JP2012234013A - Metal pattern material and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallic pattern material capable of forming a metallic pattern of thin lines or small dots with high resolution after plating, and to provide a manufacturing method of the metallic pattern material.SOLUTION: The manufacturing method of a metallic pattern material comprises the steps of: exposing a specified light sensitive material for plating formation in exposure at a pitch of 6 μm or less with a laser power of 100% or less and [(pitch (μm)×75/6+25)-30]-[(pitch (μm)×75/6+25)+15]% to optimal power at the time of exposure at 6 μm pitch; developing the light sensitive material for plating formation after exposure with a developer; and plating the light sensitive material for plating formation with a pattern formed after development at a plating bath ratio of 10 or less.

Description

  The present invention relates to a metal pattern material used for semiconductor chips, various electric wiring boards, and the like, and a method of manufacturing the metal pattern material.

2. Description of the Related Art Conventionally, a metal wiring substrate in which a wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components, semiconductor elements, and the like.
As a method for producing such a metal pattern, the applicant of the present application first forms a polymer layer on a base material by forming a graft polymer bonded to the base material, and performs plating on the polymer layer. And a method of etching the obtained metal film has been proposed (see Patent Document 1).
Further, after that, the applicant of the present application improves the method of Patent Document 1 and has a non-dissociable functional group, a radical polymerizable group, and an ionic polar group that form an interaction with the plating catalyst or its precursor. The composition for to-be-plated layer forming containing a polymer is proposed (refer patent document 2).
These proposals made it possible to easily form a metal pattern with excellent adhesion to the substrate, but further, a metal pattern capable of forming a fine line or small dot metal pattern with high resolution after plating. At present, it is strongly desired to provide materials and methods for producing metal pattern materials.

JP 2006-350307 A JP 2010-248464 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, an object of the present invention is to provide a metal pattern material and a metal pattern material manufacturing method capable of forming a fine line or small dot metal pattern with high resolution after plating.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, (1) a specific photosensitive material for plating formation is used, and (2) a pitch of less than 6 μm is used for the specific photosensitive material for plating formation. Is less than 100% of the optimum power at the time of 6 μm pitch exposure, and [(Pitch (μm) × 75/6 + 25) −30] to [(Pitch (μm) × 75/6 + 25) +15 It was found that a metal pattern of fine lines or small dots can be formed with high resolution after plating by satisfying all of exposure with a laser power of% and (3) plating with a plating bath ratio of less than 10. .

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> When exposing a photosensitive material for plating formation containing a copolymer containing units represented by the following formulas (A) to (C) at a pitch of less than 6 μm, the optimum power at the time of 6 μm pitch exposure. On the other hand, an exposure step of exposing with a laser power of less than 100% and [(Pitch (μm) × 75/6 + 25) −30] to [(Pitch (μm) × 75/6 + 25) +15]%,
A development step of developing the photosensitive material for plating formation after exposure with a developer;
A plating process in which the photosensitive material for plating formation on which the pattern after development is formed is plated at a plating bath ratio of less than 10, and
It is a manufacturing method of the metal pattern material characterized by including.
However, in said formula (A)-(C), R < ¹ > -R < ⁶ > represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group each independently, X, Y, Z , And U each independently represents a single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ , L ² , and L ³ are each independently A single bond or a substituted or unsubstituted divalent organic group, W represents a non-dissociative functional group that interacts with the plating catalyst or its precursor, and V represents an ionic polar group .
<2> Less than 100% of the optimum power at the time of 6 μm pitch exposure, and [(Pitch (μm) × 75/6 + 25) −20]% to [(Pitch (μm) × 75/6 + 25) +10]% It is a manufacturing method of the metal pattern material as described in said <1> exposed with the laser power of.
<3> The method for producing a metal pattern material according to any one of <1> to <2>, wherein the plating bath ratio is 6 or less.
<4> The metal according to any one of <1> to <3>, wherein the photosensitive material for forming a plating contains a photopolymerization initiator, and the photopolymerization initiator has a light absorption amount of 2.5% or more. It is a manufacturing method of pattern material.
<5> A metal pattern material produced by the method for producing a metal pattern material according to any one of <1> to <4>.

  ADVANTAGE OF THE INVENTION According to this invention, the various problems in the past can be solved, and the metal pattern material which can form the metal pattern of a thin line | wire or a small dot with high resolution after plating and the manufacturing method of a metal pattern material can be provided.

FIG. 1 is a graph showing the relationship among pitch, exposure power, and drawing result. FIG. 2A is a photograph showing a state where the drawing result of the metal pattern material after plating is good “◯”. FIG. 2B is a photograph showing a state where the drawing result of the metal pattern material after plating is normally “Δ”. FIG. 2C is a photograph showing a state in which the drawing result of the metal pattern material after plating is defective “x”.

(Metal pattern material and metal pattern material manufacturing method)
The method for producing a metal pattern material of the present invention includes an exposure step, a development step, and a plating step, and further includes a catalyst application step and, if necessary, other steps.
The metal pattern material of this invention is manufactured by the manufacturing method of the metal pattern material of this invention.
Hereinafter, the details of the metal pattern material of the present invention will be clarified through the description of the method for producing the metal pattern material of the present invention.

  In the present invention, when the specific photosensitive material for plating formation is exposed at a pitch of less than 6 μm in the exposure step, it is less than 100% with respect to the optimum power at the time of 6 μm pitch exposure, and [(pitch ( [mu] m) * 75/6 + 25) -30]% to [(Pitch ([mu] m) * 75/6 + 25) +15]%. That is, when a specific photosensitive material for plating formation is exposed at a narrow pitch of less than 6 μm, the exposure is performed by controlling the laser power lower than usual.

The pitch means the shortest distance between the centers of adjacent patterns, and is less than 6 μm, preferably 5 μm or less, more preferably 3 μm or less. Moreover, a minimum is 0.01 micrometer or more, 0.1 micrometer or more, and 1 micrometer or more. When the pitch is 6 μm or more, the wiring density is lowered and the substrate area is increased. If it is less than 0.01 μm, the laser beam width cannot be reduced even if a short-wave laser is used, and the effect of the present invention may not be obtained even with an appropriate exposure power.
The above “with respect to the optimum power at the time of 6 μm pitch exposure when exposing at a pitch of less than 6 μm” means “with a pitch narrower than 10 times the Airy disk diameter (λ / NA × 1.22) of the laser beam, In other words, when the photosensitive material for plating formation is exposed, it can be rephrased as “to the optimum power at the time of exposure of 10 times the airy disk diameter”. At this time, the pitch is preferably 8 times or less, more preferably 5 times or less that of the Airy disk.
Here, the optimum power at the time of 6 μm pitch exposure differs depending on the photosensitive material for plating formation, and can be selected as appropriate. In the present invention, when recording at 10 times the airy disk pitch (6 μm pitch). This means the lowest power at which the drawing result is good (◯).

Using the specific photosensitive material for plating formation, the plating bath ratio is less than 10, the pitch is changed from 2 μm to 20 μm, the laser power is changed from 2 mW to 10 mW, the pattern is exposed at an equal interval pitch, and after development, plating is performed. The drawing results of the obtained metal pattern materials were evaluated. The relationship among the pitch, laser power, and drawing result is shown in FIG.
From the result of FIG. 1, the optimum power at the time of 6 μm pitch exposure is 8 mW, and a good drawing result (◯) is obtained when the pitch is less than 6 μm is surrounded by the lines A and B in the graph of FIG. It is recognized that the region is a diagonal region, that is, a region of [(pitch (μm) × 75/6 + 25) −30]% to [(pitch (μm) × 75/6 + 25) +15]%. In “(Pitch (μm) × 75/6 + 25)”, “6” in 75/6 represents a 6 μm pitch, “75/6” represents an inclination, and 25 represents an intercept.
Therefore, when the specific photosensitive material for plating formation is exposed at a pitch of less than 6 μm, it is less than 100% with respect to the optimum power at the time of 6 μm pitch exposure, and [(pitch (μm) × 75/6 + 25) −30]% to [(Pitch (μm) × 75/6 + 25) +15]% of laser power is required, and is less than 100% with respect to the optimum power at the time of 6 μm pitch exposure, and [( Pitch (μm) × 75/6 + 25) −20]% to [(Pitch (μm) × 75/6 + 25) +10]% laser power is preferably used for exposure. Specifically, when the pitch is 2 μm, the exposure is performed with a laser power of 20% to 65%, preferably a laser power of 30% to 60% with respect to the optimum power at the time of 6 μm pitch exposure. When the pitch is 4 μm, the exposure is performed at a laser power of 45% to 90%, preferably 55% to 85% with respect to the optimum power at the time of 6 μm pitch exposure.
When the laser power exceeds [(pitch (μm) × 75/6 + 25) +15]%, the exposure power is too large, and a short circuit may occur between the wirings. [(Pitch (μm) × 75/6 + 25) If it is less than -30]%, the exposure power is insufficient and sufficient conduction may not be obtained.

Further, in the present invention, in the plating step, the photosensitive material for plating formation on which the pattern after development is formed is plated with a plating bath ratio of less than 10.
The plating bath ratio is a numerical value indicating the magnitude of the bath load (surface area or number of plating objects to be added to the plating bath), and can be obtained by the following mathematical formula 1.
<Formula 1>
Plating bath ratio = Voltage of plating tank V (cm ³ ) ÷ Surface area A (cm ² )
The plating bath ratio (V / A) is less than 10, preferably 8 or less, and more preferably 6 or less. When the plating bath ratio is 10 or more, a plating film is likely to be generated, and the wiring may be short-circuited.

  In the present invention, (1) a specific photosensitive material for plating formation is used, and (2) when the specific photosensitive material for plating formation is exposed at a pitch of less than 6 μm, the optimum power at the time of 6 μm pitch exposure. And exposure with a laser power of less than 100% and [(pitch (μm) × 75/6 + 25) −30]% to [(pitch (μm) × 75/6 + 25) +15]%, (3 The metal pattern of fine lines or small dots can be formed with high resolution after plating only when all of plating with a plating bath ratio of less than 10 is satisfied.

<Exposure process>
The exposure step is a step of applying energy to a specific photosensitive material for plating formation to cure the specific photosensitive material for plating formation in that region.

<< Photosensitive material for plating formation >>
If the said photosensitive material for plating formation contains the copolymer (henceforth a "specific polymer") containing the unit represented by following formula (A)-(C). Although there is no restriction | limiting in particular, The aspect which has a to-be-plated layer on a board | substrate and has a close_contact | adherence auxiliary | assistant layer between the said board | substrate and the to-be-plated layer is preferable. In this case, the layer to be plated is formed from a composition for forming a layer to be plated containing the specific polymer.
The composition for forming a layer to be plated contains the specific polymer, a solvent, an additive for increasing the solubility of the specific polymer, a photopolymerization initiator, a sensitizer, a surfactant, a plasticizer, and a polymerization inhibitor. , A curing agent, a curing accelerator, and, if necessary, other additives.
However, in said formula (A)-(C), R < ¹ > -R < ⁶ > represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group each independently, X, Y, Z , And U each independently represents a single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ , L ² , and L ³ are each independently A single bond or a substituted or unsubstituted divalent organic group, W represents a non-dissociative functional group that interacts with the plating catalyst or its precursor, and V represents an ionic polar group .
Note that in this specification, an organic group refers to a substituent having carbon.

When R ^{1 to} R ⁶ are a substituted or unsubstituted alkyl group, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.
R ¹ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxyl group or a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxyl group or a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxyl group or a bromine atom.
R ⁶ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxyl group or a bromine atom.
Furthermore, from the viewpoint of flexibility of the specific polymer, R ¹ , R ⁵ , and R ⁶ are all preferably hydrogen atoms.

When X, Y, Z, and U are a substituted or unsubstituted divalent organic group, the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic group, A hydrocarbon group is mentioned.
X, Y, Z, and U are preferably a single bond, an ester group, an amide group, or an ether group, more preferably a single bond, an ester group, or an amide group, and in X, Z, and U, Most preferably, they are a single bond and an ester group. Furthermore, regarding Y, in addition to the single bond and the ester group, an amide group can be mentioned as one of the most preferable ones.

In addition, L ¹ , L ² , and L ³ are each one of preferred embodiments in which a linear, branched, or cyclic alkylene group, an aromatic group, or a group that combines these is preferable. The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L ¹ , L ² , and L ³ each preferably have 1 to 15 total carbon atoms, and particularly preferably unsubstituted. Here, the total number of carbon atoms, for example, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1. The same applies to L ² and L ³ .
Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom, etc., The group which combined these is mentioned.

The total number of carbon atoms in the L ¹ in the unit (A) is more preferably 1 to 10, a divalent organic group represented by L ¹ may be linear, it has a branched chain May be. Examples of the substituent that can be introduced into L ¹ include an ester group, an amide group, a halogen atom, a boron atom, an ether group, a phosphate ester group, a sulfate ester group, and a thiol group. You may have one or more. Note that it is not preferable to have a substituent such as a hydroxyl group, a thiol group, an amino group, a carboxylic acid group, or a phosphoric acid group from the viewpoint of maintaining the hydrophobicity of the formed layer to be plated.
In particular, L ¹ is preferably an embodiment having substantially no hydroxyl group in the structure of the linking group. When L ¹ does not have a hydroxyl group, it is difficult to contain an electroless plating solution (alkaline water) in the cross-linked portion compared to a structure containing a hydroxyl group, the film strength is reduced due to the plating solution, and the metal formed accordingly A decrease in adhesion of the film is further suppressed.

In particular, in the unit represented by the formula (C), moderate acidity (does not decompose other functional groups), hydrophilicity in an alkaline aqueous solution, and hydrophobicity due to the cyclic structure when water is dried. Therefore, it is preferable that V is a carboxylic acid group and has a 4-membered to 8-membered ring structure at the connecting portion of L ³ with V. Here, examples of the 4- to 8-membered ring structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a phenyl group. Among these, a cyclohexyl group and a phenyl group are particularly preferable. That is, in this embodiment, the terminal of the unit represented by the formula (C) is an alicyclic carboxylic acid group.
The unit represented by the formula (C) is moderately acidic (does not decompose other functional groups), hydrophilic in an alkaline aqueous solution, and hydrophobic by a long-chain alkyl group structure when water is dried. From the viewpoint that it is easy, V is a carboxylic acid group, and the chain length of L ³ is preferably 6 to 18 atoms. Here, the chain length of L ³ represents the distance between U and V in the formula (C), and it is preferable that the distance between U and V is 6 to 18 atoms. means. The chain length of L ³ is more preferably 6 to 14 atoms, and still more preferably 6 to 12 atoms.

On the other hand, in the unit represented by the formula (C), it is also one of preferable embodiments that V is a carboxylic acid group and U and L ³ are single bonds.
In this embodiment, it is expected that the carboxylic acid group is shielded by the polymer main chain, and as a result, it can be hydrophobized, and immediately after the formation of the metal pattern, the adhesion between the substrate and the metal pattern can be improved. The tolerance with respect to the water of a to-be-plated layer can be improved.

In the unit represented by the formula (B), W represents a non-dissociable functional group that interacts with the plating catalyst or its precursor, and examples of the non-dissociable functional group include those described above. Among these, W is preferably a cyano group or an ether group in that it has high polarity and high adsorption ability to a plating catalyst or the like.
Among these, a unit represented by the following formula (B-1) is preferable. In the following formula (B-1), R ⁵ has the same meaning as R ^{5 in the} unit represented by the formula (B). By selecting the unit represented by the following formula (B-1) as the unit represented by the formula (B), the number of cyano groups contained per polymer weight increases, and the composition for forming a layer to be plated The adsorption efficiency of the plating catalyst per unit weight of the product is further improved.

In the unit represented by the formula (C), V represents an ionic polar group, and examples of the ionic polar group include those described above. Among these, a carboxylic acid group is preferable as described above from the viewpoint of moderate acidity (does not decompose other functional groups).
In particular, a unit represented by the following formula (C-1) is preferable. In the following formula (C-1), R ⁶ and L ³ have the same meaning as described above.

The unit represented by the formula (A) may be contained in an amount of 5 mol% to 50 mol% with respect to the entire copolymer unit from the viewpoint of reactivity (curability, polymerization) and suppression of gelation during synthesis. Preferably, it is 10 mol%-40 mol% more preferably.
The unit represented by the formula (B) is preferably contained in an amount of 5 mol% to 40 mol% with respect to the entire copolymer unit, from the viewpoint of the adsorptivity to the plating catalyst or its precursor and the ease of synthesis. Preferably they are 10 mol%-35 mol%.
The unit represented by the formula (C) is preferably contained in an amount of 20 mol% to 70 mol%, more preferably 20 mol% to 60 mol%, based on the entire copolymer unit, from the viewpoint of developability with an aqueous solution and moisture-resistant adhesion. It is. Especially preferably, it is 30 mol%-50 mol%. Within this range, both developability and moisture-resistant adhesion can be achieved.

In addition, as an ionic polar value of the specific polymer (an acid value when the ionic polar group is a carboxylic acid group), 1.5 mmol / g to 7.0 mmol / g is preferable, and 2.0 mmol / g to 5.0 mmol. / G is more preferable, and 3.0 mmol / g to 4.5 mmol / g is particularly preferable. When the ionic polar value is within this range, it is possible to achieve both impartment of developability in an aqueous solution and suppression of a decrease in adhesion strength during wet heat aging.
The optimum number of units and ionic polarity value vary depending on the molecular weight of the unit having ionic polarity. In this case, priority is given to the ionic polarity value falling within the above range.

Although the specific example of the said specific polymer is shown below, it is not limited to these. For example, the various polymers mentioned as specific examples of the specific polymer containing units (A), (B-1), and (C-1) described later can also be suitably exemplified as the specific polymer.
In addition, as for the weight average molecular weight of these specific examples, all are the range of 3,000-150,000.

The weight average molecular weight of the specific polymer is preferably 3,000 to 150,000, more preferably 5,000 to 100,000. In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the specific polymer is preferably 20,000 or more. Furthermore, the weight average molecular weight is most preferably 60,000 or more from the viewpoint of increasing the thickness of the layer to be plated obtained by photocuring and adsorbing more of the plating catalyst or its precursor. From the viewpoint of suppressing gelation during synthesis, the upper limit of the molecular weight is preferably 150,000, and more preferably 100,000 or less.
Here, the said weight average molecular weight is a value measured by polystyrene conversion using GPC (use solvent: N-methylpyrrolidone), for example, can be measured on the following conditions.
・ Column: Guard column TOSOH TSKguardcolum Super AW-H
Separation column TOSOH TSKgel Super AWM-H (3 size 6.0 mm x 15 cm connected)
Eluent: N-methylpyrrolidone (containing 10 mM LiBr)
・ Flow rate: 0.35 mL / min
・ Detection method: RI
-Temperature: Column 40 ° C, inlet 40 ° C, RI 40 ° C
Sample concentration: 0.1% by mass
・ Injection volume: 60 μL

  The method for synthesizing the copolymer containing the units represented by (A) to (C) is described in detail in paragraphs [0055] to [0084] of JP 2010-248464 A.

When only the organic solvent is used as the solvent, the composition for forming a layer to be plated contains the specific polymer at 0.01% by mass to 50% by mass with respect to the entire composition for forming the layer to be plated. It is preferable to carry out, and 0.01 mass%-30 mass% are more preferable.
Moreover, when using the liquid mixture of water and a water-soluble organic solvent as a solvent in the said composition for forming a to-be-plated layer, as the optimal concentration range of a specific polymer, it is with respect to the said whole composition for to-be-plated layer forming. 0.01 mass% to 25 mass% is preferable, and 0.01 mass% to 15 mass% is more preferable.

-Solvent-
The composition for forming a layer to be plated preferably contains a solvent capable of dissolving the specific polymer in addition to the specific polymer.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether; acids such as acetic acid; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; formamide, dimethylacetamide Amide solvents such as N-methylpyrrolidone; Nitrile solvents such as acetonitrile and propyronitrile; Ester solvents such as methyl acetate and ethyl acetate; Carbonate solvents such as dimethyl carbonate and diethyl carbonate; Ether solvents and glycols A solvent, an amine solvent, a thiol solvent, a halogen solvent, etc. are mentioned.
Moreover, when apply | coating the composition containing the specific polymer which has a cyano group as an interactive group, the solvent whose boiling point is 50 to 150 degreeC is preferable from handling ease. In addition, these solvents may be used alone or in combination.

-Water-soluble organic solvent-
In the composition for forming a layer to be plated, water can be used as a solvent by neutralizing an ionic polar group with a base to increase hydrophilicity. In consideration of applicability at the time of application, it is preferable to use water and a water-soluble organic solvent in combination as the solvent. % Is preferred. Here, the water-soluble organic solvent means a solvent that can dissolve in water within the range of the content. If it is an organic solvent which has such a property, it will not specifically limit, It can use as a solvent of a composition. As the water-soluble organic solvent, for example, ketone solvents, ester solvents, alcohol solvents, ether solvents, amine solvents, thiol solvents, halogen solvents and the like are preferably used.

  Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, γ-butyrolactone, and hydroxyacetone. Examples of the ester solvent include 2- (2-ethoxyethoxy) ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methyl cellosolve acetate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, and glycolic acid. Examples include methyl and ethyl glycolate.

  Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 3-acetyl-1-propanol, 2- (allyloxy) ethanol, 2-aminoethanol, 2-amino-2-methyl-1- Propanol, (±) -2-amino-1-propanol, 3-amino-1-propanol, 2-dimethylaminoethanol, 2,3-epoxy-1-propanol, ethylene glycol, 2-fluoroethanol, diacetone alcohol, 2-methylcyclohexanol, 4-hydroxy-4-methyl-2-pentanone, glycerin, 2,2 ', 2 "-nitrilotriethanol, 2-pyridinemethanol, 2,2,3,3-tetrafluoro-1-propanol , 2- (2-Aminoethoxy Ethanol, 2- [2- (benzyloxy) ethoxy] ethanol, 2,3-butanediol, 2-butoxyethanol, 2,2′-thiodiethanol, 1,3-butanediol, 1,4-butanediol, 2 , 3-butanediol, 2-methyl-2,4-pentanediol, 1,3-propanediol, diglycerin, 2,2′-methyliminodiethanol, 1,2-pentanediol and the like.

  Examples of the ether solvent include bis (2-ethoxyethyl) ether, bis [2- (2-hydroxyethoxy) ethyl] ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- ( 2-methoxyethoxy) ethyl] ether, bis (2-methoxyethyl) ether, 2- (2-butoxyethoxy) ethanol, 2- [2- (2-chloroethoxy) ethoxy] ethanol, 2-ethoxyethanol, 2- (2-ethoxyethoxy) ethanol, 2-isobutoxyethanol, 2- (2-isobutoxyethoxy) ethanol, 2-isopropoxyethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, 2- (2 -Methoxyethoxy) ethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propyl Propanol, tripropylene glycol monomethyl ether, methoxy acetic acid and 2-methoxy ethanol.

Examples of the glycol solvent include diethylene glycol, triethylene glycol, ethylene glycol, hexaethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
Examples of the amine solvent include N-methyl-2-pyrrolidone and N, N-dimethylformamide.
Examples of the thiol-based solvent include mercaptoacetic acid and 2-mercaptoethanol.
Examples of the halogen solvent include 3-bromobenzyl alcohol, 2-chloroethanol, 3-chloro-1,2-propanediol, and the like.

  The boiling point of the water-soluble organic solvent is preferably 70 ° C. to 150 ° C., more preferably 65 ° C. to 120 ° C., from the viewpoint of easiness of evaporation. Examples of such water-soluble organic solvents include ethanol (boiling point: 78 ° C), isopropyl alcohol (boiling point: 82 ° C), n-propyl alcohol (boiling point: 97 ° C), tetrahydrofuran (THF) (boiling point: 66 ° C). 1-methoxy-2-propanol (boiling point: 119 ° C.), methyl ethyl ketone (MEK) (boiling point: 80 ° C.) and the like are preferable.

In addition, as described above, when using a mixed solution of water and a water-soluble organic solvent, the flash point is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of ease of work. More preferably, it is at least ° C.
The flash point means a measurement value obtained by a tag sealing method in accordance with JIS-K2265.

-Water-
The water used in the composition for forming a layer to be plated preferably contains no impurities, preferably RO water, deionized water, distilled water, purified water, and more preferably deionized water or distilled water.

-Additives for enhancing the solubility of specific polymers-
When using the liquid mixture of water and a water-soluble organic solvent for the said to-be-plated layer forming composition, in order to improve the solubility of a specific polymer, an additive can be used.
For example, when a specific polymer that is a solute has an acidic group such as a carboxylic acid group, the specific polymer is a mixture of water and a water-soluble organic solvent by converting the acidic group into a salt such as sodium carboxylate. It becomes easy to dissolve in. As an additive used for converting a carboxylic acid group to sodium carboxylate, a basic compound can be used. Specifically, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, tetramethylammonium hydroxy Potassium carbonate, potassium carbonate, potassium hydroxide, lithium bicarbonate, lithium carbonate, lithium hydroxide, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ammonia, DBU, DBN or the like can be used. Particularly preferred are sodium hydrogen carbonate, sodium carbonate, and sodium hydroxide from the viewpoint of water solubility and optimum basicity.

-Photopolymerization initiator-
The composition for forming a layer to be plated preferably contains a photopolymerization initiator in order to increase sensitivity to energy application.
As the photopolymerization initiator, a radical generator that generates radicals by irradiation with ultraviolet rays, electron beams, or the like, and that radicals trigger polymerization is suitable.
Examples of the radical generator include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, active ester compounds, and carbon halogen bonds. And the like, and pyridium compounds.
The light absorption amount in the photopolymerization initiator is preferably 2.5% or more, more preferably 3% or more, and still more preferably 3.5% or more. The upper limit is preferably 90% or less, more preferably 80% or less, and still more preferably 20% or less. If the light absorption amount is less than 2.5%, the sensitivity may be insufficient and an exposure pattern may not be obtained.
The light absorption amount can be measured by, for example, a laser power meter.

-Sensitizer-
In the composition for forming a layer to be plated, when energy is applied by exposure, a sensitizer is added in addition to the photopolymerization initiator (radical generator) for the purpose of further increasing sensitivity to the exposure. You can also.
The sensitizer is excited by active energy rays, and can promote the generation of radicals by interacting with the radical generator (for example, energy transfer, electron transfer, etc.).

There is no restriction | limiting in particular as said sensitizer, According to exposure wavelength, it can select suitably from well-known sensitizers.
Specifically, for example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal, etc.), cyanines (for example, indocarbocyanine) , Thiacarbocyanine, oxacarbocyanine, etc.), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue, etc.), acridines (eg, acridine orange, chloroflavin, acriflavine, etc.) ), Anthraquinones (for example, anthraquinone, etc.), squariums (for example, squalium, etc.), acridones (for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl) -Chloroacridone and the like), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin) 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-be Nzoyl-5,7-dipropoxycoumarin, etc. Other examples include JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208. And coumarin compounds described in JP-A-2002-363209 and the like.

As a combination of the radical generator and the sensitizer, for example, an electron transfer type initiation system described in JP-A No. 2001-305734 [(1) electron donating type initiator and sensitizing dye, (2) electron accepting Type initiators and sensitizing dyes, (3) electron donating initiators, sensitizing dyes and electron accepting initiators (ternary initiation system)], and the like.
Among these, a combination of a triazine-based photopolymerization initiator and a sensitizer having a maximum absorption at a wavelength of 360 nm to 700 nm is preferable.

  As other sensitizers, a sensitizer having a basic nucleus, a sensitizer having an acidic nucleus, a sensitizer having a fluorescent whitening agent, and the like can be used.

  The sensitizer is preferably contained in the composition for forming a layer to be plated in an amount of about 1% by mass to 30% by mass with respect to the mass of the specific polymer.

-Surfactant-
The composition for forming a layer to be plated may contain a surfactant.
The surfactant only needs to be soluble in the above-mentioned solvent. Examples of such surfactant include anionic surfactants such as sodium n-dodecylbenzenesulfonate; n-dodecyltrimethylammonium chloride. Cationic surfactants such as polyoxyethylene nonylphenol ether (commercially available products such as Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available products such as trade name “Tween”) 20 "), and nonionic surfactants such as polyoxyethylene lauryl ether.

-Plasticizer-
A plasticizer can be added to the composition for forming a layer to be plated, if necessary. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, diethyl ester, dibutyl ester, di-2-ethylhexyl ester, dinormal octyl ester, diisononyl ester, dinonyl ester). , Diisodecyl ester, butyl benzyl ester), adipic acid esters (dioctyl ester, diisononyl ester), azelain dioctyl, sebacin sun esters (dibutyl ester, dioctyl ester) tricresyl phosphate, tributyl acetyl citrate, epoxidized soybean oil, High boiling solvents such as trioctyl trimellitic acid, chlorinated paraffin, dimethylacetamide, N-methylpyrrolidone can also be used.

-Polymerization inhibitor-
A polymerization inhibitor can be added to the composition for forming a layer to be plated, if necessary.
Examples of the polymerization inhibitor include hydroquinones such as hydroquinone, ditertiary butyl hydroquinone and 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone; phenols such as p-methoxyphenol and phenol. Benzoquinones, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy free radical), free radicals such as 4-hydroxy TEMPO; phenothiazines, N-nitrosophenylhydroxyamine, aluminum salts thereof, etc. Nitrosamines; catechols can be used.

-Curing agent, curing accelerator-
When a plating layer is formed on the adhesion auxiliary layer using the composition for forming a plating layer, a curing agent and / or a curing accelerator is added to the composition for forming the plating layer in order to advance curing of the adhesion auxiliary layer. Can be added. For example, as a curing agent and / or a curing accelerator when an epoxy compound is contained in the adhesion auxiliary layer, in the polyaddition type, aliphatic polyamine, alicyclic polyamine, aromatic polyamine, polyamide, acid anhydride, phenol, phenol Examples of catalyst types such as novolak, polymercaptan, compounds having two or more active hydrogens include aliphatic tertiary amines, aromatic tertiary amines, imidazole compounds, and Lewis acid complexes.
Examples of those that start curing by heat, light, moisture, pressure, acid, base, etc. include, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamidoamine, mensendiamine, isophoronediamine, N -Aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-Aminocyclohexyl) methane, m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate) , Methylcyclohexene tetracarboxylic anhydride, trimellitic anhydride, polyazeline acid anhydride, phenol novolak, xylylene novolak, bisphenol A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol novolak, terpene phenol novolak, poly Mercaptan, polysulfide, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol-to 2-ethylhexylate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl S-triazine, BF ₃ monoethylamine complex, Lewis Acid complex, organic acid hydrazide, diaminomaleonitrile, melamine derivative, imidazole derivative, polyamine salt, amine imide compound, aromatic diazonium salt, diaryl iodonium salt, triarylsulfonium salt, triaryl selenium salt, ketimine compound Etc., and the like.

These curing agents and / or curing accelerators are used in an amount of 0 to 50% by mass of the remaining non-volatile components from which the solvent has been removed from the viewpoints of the coating properties of the composition for forming a layer to be plated and the adhesion between the substrate and the plating film. It is preferable to add to the extent.
The curing agent and / or curing accelerator may be added to the adhesion auxiliary layer, and in that case, the above range is determined by the amount added to the adhesion auxiliary layer and the total amount added in the composition for forming a layer to be plated. It is preferable to satisfy.

-Other additives-
The composition for forming a layer to be plated further includes a rubber component (for example, CTBN), a flame retardant (for example, a phosphorus flame retardant), a diluent, a thixotropic agent, a pigment, an antifoaming agent, and a leveling. Agents, coupling agents, water-soluble substances (for example, mineral components such as calcium oxide and magnesium oxide), soluble low-molecular substances (for example, polyalkyl glycols such as ε-caprolactam and polyethylene glycol) and the like may be added. Moreover, you may add these additives to a close_contact | adherence auxiliary | assistant layer as needed.

  In the composition for forming a layer to be plated, it is preferable that the specific polymer in the layer to be plated is bonded to the substrate by a radical polymerizable group in the molecule.

When the composition for forming a layer to be plated is brought into contact with the substrate, the coating amount is 0.1 g / in terms of solid content from the viewpoint of sufficient interaction formation with the plating catalyst or its precursor. m ^{2 to} 10 g / m ² are preferable, and 0.5 g / m ^{2 to} 5 g / m ² are more preferable.
In addition, when apply | coating the composition for to-be-plated layer containing a specific polymer on a board | substrate and making it dry and form the layer containing a specific polymer, it is 20 to 40 degreeC between application | coating and drying. May be left for 0.5 to 2 hours to remove the remaining solvent.

The contact between the composition for forming a layer to be plated and the substrate may be carried out by immersing the substrate in the composition for forming a layer to be plated. However, from the viewpoint of handleability and production efficiency, it will be described later. Thus, it is preferable to form the layer which consists of a to-be-plated layer forming composition on a substrate surface (adhesion auxiliary | assistant layer surface) by the apply | coating method.
In addition, when a board | substrate is a resin film and forms a to-be-plated layer with respect to both surfaces of this resin film, it is preferable to use the coating method from a viewpoint that it is easy to form a to-be-plated layer on both surfaces simultaneously.

-Board-
The substrate is not particularly limited as long as it has shape-retaining properties, and the surface thereof preferably has a function capable of chemically bonding with the specific polymer. Specifically, the substrate itself is capable of generating radicals upon exposure, or an intermediate layer (for example, an adhesion assisting layer described later) capable of generating radicals upon exposure is provided on the base material. The substrate may be composed of the intermediate layer.

The substrate is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.). , Plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyimide, epoxy, bismaleimide resin, Polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), paper or plastic film on which the above metal is laminated or vapor-deposited. Among these, an epoxy resin or a polyimide resin is particularly preferable.
In addition, when these base material surfaces have a function capable of forming a state in which a specific polymer is directly chemically bonded, the base material itself may be used as a substrate.

  As the substrate, a base material including polyimide having a polymerization initiation site described in paragraphs [0028] to [0088] of JP-A-2005-281350 in the skeleton can also be used.

  Moreover, the metal pattern material obtained by the manufacturing method of the metal pattern material of the present invention can be applied to semiconductor packages, various electric wiring boards, and the like. When used in such applications, the following substrate containing an insulating resin, specifically, a substrate made of an insulating resin or a substrate having a layer made of an insulating resin on a base material is used. It is preferable.

When obtaining the board | substrate which consists of the said insulating resin, and the layer which consists of insulating resins, a well-known insulating resin composition is used. In addition to the main resin, various additives can be used in combination with the insulating resin composition depending on the purpose. For example, a means such as adding a polyfunctional acrylate monomer for the purpose of increasing the strength of the insulating layer, or adding inorganic or organic particles for the purpose of increasing the strength of the insulating layer and improving electrical characteristics, etc. It can also be taken.
The “insulating resin” in the present invention means a resin having an insulating property that can be used for a known insulating film and insulating layer, and is not a perfect insulator. In addition, any resin having insulating properties according to the purpose can be applied to the present invention.

Specific examples of the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, and ABS resins.
Examples of the epoxy resin include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolak type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, Examples thereof include cyclopentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.
Examples of the polyolefin resin include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins.

Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.
Other thermoplastic resins include 1,2-bis (vinylphenylene) ethane resin (1,2-Bis (vinylphenyl) ethane), or a modified resin of this and a polyphenylene ether resin (Satoru Amaha et al., Journal of Applied Polymer Science). Vol. 92, 1252-1258 (2004)), liquid crystal polymers (specifically, Bexter manufactured by Kuraray Co., Ltd.), fluororesin (PTFE), and the like.

  The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is performed for the purpose of compensating for each defect and producing a superior effect. For example, thermoplastic resins such as polyphenylene ether (PPE) have a low resistance to heat, and are therefore alloyed with thermosetting resins. For example, it is used for alloying PPE with epoxy and triallyl isocyanate, or alloying PPE resin having a polymerizable functional group introduced and other thermosetting resins. Cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but it is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. Details thereof are described in “Electronic Technology” No. 2002/9, P35. Moreover, what contains an epoxy resin and / or a phenol resin as a thermosetting resin, and contains a phenoxy resin and / or polyether sulfone (PES) as a thermoplastic resin is also used in order to improve a dielectric characteristic.

  The insulating resin composition may contain a compound having a polymerizable double bond in order to promote crosslinking, specifically, an acrylate or methacrylate compound, and particularly a polyfunctional one. Is preferred. In addition, as a compound having a polymerizable double bond, methacrylic acid, acrylic acid, or the like is used for a thermosetting resin or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, or the like. Alternatively, a resin obtained by subjecting a part of the resin to (meth) acrylation reaction may be used.

  The insulating resin composition includes a composite of a resin and other components (composite material) in order to enhance the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical characteristics, etc. of the resin coating. ) Can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluorine resin, polyphenylene oxide resin, and the like.

Furthermore, the insulating resin composition includes a filler used for a general wiring board resin material as necessary, for example, an inorganic filler such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, and curing. You may mix | blend 1 type, or 2 or more types of organic fillers, such as an epoxy resin, crosslinked benzoguanamine resin, and a crosslinked acrylic polymer. Among these, it is preferable to use silica as the filler.
Furthermore, the insulating resin composition may contain one or two various additives such as a colorant, a flame retardant, an adhesion imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. More than seeds may be added.

  When these materials are added to the insulating resin composition, 1 part by mass to 200 parts by mass is preferable with respect to 100 parts by mass of the resin, and 10 parts by mass to 80 parts by mass are more preferable. When the addition amount is less than 1 part by mass, the above-described properties are not enhanced. When the addition amount exceeds 200 parts by mass, characteristics such as strength specific to the resin may be deteriorated.

Specifically, the substrate used in such applications is a substrate made of an insulating resin having a dielectric constant (relative dielectric constant) at 1 GHz of 3.5 or less, or made of the insulating resin. A substrate having a layer on a substrate is preferred. Moreover, the board | substrate which consists of an insulating resin whose dielectric loss tangent in 1 GHz is 0.01 or less, or the board | substrate which has the layer which consists of this insulating resin on a base material is preferable.
The dielectric constant and dielectric loss tangent of the insulating resin can be measured by a conventional method. For example, the cavity resonator perturbation method (for example, εr, tanδ measuring instrument for ultra-thin sheet, manufactured by Keycom Corporation) based on the method described in “18th Annual Conference of Electronics Packaging Society”, p189, 2004. ).
Thus, in the present invention, it is also useful to select an insulating resin material from the viewpoint of dielectric constant and dielectric loss tangent. Examples of insulating resins having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.01 or less include liquid crystal polymers, polyimide resins, fluororesins, polyphenylene ether resins, cyanate ester resins, and bis (bisphenylene) ethane resins. Furthermore, those modified resins are also included.

  The substrate has a surface irregularity of preferably 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and particularly preferably 20 nm or less in consideration of applications to semiconductor packages, various electric wiring boards and the like. The smaller the surface irregularity of this substrate (the surface irregularity of the intermediate layer or the adhesion auxiliary layer when it is provided), the smaller the electrical loss during high-frequency power transmission when the obtained metal pattern material is applied to wiring etc. Is preferable.

If the substrate is a plate-like material, for example, a resin film (plastic film), an exposure process is performed on both surfaces thereof, and a plated layer can be formed on both surfaces of the resin film through a development process described later. .
Thus, when the layer to be plated is formed on both surfaces of the resin film (substrate), a metal pattern material having a metal film formed on both surfaces can be obtained by performing a catalyst application step and a plating step described later. Can be obtained.

-Adhesion auxiliary layer-
Hereinafter, the adhesion auxiliary layer will be described. In addition, if the said base material is a plate-shaped object, you may form a close_contact | adherence auxiliary | assistant layer on both surfaces. As the adhesion auxiliary layer, those in which a specific polymer forms a chemical bond during photocuring are preferable. It is preferable to introduce a photopolymerization initiator into the adhesion auxiliary layer that generates such a chemical bond. Moreover, it is preferable that the said adhesion assistance layer is formed using water-dispersed latex from a workable viewpoint.

The adhesion auxiliary layer is an intermediate layer that ensures adhesion between the substrate and the layer to be plated. This layer may have an affinity between the substrate and the layer to be plated, and reacts with a specific polymer during curing to cause chemical bonding. You may form.
The adhesion auxiliary layer is preferably formed using a resin composition having good adhesion to the substrate and a compound capable of generating radicals upon exposure. In addition, when the resin which comprises a resin composition has the site | part which can generate a radical, it is not necessary to add the compound which can generate a radical separately.

As the adhesion auxiliary layer, for example, in the case where the substrate is made of a known insulating resin that has been used as a material for a multilayer laminate, a build-up substrate, or a flexible substrate, the viewpoint of adhesion to the substrate Therefore, it is preferable to use an insulating resin composition as the resin composition used when forming the adhesion auxiliary layer.
Hereinafter, a mode in which the base material is made of an insulating resin and the adhesion auxiliary layer is formed of an insulating resin composition will be described.

  The insulating resin composition used when forming the adhesion auxiliary layer may contain the same or different electrically insulating resin that constitutes the base material, but may have a glass transition point, elasticity It is preferable to use materials having similar thermophysical properties such as rate and linear expansion coefficient. Specifically, for example, it is preferable in terms of adhesion to use the same type of insulating resin as that constituting the base material. Further, as other components, inorganic or organic particles may be added in order to increase the strength of the adhesion auxiliary layer and to improve electrical characteristics.

In the present invention, the insulating resin used for the adhesion auxiliary layer means a resin having an insulating property that can be used for a known insulating film, and is not a perfect insulator. In addition, any resin having insulating properties according to the purpose can be applied to the present invention.
Specific examples of the insulating resin may be a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, and isocyanate resins. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.

  In addition, as the insulating resin used for the adhesion auxiliary layer, a resin having a skeleton that generates active sites capable of forming an interaction with the plating catalyst-receptive photosensitive resin composition can also be used. For example, a polyimide having a polymerization initiation site described in paragraphs [0018] to [0078] of JP-A-2005-307140 in the skeleton is used.

A polymer latex may be used for forming the adhesion auxiliary layer. The polymer latex is a dispersion of water-insoluble polymer fine particles in water. Details are described, for example, in “Polymer Latex Chemistry” by Soichi Muroi, published by Kobunshi Shuppankai, 1973.
The polymer latex is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester, polyurethane, polyurea / urethane, SBR (styrene-butadiene), MBR (MMA / butadiene, acrylic / butadiene). , NBR (acrylonitrile / butadiene), NR (natural rubber), acrylic rubber, BR (butadiene rubber), CR (chloroprene rubber), IR (isoprene rubber), VP (SBR / divinylpyridine), EPDM (ethylene propylene diene rubber) Or the polymer latex which consists of these copolymers, etc. are mentioned. In particular, a polymer latex containing a cyano group is preferable. Specifically, Nipol 1561 (manufactured by ZEON Corporation), Nipol 1562 (manufactured by ZEON Corporation), Nipol 1577K (manufactured by ZEON Corporation), LX 531 (Japan) Zeon Corporation), LX 531B (Nippon Zeon Corporation), Nipol SX1503A (Nippon Zeon Corporation), NK-300 (Nippon A & L Co., Ltd.) and the like.
In addition, different types of polymer latex can be used in combination with the polymer latex. Examples of polymer latexes that can be used in combination include SBR and NR, IR and NR, CR and NR, NBR with different nitrile amounts, SBR with different styrene amounts, SBR and VP, NBR and MBR, SBR and NBR, and SBR. And MBR, BR and CR, NBR and VP, CR and VP, and the like.
When the adhesion auxiliary layer is formed of polymer latex, a polymer latex dispersion may be applied and dried.

  As long as the effect of the present invention is not impaired, various compounds can be added to the adhesion auxiliary layer depending on the purpose. Specific examples include materials such as rubber and SBR latex that can relieve stress during heating, binders for improving film properties, plasticizers, surfactants, viscosity modifiers, and the like.

  In addition, the adhesion auxiliary layer includes a composite of a resin and other components (composite material) in order to enhance the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical properties, etc. of the resin coating. ) Can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluorine resin, and polyphenylene oxide resin.

  Furthermore, for the adhesion auxiliary layer, if necessary, a filler used for a general resin material for a wiring board, for example, an inorganic filler such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, cured epoxy, etc. You may mix | blend 1 type, or 2 or more types of organic fillers, such as resin, crosslinked benzoguanamine resin, and a crosslinked acrylic polymer.

  Further, the adhesion auxiliary layer may contain one or more various additives such as a colorant, a flame retardant, an adhesiveness imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. It may be added.

  When these materials are added, it is preferable to add them in the range of 0% by mass to 200% by mass, and more preferably in the range of 0% by mass to 80% by mass with respect to the resin as the main component. Is added. When the adhesion auxiliary layer and the adjacent base material exhibit the same or close physical property values to heat and electricity, it is not always necessary to add these additives. When the additive is used in a range exceeding 200% by mass with respect to the resin, there is a concern that characteristics such as strength inherent in the resin itself are deteriorated.

As described above, it is preferable to use a resin composition and a compound capable of generating radicals upon exposure as the adhesion auxiliary layer.
Here, conventionally known photopolymerization initiators are used as compounds capable of generating radicals upon exposure.
Examples of the photopolymerization initiator include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone ( Ketones such as 4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether Ethers; benzyl ketals such as benzyldimethyl ketal and hydroxycyclohexyl phenyl ketone; triphenylsulfonium chloride, triphenylsulfonium pentafluorophore Sulfonium salts such as Feto; diphenyliodonium chloride, etc. iodonium salts such as diphenyl iodonium sulfate and the like.

  The amount of the photopolymerization initiator (compound capable of generating radicals upon exposure) to be contained in the adhesion auxiliary layer is preferably 0.1% by mass to 50% by mass, and 1.0% by mass to 30% by mass in terms of solid content. More preferred.

  The thickness of the adhesion auxiliary layer is preferably 0.1 μm to 10 μm, and more preferably 0.2 μm to 5 μm. When providing the adhesion auxiliary layer, if the thickness is in the general range, sufficient adhesion strength between the adjacent substrate and the layer to be plated can be obtained, and compared to using a general adhesive. Although it is a thin layer, the same adhesion as that of the adhesive layer is achieved.

  The surface of the adhesion auxiliary layer is preferably 3 μm or less in surface roughness Rz measured by JIS B 0601 (1994), 10-point average height method, from the viewpoint of improving the physical properties of the formed plated metal film. Rz is more preferably 1 μm or less. If the surface smoothness of the adhesion auxiliary layer is within the above value range, that is, if the smoothness is high, the circuit is extremely fine (for example, a circuit pattern having a line / space value of 25/25 μm or less). It is used suitably when manufacturing.

The adhesion auxiliary layer is formed on the substrate surface by applying a known layer forming method such as a coating method, a transfer method, or a printing method.
The adhesion auxiliary layer may be formed by a printing method (for example, a gravure printing method, a screen printing method, a flexographic printing method, an ink jet printing method, an imprinting method, etc.) or a developing method (for example, wet etching, dry etching, ablation, light). It may be patterned by curing / plasticizing (negative type / positive type) or the like.

  Moreover, after the said adhesion assistance layer is formed on a base material, you may give a certain energy and may perform a hardening process. Examples of the energy to be applied include light, heat, pressure, electron beam, etc., and heat or light is common. In the case of heat, it is preferable to add heat at 100 ° C. to 300 ° C. for 5 minutes to 120 minutes. . In addition, the conditions for heat curing differ depending on the type of the material of the base material, the type of the resin composition constituting the adhesion auxiliary layer, and the like, and depending on the curing temperature of these materials, 120 ° C to 220 ° C for 20 minutes to It is preferably selected in the range of 120 minutes.

  This curing treatment may be performed immediately after the formation of the adhesion assisting layer, and if the preliminary curing treatment is performed for about 5 minutes to 10 minutes after the formation of the adhesion assisting layer, all other operations performed after the formation of the adhesion assisting layer are performed. You may implement after performing the process of.

  After the formation of the adhesion auxiliary layer, the surface may be roughened by a dry method and / or a wet method for the purpose of improving the adhesion to the layer to be plated formed on the surface. Examples of the dry roughening method include mechanical polishing such as buffing and sandblasting, plasma etching, and the like. On the other hand, the wet roughening method includes chemical treatment such as a method using an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, a strong base, or a resin swelling solvent. .

  In the exposure step, energy is imparted to the photosensitive material for forming the specific plating. As described above, when the specific photosensitive material for plating formation is exposed at a pitch of less than 6 μm, the energy application is less than 100% with respect to the optimum power at the time of 6 μm pitch exposure, and [(pitch (μm ) × 75/6 + 25) −30]% to [(Pitch (μm) × 75/6 + 25) +15]%.

  When the energy is applied, the curing reaction of the specific polymer occurs only in that region. As a result, only the energy application region of the photosensitive material for plating formation is cured on the substrate.

The exposure is preferably autofocus recording. At that time, the reflectance of the exposed layer is preferably 5% or more, more preferably 10% or more, and still more preferably 15% or more.
Under this condition, a pattern having a uniform width and shape can be formed over the entire surface. As a result, a margin in circuit design is increased, and a design with a high degree of freedom is possible.

-Types of laser light-
There is no restriction | limiting in particular as a kind of said laser beam, According to the objective, it can select suitably, For example, a liquid laser, a gas laser, a solid state laser, a semiconductor laser, a free electron laser etc. are mentioned. Among these, in order to be incorporated in the apparatus, a small one that does not require liquid and cooling is preferable, a semiconductor laser and a solid-state laser are preferable, and a semiconductor laser is particularly preferable in that self-modulation is possible.

-Laser linear velocity-
In the present invention, since exposure can be performed with low power, the linear velocity can be increased and the productivity can be increased. The lower limit of the linear velocity is preferably 0.1 m / s or more, more preferably 0.3 m / s or more, and still more preferably 0.5 m / s or more.
The upper limit of the linear velocity is preferably 40 m / s or less, more preferably 30 m / s or less, and still more preferably 20 m / s or less.
If the line speed is too low, stable servo and line width may not be obtained. If the line speed is too high, the servo may deviate, the line width may become thin, or writing may not be possible.

-Servo gain-
The upper limit of the servo gain (reference 50) is preferably 80 or less, more preferably 70 or less, and still more preferably 60 or less.
The lower limit value of the servo gain is preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more.
If the servo gain is too high, the servo may oscillate and the servo may come off. If the servo gain is too low, the servo may not be applied.

-Servo offset-
The upper limit of the servo offset (reference 50) is preferably 100 or less, more preferably 90 or less, and still more preferably 80 or less.
The lower limit value of the servo offset is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more.

-Laser wavelength-
The upper limit of the laser wavelength is preferably 1,600 nm or less, more preferably 1,100 nm, still more preferably 900 nm or less, and particularly preferably 700 nm or less.
The lower limit of the laser wavelength is preferably 150 nm or more, more preferably 200 nm or more, still more preferably 250 nm or more, and particularly preferably 300 nm or more.
A preferable range of the laser wavelength is more preferably 150 nm to 1,600 nm.

-Numerical aperture (NA)-
The upper limit of the numerical aperture (NA) of the objective lens is preferably 1.4 or less, more preferably 0.98 or less, and even more preferably 0.9 or less.
The lower limit of the numerical aperture (NA) is preferably 0.2 or more, more preferably 0.4 or more, and still more preferably 0.5 or more.
If the numerical aperture (NA) is too high, the depth of focus may be too small, and the servo may be easily released. If it is too low, the spot may become large and fine lines may not be cut.

-Laser power-
The upper limit of the laser power is preferably 200 mW or less, more preferably 100 mW or less, and even more preferably 50 mW or less.
The lower limit is preferably 0.5 mW or more, more preferably 1 mW or more, and still more preferably 2 mW or more.
If the laser power is too high, the material may be deformed by heating, and if it is too low, the linear velocity may be slow and productivity may not increase.

-Laser oscillation mode-
The laser beam may be continuous oscillation or pulse oscillation. However, continuous oscillation is preferable because the semiconductor laser can modulate light emission on / off. In the case of pulse oscillation, a solid laser capable of increasing the output is preferable. The pulse oscillation is preferable when the light emission time is 1 nsec or less because the effect of expanding the hole due to heat conduction can be reduced.

-Number of lasers-
The laser is basically used alone. However, the power may be increased by combining a plurality of lasers. Further, lasers having different wavelengths may be combined. In the case of a plurality of lasers, one can be used for servo such as focus, and the other can be used for processing.

-Laser pattern-
There is no restriction | limiting in particular as a pattern (shape) which can be formed by laser processing, According to the objective, it can select suitably, For example, various patterns, such as a linear form, a dot form, and planar form, can be formed.

<Development process>
The developing step is a step of developing an uncured portion of the specific plating-forming photosensitive material to form a specific plating-forming photosensitive material.

Examples of the aqueous solution used in the development step include an acidic aqueous solution, a neutral aqueous solution, and an alkaline aqueous solution.
As said acidic aqueous solution, hydrochloric acid aqueous solution, sulfuric acid aqueous solution, nitric acid aqueous solution is used, for example.
As the neutral aqueous solution, a solution obtained by dissolving a surfactant in water is used, and an anionic, nonionic or cationic surfactant can be used.
Among these, an alkaline aqueous solution is preferable, specifically, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, An aqueous solution of magnesium hydrogen carbonate or calcium hydrogen carbonate is used.
The concentration of these aqueous solutions is preferably 0.01% by mass to 10% by mass. The concentration is determined by the pKa of the ionic polar group and the desired development time.

Moreover, as a developing method, shower washing, a dipping method, etc. can be used. It is also possible to stir the developer and immerse and develop the photosensitive material for plating formation after exposure therein.
As development conditions, the development temperature is preferably from room temperature to 50 ° C., and the development time is preferably from 5 seconds to 10 minutes.

By the development, a patterned layer to be plated is formed on the substrate.
From the viewpoint of sufficient interaction formation with the plating catalyst or its precursor, the obtained layer to be plated preferably has a thickness of 0.2 to 1.5 μm, preferably 0.3 to 1 μm. 5 μm is more preferable, and 0.6 μm to 1.2 μm is particularly preferable.

<Catalyst application step>
The catalyst application step is a step of applying a plating catalyst or a precursor thereof to the light-sensitive material for plating formation on which the patterned layer to be plated is formed.

In the catalyst application step, the interactive group possessed by the specific polymer constituting the layer to be plated adheres (adsorbs) the applied plating catalyst or its precursor depending on its function.
Here, examples of the plating catalyst or a precursor thereof include those that function as a plating catalyst and an electrode in a plating step described later. Therefore, a plating catalyst or its precursor is determined by the kind of plating in a plating process.
The plating catalyst or its precursor used in the catalyst application step is preferably an electroless plating catalyst or its precursor.

-Electroless plating catalyst-
Any electroless plating catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, the electroless plating catalyst is a metal (Ni And the like, and more specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, and the like. Among them, those capable of multidentate coordination are preferable, and Ag and Pd are particularly preferable in view of the number of types of functional groups capable of coordination and high catalytic ability.
This electroless plating catalyst may be used as a metal colloid. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or protective agent used here.

-Electroless plating catalyst precursor-
The electroless plating catalyst precursor used in the catalyst application step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of the metals mentioned as the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion, which is an electroless plating catalyst precursor, may be used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating bath, by separately changing to a zero-valent metal by a reduction reaction. The electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

Actually, the metal ion which is the electroless plating precursor is applied onto the layer to be plated using a metal salt. The metal salt to be used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n, M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which the said metal salt dissociated can be used suitably. Specific examples include Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among these, those capable of multidentate coordination are preferable, and Ag ions and Pd ions are particularly preferable in terms of the number of types of functional groups capable of coordination and catalytic ability.

  One preferred example of the electroless plating catalyst or a precursor thereof is a palladium compound. This palladium compound acts as a plating catalyst (palladium) or a precursor thereof (palladium ions), which acts as an active nucleus during the plating treatment and plays a role of depositing metal. The palladium compound is not particularly limited as long as it contains palladium and acts as a nucleus in the plating process, and examples thereof include a palladium (II) salt, a palladium (0) complex, and a palladium colloid.

Examples of the palladium salt include palladium acetate, palladium chloride, palladium nitrate, palladium bromide, palladium carbonate, palladium sulfate, bis (benzonitrile) dichloropalladium (II), bis (acetonitrile) dichloropalladium (II), bis ( Ethylenediamine) palladium (II) chloride and the like. Among these, palladium nitrate, palladium acetate, palladium sulfate, and bis (acetonitrile) dichloropalladium (II) are particularly preferable from the viewpoint of ease of handling and solubility.
Examples of the palladium complex include a tetrakistriphenylphosphine palladium complex and a tris (benzylideneacetone) dipalladium complex.
The palladium colloid is particles composed of palladium (0), and the size thereof is not particularly limited, but is preferably 5 nm to 300 nm, more preferably 10 nm to 100 nm, from the viewpoint of stability in the liquid. The palladium colloid may contain other metals as necessary, and examples of the other metals include tin. Examples of the palladium colloid include tin-palladium colloid. The palladium colloid may be synthesized by a known method or a commercially available product may be used. For example, a palladium colloid can be prepared by reducing palladium ions in a solution containing a charged surfactant or a charged protective agent.

Examples of the electroless plating catalyst or a precursor thereof include silver and silver ions, which are preferable from the viewpoint that they can be selectively adsorbed on the plating layer.
When silver ions are used as the plating catalyst precursor, those obtained by dissociating silver compounds as shown below can be suitably used. Specific examples of the silver compound include, for example, silver nitrate, silver acetate, silver sulfate, silver carbonate, silver cyanide, silver thiocyanate, silver chloride, silver bromide, silver chromate, silver chloranilate, silver salicylate, diethyldithiocarbamic acid. Examples thereof include silver, silver diethyldithiocarbamate, and silver p-toluenesulfonate. Among these, silver nitrate is particularly preferable from the viewpoint of water solubility.

  As a method of applying a metal that is an electroless plating catalyst or a metal salt that is an electroless plating precursor to a layer to be plated, a dispersion in which the metal is dispersed in an appropriate dispersion medium, or a metal salt that is an appropriate solvent. Prepare a solution containing dissolved and dissociated metal ions and apply the dispersion or solution on the layer to be plated, or immerse the substrate on which the layer to be plated is formed in the dispersion or solution. That's fine.

  Moreover, in the said exposure process, although the said composition for to-be-plated layer formation is made to contact on a board | substrate, you may use the method of adding an electroless-plating catalyst or its precursor in this composition. That is, a composition containing a specific polymer and an electroless plating catalyst or a precursor thereof (a composition for forming a layer to be plated of the present invention) is brought into contact with the substrate, and exposure and development are performed in a pattern. By this, the to-be-plated pattern (patterned to-be-plated layer) containing a plating catalyst or its precursor can be formed. In addition, if this method is used, a metal pattern can be formed without performing an etching process.

  When a resin film is used as the substrate and the plated layers are formed on both sides of the resin film, the electroless plating catalyst or its precursor is simultaneously brought into contact with the plated layers on both sides. Therefore, it is preferable to use the above immersion method.

By contacting the electroless plating catalyst or a precursor thereof, the interaction group in the layer to be plated is caused to interact by an intermolecular force such as van der Waals force or by coordinate bond by a lone electron pair. The electroless plating catalyst or its precursor can be adsorbed by utilizing the interaction.
From the viewpoint of sufficiently performing such adsorption, the metal concentration in the dispersion, solution, composition, or metal ion concentration in the solution is preferably 0.001% by mass to 50% by mass, and 0.005%. The mass% to 30 mass% is more preferable. Moreover, as contact time, 30 second-24 hours are preferable, and 1 minute-1 hour are more preferable.

When a palladium compound is used in the solution, dispersion, or composition containing the electroless plating catalyst or its precursor, the palladium compound is 0.001 mass relative to the total amount of the solution, dispersion, or composition. % To 10% by mass is preferable, 0.05% to 5% by mass is more preferable, and 0.10% to 1% by mass is still more preferable.
Moreover, when using a silver compound for the solution containing an electroless-plating catalyst precursor, 0.1 mass%-20 mass% are preferable with respect to the whole quantity of a solution, and 0.1 mass%-20 mass. % Is more preferable, and 0.5 mass% to 10 mass% is still more preferable.
Regardless of which compound is used, if the content is too small, it will be difficult to deposit the plating described later. If the content is too large, the plating may be deposited to an undesired region, or etching residue removal. Sexuality may be impaired.

The amount of adsorption of the plating catalyst of the layer to be plated or the precursor thereof depends on the type of the electroless plating catalyst or the precursor to be used. Therefore, 300 mg / m ² or more is preferable, 500 mg / m ² or more is more preferable, and 600 mg / m ² or more is more preferable. Further, from the viewpoint of producing a metal pattern having high adhesion to the substrate, the amount of silver ions adsorbed on the layer to be plated is preferably 1,000 mg / m ² or less.
In the case of palladium ions, the adsorption amount of the layer to be plated is preferably 5 mg / m ² or more, more preferably 10 mg / m ² or more, from the viewpoint of the depositability of electroless plating. Further, from the viewpoint of producing a metal pattern with high adhesion to the substrate, the amount of palladium ions adsorbed on the layer to be plated is preferably 1,000 mg / m ² or less.

-Other catalysts-
In the present invention, a zero-valent metal can be used as a catalyst used for direct electroplating on the layer to be plated without performing electroless plating in the plating step described later. Examples of the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, Co and the like. Among them, those capable of multidentate coordination are preferable, and in particular, an interactive group (cyano group / ether group). Pd, Ag, and Cu are preferable because of their high adsorptive (adhesive) property and catalytic ability.

-Organic solvent and water-
As described above, the plating catalyst or precursor is applied to the layer to be plated as a dispersion or solution (catalyst solution).
An organic solvent and water are used for the catalyst solution.
By containing this organic solvent, the permeability of the plating catalyst or precursor to the layer to be plated is improved, and the plating catalyst or precursor thereof can be efficiently adsorbed to the interactive group.

  Water may be used for the catalyst solution, and it is preferable that the water does not contain impurities. From such a viewpoint, RO water, deionized water, distilled water, purified water, and the like are used. It is preferable to use deionized water or distilled water.

  The organic solvent used for the preparation of the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the layer to be plated. Specifically, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate , Cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve and the like.

  Examples of other organic solvents include diacetone alcohol, γ-butyrolactone, methanol, ethanol, isopropyl alcohol, normal propyl alcohol, propylene glycol monomethyl ether, methyl cellosolve, ethyl cellosolve, ethylene glycol tertiary butyl ether, tetrahydrofuran, 1, 4-dioxane, n-methyl-2-pyrrolidone and the like.

  In particular, a water-soluble organic solvent is preferable from the viewpoint of compatibility with a plating catalyst or a precursor thereof, and permeability to a layer to be plated. Acetone, dimethyl carbonate, dimethyl cellosolve, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether is preferred.

  Furthermore, the catalyst solution may contain other additives depending on the purpose. Other additives include, for example, swelling agents (organic compounds such as ketones, aldehydes, ethers, esters, etc.), surfactants (anionic, cationic, zwitterionic, nonionic, low molecular or polymeric) Etc.).

  By passing through the catalyst provision process demonstrated above, interaction can be formed between the interactive group in a to-be-plated layer, and a plating catalyst or its precursor.

<Plating process>
The plating step is a step of plating a specific photosensitive material for plating formation to which the plating catalyst or its precursor is applied.
In the present invention, as described above, plating is performed at a plating bath ratio of less than 10.

Examples of the type of plating performed in the plating step include electroless plating, electroplating, etc., and in the plating step, depending on the function of the plating catalyst or its precursor that forms an interaction with the layer to be plated, You can choose.
That is, in the plating step, electroplating or electroless plating may be performed on the layer to be plated to which the plating catalyst or its precursor is applied.
Among these, it is preferable to perform electroless plating from the viewpoint of improving the formability and adhesion of the hybrid structure that appears in the layer to be plated. In order to obtain a plating layer having a desired film thickness, it is a more preferable aspect that electroplating is further performed after electroless plating.
Hereinafter, the plating suitably performed in the plating step will be described.

-Electroless plating-
The electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in the plating step is performed, for example, by immersing the substrate provided with the electroless plating catalyst in water and removing the excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
In addition, when the substrate to which the electroless plating catalyst precursor is applied is immersed in the electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the layer to be plated, the substrate is washed with water to remove excess. After removing the precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above.
In addition, the reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above. Is possible. The catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 mass% to 50%. % By mass is preferable, and 1% by mass to 30% by mass is more preferable. Examples of the reducing agent that can be used include boron-based reducing agents such as sodium borohydride and dimethylamine borane, and reducing agents such as formaldehyde and hypophosphorous acid.
When dipping, maintain the concentration of the electroless plating catalyst or its precursor in the vicinity of the surface of the layer to be plated with which the electroless plating catalyst or its precursor comes into contact, and soak with stirring or shaking. Is preferred.

  The composition of a general electroless plating bath includes (1) metal ions for plating, (2) reducing agents, and (3) additives (stabilizers) that improve the stability of metal ions, in addition to solvents. Mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.

  The organic solvent used in the plating bath needs to be a solvent that can be used in water, and in that respect, ketones such as acetone; alcohols such as methanol, ethanol, and isopropanol are listed.

  Examples of the metal used in the electroless plating bath include copper, tin, lead, nickel, gold, palladium, rhodium, etc. Among them, copper and gold are particularly preferable from the viewpoint of conductivity.

Moreover, the optimal reducing agent and additive are selected according to the said metal.
For example, a copper electroless plating bath contains CuSO ₄ as a copper salt, HCOH as a reducing agent, EDTA as a copper ion stabilizer, a chelating agent such as Rochelle salt, trialkanolamine, and the like. .
The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as complexing agents. It is included. Further, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

The thickness of the plating film formed by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. From the viewpoint, 0.1 μm or more is preferable, and 0.2 μm to 2 μm is more preferable.
However, in the case where electroplating described later is performed using a plating film formed by electroless plating as a conductive layer, it is sufficient that a film of at least 0.1 μm is uniformly applied.
The immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.

The plating layer obtained by the electroless plating obtained as described above has fine particles of a plating catalyst and a plating metal dispersed at a high density in the layer to be plated by cross-sectional observation using a scanning electron microscope (SEM). Further, it is confirmed that the plating metal is deposited on the layer to be plated. Since the interface between the layer to be plated and the plating layer is a hybrid state of the resin composite and fine particles, the interface between the layer to be plated (organic component) and the inorganic substance (plating catalyst metal or plating metal) is smooth (for example, 1 mm Adhesiveness is good even if Ra is 1.5 μm or less in the region ² .

-Electroplating-
In the plating step, when the plating catalyst or its precursor applied in the catalyst application step has a function as an electrode, electroplating is performed on the layer to be plated with the catalyst or the precursor. It can be carried out.
In addition, after the above-described electroless plating, the formed plating film may be used as an electrode, and electroplating may be further performed. As a result, a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate. Thus, since electroplating is performed after electroless plating, the metal film can be formed to a thickness according to the purpose, and therefore, the metal film of the present invention is suitable for various applications.

  As the electroplating method, a conventionally known method can be used. Examples of the metal used for electroplating in the plating step include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, Copper is more preferred.

Moreover, the film thickness of the metal film obtained by electroplating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
In addition, the film thickness of the metal film in the case where the obtained metal pattern material is applied to general electric wiring or the like is preferably 0.5 μm or more, more preferably 1 μm to 30 μm from the viewpoint of conductivity.
In addition, the thickness of the electrical wiring becomes thinner in order to maintain the aspect ratio as the line width of the electrical wiring becomes narrower, that is, as the size becomes finer. Therefore, the thickness of the plating layer formed by electroplating is not limited to the above, and can be set arbitrarily.

As another manufacturing method of the above-mentioned plating film, when forming a layer to be plated in the above-described exposure step, a plating catalyst or a precursor thereof is mixed in advance with the composition for forming a layer to be plated, and the above-described coating method Further, a method of laminating a layer to be plated on a substrate using an extrusion molding method or a laminating method is also mentioned.
In the case of this method, a plating layer containing a plating catalyst or a precursor thereof can be produced in one step without carrying out the above-described catalyst application step, which is preferable from the viewpoint of work efficiency and productivity.

<Metal pattern material>
The metal pattern material of this invention can be manufactured with the manufacturing method of the metal pattern material of this invention.
In the manufacturing method of the metal pattern material, if a resin film or the like is used as a substrate, a metal pattern material in which a metal pattern is formed on both surfaces of the resin film can be obtained.
The metal pattern material of this invention is excellent in the adhesive force of the metal pattern with respect to a board | substrate.

  The metal pattern material of the present invention preferably has a plating film locally provided on a substrate having a surface irregularity of 500 nm or less and 5 nm or more (more preferably 100 nm or less). The adhesion between the substrate and the metal pattern is preferably 10 or less out of 100 in the grid eye test, and particularly preferably 0. That is, it is characterized in that the substrate surface is smooth and the adhesion between the substrate and the metal pattern is excellent.

The unevenness of the substrate surface is a value measured by cutting the substrate perpendicular to the substrate surface and observing the cross section with an SEM.
More specifically, Rz measured in accordance with JIS B 0601, that is, “the difference between the average value of the Z data of the peak from the maximum to the fifth in the designated plane and the average value of the valley from the minimum to the fifth. ], 500 nm or less and 5 nm or more are preferable.

<Application>
The metal pattern material manufactured by the metal pattern material manufacturing method of the present invention is applied to various uses such as semiconductor chips, various electric wiring boards, FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, and the like. be able to.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
-Synthesis of polymer A-
In a 2 L three-necked flask, 1 L of ethyl acetate and 159 g of 2-aminoethanol were placed and cooled in an ice bath. Thereto, 150 g of 2-bromoisobutyric acid bromide was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed 4 times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.

Next, 47.4 g of the obtained raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath. Thereto, 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water and dried over magnesium sulfate, and the ethyl acetate was further distilled off. Thereafter, the following monomer M was purified by column chromatography to obtain 20 g.

Next, 8 g of N, N-dimethylacetamide was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream. 14.3 g of the monomer M obtained above, 3.0 g of acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.5 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and V-65 (Wako Pure Chemical Industries, Ltd.) 0.4 g N, N-dimethylacetamide 8 g solution was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred for 3 hours. Thereafter, 41 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. To the reaction solution, 0.09 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 54.8 g of diazabicycloundecene (DBU) were added and reacted at room temperature for 12 hours. Thereafter, 54 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 12 g of specific polymer A was obtained.
The obtained polymer A had a weight average molecular weight of 53,000.

Example 1
<Production of photosensitive material for plating formation>
A silicon wafer (manufactured by Electronics End Materials Corporation) having a diameter of 100 mm and a thickness of 0.5 mm was used as the substrate.

<Composition of adhesion auxiliary layer coating solution>
・ Acrylonitrile butadiene rubber (Product name: Nipol 101L, manufactured by Nippon Zeon Co., Ltd.): 5% by mass
・ Cyclopentanone: 95% by mass
The adhesion auxiliary layer coating solution having the above composition was spin-coated on the substrate at 1,500 rpm to form an adhesion auxiliary layer having a thickness of 1.8 μm. Thereafter, the obtained adhesion auxiliary layer was heat-treated at 150 ° C. for 1 hour.

<Composition of plating layer coating solution>
・ Polymerizable polymer A: 3.5% by mass
Photopolymerization initiator (Product name: Irgacure 819, manufactured by Ciba Japan Co., Ltd.) 0.7 mass% (light absorption 4.1%)
・ 1-methoxy-2-propanol (MFG): 86.5% by mass
・ Water: 9.3 mass%
The plating layer coating solution having the above composition was spin-coated on the adhesion auxiliary layer at a rotational speed of 750 rpm to form a plating layer having a thickness of 0.3 μm. Thereafter, it was naturally dried at room temperature. The photosensitive material for plating formation was produced by the above.

<Laser exposure>
About the produced photosensitive material for plating formation, using a laser processing apparatus (manufactured by Pulstec Industrial Co., Ltd., NEO1000), wavelength 405 nm, NA (numerical aperture) 0.85, linear velocity 0.6 m / s, focus gain No. 30, Airy disk diameter 0.58 μm, laser power 2 mW, pitch 2 μm.

<Development conditions>
The photosensitive material for plating formation after exposure was immersed in 1% by mass of sodium bicarbonate water for 15 minutes, then washed with water and allowed to dry naturally. Thereby, the photosensitive material for plating formation which has a pattern-like to-be-plated layer was obtained.

<Applying plating catalyst>
The photosensitive material for plating formation having a patterned layer to be plated was immersed in a 10% by mass aqueous silver nitrate solution for 10 minutes and then immersed in acetone for cleaning.

<Electroless plating>
Electroless plating was performed at 50 ° C. for 30 minutes using an electroless plating bath having the following composition on a photosensitive material for plating formation having a layer to be plated with a plating catalyst. The thickness of the obtained electroless copper plating film was 0.3 μm. The metal pattern material was produced by the above.
-Composition of electroless plating bath-
・ OPC Copper T (Okuno Pharmaceutical Co., Ltd.)
Plating bath ratio is 3
However, the plating bath ratio is a value obtained from the capacity V (cm ³ ) of the plating tank / the surface area A (cm ² ) of the object to be plated.

  Next, with respect to the obtained metal pattern material, the optimum power and the optimum power ratio, the evaluation of the drawing result, and the conductivity were evaluated as follows. The results are shown in Table 1.

<Optimum power and optimal power ratio>
This is the lowest power among the laser powers at which the evaluation of the drawing result is good (◯) when recording at 10 times the airy disk. In Example 1, the optimum power is 8 mW.
The optimum power ratio was obtained by (laser power / optimum power) × 100.

<Drawing result evaluation method>
About the produced metal pattern material, the optical microscope observation was performed in a 100-micrometer square field, and the drawing result was evaluated on the following reference | standard.
〔Evaluation criteria〕
○: Uniform wiring is obtained (good; see FIG. 2A)
Δ: Partially thin wiring (normal; see Figure 2B)
×: The wiring is not connected (defective; refer to FIG. 2C)

<Conductivity evaluation method>
The electrode was contacted at both ends with a contact probe, conductivity was confirmed with a tester, and the conductivity was evaluated according to the following criteria.
〔Evaluation criteria〕
○: When there is all conduction ×: When there is wiring with NG conduction

(Examples 2-4 and Comparative Examples 1-2)
In Example 1, except that the laser power was changed as shown in Table 1, metal pattern materials of Examples 2 to 4 and Comparative Examples 1 to 2 were produced in the same manner as Example 1.
About each obtained metal pattern material, it carried out similarly to Example 1, and evaluated the optimal power and the optimal power ratio, the evaluation of a drawing result, and electroconductivity. The results are shown in Table 1.

(Examples 5-8 and Comparative Examples 3-4)
In Example 1, the metal pattern materials of Examples 5 to 8 and Comparative Examples 3 to 4 were prepared in the same manner as Example 1 except that the pitch was changed to 4 μm and the laser power was changed as shown in Table 2. did.
About each obtained metal pattern material, it carried out similarly to Example 1, and evaluated the optimal power and the optimal power ratio, the evaluation of a drawing result, and electroconductivity. The results are shown in Table 2.

(Comparative Example 5)
In Example 1, when the content of the photopolymerization initiator (product name: Irgacure 819, manufactured by Ciba Japan Co., Ltd.) in the plating layer coating solution is 0.35% by mass (light absorption 2.0%) No patterning was possible under any conditions.

(Examples 9 to 11 and Comparative Example 6)
In Example 1, the content of the photopolymerization initiator (product name: Irgacure 819, manufactured by Ciba Japan Co., Ltd.) in the plating layer coating solution is 1.05% by mass (light absorption amount 6.2%), and the pitch Was changed to 4 μm, and the metal pattern materials of Examples 9 to 11 and Comparative Example 6 were produced in the same manner as in Example 1 except that the laser power was changed as shown in Table 3.
About each obtained metal pattern material, it carried out similarly to Example 1, and evaluated the optimal power and the optimal power ratio, the evaluation of a drawing result, and electroconductivity. The results are shown in Table 3. In Examples 9 to 11, the optimum power was 6 mW.

(Examples 12 and 13 and Comparative Example 7)
In Example 1, Examples 12 and 13 and Comparative Example were the same as Example 1 except that the capacity V (cm ³ ) of the plating tank was adjusted and the plating bath ratio was changed as shown in Table 4. 7 metal pattern materials were produced.
About each obtained metal pattern material, it carried out similarly to Example 1, and measured the optimal power, evaluation of the drawing result, and evaluation of electroconductivity. The results are shown in Table 4.

  The metal pattern material of the present invention manufactured by the method of manufacturing the metal pattern material of the present invention can be used in various applications such as semiconductor chips, various electric wiring boards, FPC, COF, TAB, antennas, multilayer wiring boards, motherboards, etc. Can be applied to.

Claims (5)

When exposing a photosensitive material for plating formation containing a copolymer containing units represented by the following formulas (A) to (C) at a pitch of less than 6 μm, the optimal power at the time of 6 μm pitch exposure is 100 And an exposure step of exposing with a laser power of [(pitch (μm) × 75/6 + 25) −30] to [(pitch (μm) × 75/6 + 25) +15]%,
A development step of developing the photosensitive material for plating formation after exposure with a developer;
A plating process in which the photosensitive material for plating formation on which the pattern after development is formed is plated at a plating bath ratio of less than 10, and
A method for producing a metal pattern material, comprising:
However, in said formula (A)-(C), R < ¹ > -R < ⁶ > represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group each independently, X, Y, Z , And U each independently represents a single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group, and L ¹ , L ² , and L ³ are each independently A single bond or a substituted or unsubstituted divalent organic group, W represents a non-dissociative functional group that interacts with the plating catalyst or its precursor, and V represents an ionic polar group .   The laser power is less than 100% of the optimum power at the time of 6 μm pitch exposure, and [(pitch (μm) × 75/6 + 25) −20]% to [(pitch (μm) × 75/6 + 25) +10]%. The manufacturing method of the metal pattern material of Claim 1 exposed by.   The method for producing a metal pattern material according to claim 1, wherein the plating bath ratio is 6 or less.   The method for producing a metal pattern material according to any one of claims 1 to 3, wherein the photosensitive material for forming a plating contains a photopolymerization initiator, and the photoabsorption amount of the photopolymerization initiator is 2.5% or more.   A metal pattern material produced by the method for producing a metal pattern material according to claim 1.