thermometer, and the temperature was raised to 80 ° C. in a nitrogen gas atmosphere. While keeping the reaction temperature at 80 ° C. ± 2 ° C., the component (2) shown in Table 3 was uniformly added dropwise over 4 hours. After dropwise addition of component (2), stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution (solid content 50% by mass) (A3) having a weight average molecular weight (Mw) of 60000 and an acid value of 0 mgKOH / g. .

<Evaluation of binder polymer solution>
The weight average molecular weight and acid value of the produced binder polymer solutions (A1) to (A3) were measured by the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
[GPC conditions]
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)

(2) Acid value The acid value was measured as follows. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile components, thereby obtaining a solid polymer. Then, after precisely weighing 1 g of the solid polymer, the precisely weighed polymer was put into an Erlenmeyer flask, and 30 g of acetone was added and dissolved uniformly. Next, an appropriate amount of an indicator, phenolphthalein, was added to the solution to obtain a resin solution, followed by titration using a 0.1N aqueous KOH solution. And the acid value was computed by following Formula.
Acid value = 10 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I represents the ratio (mass%) of the non-volatile content in the measured resin solution. Show.

<Preparation of photosensitive resin composition solution (E)>
Using a stirrer, the materials shown in Table 4 were mixed at the blending amounts (unit: parts by mass) shown in Table 4 for 15 minutes to prepare a photosensitive resin composition solution. In addition, the compounding quantity of (A) component in Table 4 is a mass part of solid content except a solvent. “SH-30” in Table 4 is a silicone leveling agent (manufactured by Toray Dow Corning Co., Ltd.).

<Preparation of plating seed layer resin composition solution (F)>
Using a stirrer, the materials shown in Table 5 were mixed at the blending amount (unit: parts by mass) shown in Table 5 for 15 minutes to prepare a plating seed layer resin composition solution. In addition, the compounding quantity of the binder polymer in Table 5 is the mass part of solid content except a solvent. “SH-30” in Table 5 is a silicone leveling agent (manufactured by Toray Dow Corning Co., Ltd.). As 3-aminopropyltriethoxysilane, trade name “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd. was used.

<Example 1>
[Preparation of photosensitive film]
The photosensitive resin composition solution (E1) in Table 4 was uniformly applied onto a 50 μm-thick support film (PET film, manufactured by Teijin Ltd., trade name “G2-50”), and then dried at 100 ° C. with hot air convection. The photosensitive resin layer was formed by drying for 5 minutes with a machine. The film thickness after drying of the photosensitive resin layer was about 2 μm.

  Next, the plating seed layer resin composition solution (F1) shown in Table 5 was uniformly applied on the photosensitive resin layer, and then dried for 5 minutes with a hot air convection dryer at 100 ° C. to form a plating seed layer. . The plating seed layer was covered with a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-13”, protective film) to obtain a photosensitive film. The film thickness after drying of the plating seed layer was about 5 μm, and the film thickness after drying of the entire photosensitive layer was about 7 μm.

[Formation of cured resin pattern with exposed plating seed layer]
While peeling the protective film from the photosensitive film on the easy-adhesion treated surface of a 50 μm thick pattern forming substrate (PET film, manufactured by Toyobo Co., Ltd., trade name “A4100”, hereinafter referred to as “A4100”), plating seed In a direction where the layer is positioned on the side of the PET film (pattern forming substrate), a substrate was obtained by laminating under conditions of 110 ° C. and 0.4 MPa, and then the substrate was cooled. When the temperature of the substrate reached 23 ° C., an artwork having a wiring pattern with a line width / space width of 100 μm / 100 μm and a length of 100 mm was brought into close contact with the surface on the side of the PET film as the support film. Then, using a parallel light exposure machine (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.) having a high-pressure mercury lamp, exposure is performed at an exposure amount of 30 mJ / cm ² (measured value at i-line) from the support film side. The photosensitive resin layer and the plating seed layer were irradiated with light.

  After the exposure, the artwork was removed and left at room temperature (25 ° C.) for 15 minutes. Subsequently, after removing the support film, development was performed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. By development, a cured resin pattern (photosensitive resin layer pattern) having a line width / space width of about 100 μm / 100 μm was formed on the plating seed layer. A pattern was produced in which an exposed portion having a width of 100 μm of the plating seed layer was exposed in the space portion (unexposed portion) of the resin cured pattern. The level difference between the surface of the photosensitive resin layer and the exposed portion of the plating seed layer was about 2 μm.

Subsequently, using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd., ultraviolet rays were irradiated from the resin cured pattern (photosensitive resin layer pattern) side with an exposure amount of 1000 mJ / cm ² (measured value in i-line).

[Metal layer formation by electroless plating]
The base material having a resin curing pattern with the plating seed layer exposed was immersed in an ICP clean S-135 aqueous solution (100 mL / L, trade name, manufactured by Okuno Pharmaceutical Co., Ltd.) having a liquid temperature of 50 ° C. for 1 minute. And after wash | cleaning with the pure water with a liquid temperature of 50 degreeC, it washed with running water for 1 minute. Subsequently, after immersing in an activator Neogant 834 conc aqueous solution (100 mL / L, Atotech Japan Co., Ltd., trade name) at a liquid temperature of 25 ° C. and an immersion time of 5 minutes, it was washed with running water for 1 minute. Then, after immersing in a sodium hypophosphite aqueous solution (sodium hypophosphite: 15 g / L) at a liquid temperature of 90 ° C. for 2 minutes, it was washed with running water for 1 minute.

Then, the metal layer was formed by immersing for 4 minutes in the electroless-plating bath (liquid temperature of 80 degreeC) of the following composition, and performing electroless nickel plating.
{Electroless nickel plating composition}
ICP Nicolon GM-SD-1 (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.): 50 mL / L
ICP Nicolon GM-SD-M (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.): 120 mL / L

  After rinsing with water, the depositing property of the plating was observed visually and with a digital microscope, and it was confirmed that the plating was selectively deposited only on the exposed portion of the plating seed layer. FIG. 4 is a photograph obtained by photographing a metal pattern obtained by electroless plating with a digital microscope (magnification: 100 times). In FIG. 4, the line width / space width is 100 μm / 100 μm.

Precipitation of plating (metal layer) by electroless plating was determined according to the following criteria. The results are shown in Table 6. 5-7, the code | symbol 42 is a metal pattern (plating pattern) containing the metal (plating) deposited on the exposed part of a plating seed layer, the code | symbol 44 is a photosensitive resin layer, the code | symbol 46 Indicates a metal (plating) deposited out of the exposed portion of the plating seed layer.
A: Plating is selectively deposited only on the exposed portion of the plating seed layer (FIG. 5).
B: Plating is selectively deposited on and around the exposed portion of the plating seed layer (FIG. 6).
C: Plating is deposited on the entire periphery of the exposed portion of the plating seed layer, and plating is deposited on the entire surface of the sample (FIG. 7).
D: No plating is deposited on the entire surface of the sample.

<Examples 2 to 5>
A photosensitive film was produced in the same manner as in Example 1 except that the photosensitive resin composition solution shown in Table 6 was used. And like Example 1, after forming the resin hardening pattern which the plating seed layer exposed, after forming the metal layer by electroless plating, the depositing property of plating was evaluated. The results are shown in Table 6.

<Examples 6 to 7>
A photosensitive film was produced in the same manner as in Example 1 except that the plating seed layer resin composition solution shown in Table 6 was used. And like Example 1, after forming the resin hardening pattern which the plating seed layer exposed, after forming the metal layer by electroless plating, the depositing property of plating was evaluated. The results are shown in Table 6.

<Examples 8 to 10>
Various substrate for pattern formation shown in Table 6 (untreated surface of PET film A4100, PET film (product name “A4300” manufactured by Toyobo Co., Ltd.), resin substrate with copper foil (product name “manufactured by Hitachi Chemical Co., Ltd., product name“ A photosensitive film was prepared in the same manner as in Example 1 except that MCL-E-679 ")) was used. And like Example 1, after forming the resin hardening pattern which the plating seed layer exposed, after forming the metal layer by electroless plating, the depositing property of plating was evaluated. The results are shown in Table 6.

<Comparative Example 1>
A substrate having a plating seed layer was produced through the same steps as in Example 1 except that the photosensitive resin layer was not formed. A substrate with the plating seed layer exposed on the entire surface was obtained. After the metal layer was formed by electroless plating, the plating deposition property was evaluated. The results are shown in Table 7.

<Comparative Example 2>
Resin curing through the same steps as in Example 1 except that the plating seed layer was not formed, PET film A4100 was used as a pattern forming substrate, and a photosensitive film was laminated on the untreated surface of A4100. A substrate having a pattern (photosensitive resin layer pattern) was produced. A substrate having a cured resin pattern formed on the untreated surface of the PET film A4100 was obtained. After the metal layer was formed by electroless plating, the plating deposition property was evaluated. The results are shown in Table 7.

<Comparative Examples 3-6>
Photosensitive film for various substrate for pattern formation shown in Table 7 (Easily adhesive surface of PET film A4100, Untreated surface of PET film A4100, PET film A4300, Resin substrate MCL-E-679 with copper foil) The metal layer was formed on the substrate as it was under the same electroless plating conditions as in Example 1, and then the plating deposition property was evaluated. The results are shown in Table 7.

  By using a photosensitive film having a photosensitive resin layer and a plating seed layer, plating is selectively deposited on the exposed portion of the plating seed layer, and a metal pattern is formed by plating without depending on the type of substrate. (Examples 1 to 10). In particular, when the photosensitive resin layer contained 2-mercaptobenzothiazole or o-iodobenzoic acid, the plating was selectively deposited without protruding from the exposed portion of the plating seed layer (Examples 4 and 5). Further, when the plating seed layer contains 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin-TPO) or 3-aminopropyltriethoxysilane, the plating does not protrude from the exposed portion of the plating seed layer. Plating was selectively deposited (Examples 6 and 7).

  When the photosensitive resin layer was not formed, plating was deposited on the entire surface of the plating seed layer, and a metal pattern was not obtained (Comparative Example 1). When an evaluation is made using a photosensitive film that does not form a plating seed layer on an untreated surface of the PET film A4100, which is a substrate surface on which plating is difficult to deposit, plating does not deposit on the entire surface, and a metal pattern is obtained. There was no (Comparative Example 2). When the photosensitive resin layer and the plating seed layer were not formed, plating was deposited on the entire surface of the plating seed layer, or plating was not deposited on the entire surface, and no metal pattern was obtained (Comparative Examples 3 to 6).

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2,44 ... Photosensitive resin layer, 2a ... Resin hardening pattern, 3 ... Plating seed layer, 3a ... Cured material of plating seed layer, 3b ... Exposed part of plating seed layer, 4 ... Photosensitive layer, 5 ... Mask pattern, 10 ... Photosensitive film, 20 ... Substrate, 22 ... Plating catalyst, 24 ... Metal layer, 26, 42 ... Metal pattern, 30 ... Pattern substrate with exposed portion of plating seed layer, 40 ... Pattern substrate, 46 ... metal, L ... active light.

Claims (7)

  A photosensitive film having a support film, a photosensitive resin layer provided on the support film, and a plating seed layer provided on the photosensitive resin layer.   The photosensitive film according to claim 1, wherein the plating seed layer contains a compound containing at least one atom selected from the group consisting of P, O, and N.   The photosensitive film of Claim 1 or 2 in which the said photosensitive resin layer contains a binder polymer, the photopolymerizable compound which has an ethylenically unsaturated bond, and a photoinitiator.   The photosensitive film of Claim 3 in which the said photoinitiator of the said photosensitive resin layer contains an oxime ester compound.   The photosensitive film as described in any one of Claims 1-4 in which the said photosensitive resin layer contains the compound containing at least 1 type of atom selected from the group which consists of S and I. Laminating the photosensitive film according to any one of claims 1 to 5 on a substrate such that the plating seed layer is located on the substrate side with respect to the photosensitive resin layer;
An exposure step of irradiating a predetermined part of the photosensitive resin layer with an actinic ray to form an exposed portion;
After the exposure step, the unexposed portion of the photosensitive resin layer is removed by developing the photosensitive resin layer, and an exposed portion is formed on the plating seed layer;
Forming a metal layer covering the exposed portion of the plating seed layer by electroless plating;
A method for forming a metal pattern including: A substrate, and a metal pattern provided on the substrate,
A pattern substrate, wherein the metal pattern is formed by the method for forming a metal pattern according to claim 6.