JP2013027837A - Method for manufacturing laminated body having metal film, ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminated body capable of making a metal film showing superior adhesion to a polycarbonate substrate, and having the metal film superior in productivity showing a superior discharge stability even when discharge of an ink composition is stopped and left for a fixed time, and the discharge is restarted thereafter.SOLUTION: The method for manufacturing a laminated body 18 having a metal film includes: an ink discharge step of discharging the ink composition containing at least a prescribed kind of monomer and a polymerization initiator on the polycarbonate substrate 10 by an ink jet method; a cured film forming step of forming a cured film 14 by curing the ink composition 12 discharged on the polycarbonate substrate by applying exposure processing or heat treatment; a catalyst imparting step of imparting a plating catalyst or a precursor thereof on the cured film; and a plating step of applying plating treatment to the cured film on which the plating catalyst or the precursor thereof is imparted, and forming the metal film 16 on the cured film.

Description

  The present invention relates to a method for producing a laminate having a metal film, and an ink composition used in the production method.

2. Description of the Related Art Conventionally, a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
As a method for producing such a metal pattern material, a “subtractive method” is mainly used. In this subtractive method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image. In this method, the metal film is etched to form a metal pattern, and finally the resist is removed.

  In the metal pattern obtained by this method, the adhesion between the substrate and the metal film is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, there is a problem that the high frequency characteristics when used as a metal wiring are deteriorated due to the unevenness of the obtained metal pattern at the substrate interface. In addition, in order to obtain a metal pattern with excellent adhesion between the metal film and the substrate, it is necessary to treat the substrate surface with a strong acid such as chromic acid in order to make the substrate surface uneven. There was a problem that a complicated process was required.

As a means for solving this problem, a patterned polymer layer is formed on a substrate by forming a graft polymer with high adhesion to the substrate, and plating is performed on the polymer layer, and a metal film is formed on the polymer layer. A method is known in which a metal pattern (conductive pattern) is obtained by manufacturing (Patent Document 1). According to this method, the adhesion between the substrate and the metal film can be improved without roughening the surface of the substrate.
In particular, in Patent Document 1, when a graft polymer directly bonded to the substrate surface is obtained, a liquid containing an unsaturated compound capable of radical polymerization is arranged in a pattern by an inkjet method.

Special table 2009-503806

2. Description of the Related Art In recent years, in response to increasing demands for reducing the cost of semiconductor devices and improving production efficiency, it has been desired to manufacture a laminate including a predetermined metal film or metal pattern with higher productivity. In particular, in the inkjet method, in order to achieve high productivity, after discharging the ink composition and leaving it for a certain period of time, it is possible to resume stable discharge without causing clogging of the nozzle (hereinafter referred to as recovery after storage). Also referred to as sex).
The inventors of the present invention have examined the recoverability after leaving using the ink composition specifically disclosed in Patent Document 1, and found that nozzle clogging frequently occurs.

On the other hand, attention has been focused on polycarbonate (hereinafter also referred to as PC as appropriate) as a substrate having metal wiring. Since PC has excellent heat resistance and formability, it can be said that it is useful as a substrate for supporting metal wiring.
When the present inventors made a metal film on a PC using a PC and the ink composition disclosed in Patent Document 1 as a substrate, the adhesion of the obtained metal film to the PC is not necessarily limited. It was not enough and further improvements were needed.

In view of the above circumstances, the present invention can produce a metal film exhibiting excellent adhesion to a polycarbonate substrate, stop discharging the ink composition and leave it for a certain time, and then restart discharging. It is an object of the present invention to provide a method for producing a laminate having a metal film with excellent productivity and excellent discharge stability.
Another object of the present invention is to provide an ink composition used in the method for producing the laminate.

As a result of intensive studies on the above problems, the present inventors have found that the metal film formed on the cured film because the adhesion between the polycarbonate substrate and the cured film (film to be plated) formed on the substrate is not sufficient. As a result, the present inventors have found that the adhesiveness of the resin becomes poor, and have completed the present invention based on the findings.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) an ink discharge step of discharging an ink composition containing at least a monomer component and a polymerization initiator onto a polycarbonate substrate by an inkjet method;
A cured film forming step of curing the ink composition ejected on the polycarbonate substrate by exposure treatment or heat treatment to form a cured film;
A catalyst application step of applying a plating catalyst or a precursor thereof to the cured film;
A method for producing a laminate including a metal film, comprising a plating step of performing a plating process on a cured film provided with a plating catalyst or a precursor thereof, and forming a metal film on the cured film,
The monomer component is represented by a first monomer having a cyano group, a second monomer having a plurality of polymerizable groups, and a general formula (A) described later, and the viscosity (25 ° C.) is 7.5 mPa · s or less. And containing at least a monofunctional third monomer,
The content of the monomer component is 85% by mass or more based on the total amount of the ink composition,
The manufacturing method of a laminated body provided with a metal film whose content of a 3rd monomer is 5-25 mass% with respect to the whole quantity of a monomer component.

(2) The manufacturing method of a laminated body provided with the metal film as described in (1) whose logP value is 0-2.6.
(3) A method for producing a laminate including the metal film according to (1) or (2), wherein the content of the third monomer is 7 to 17% by mass with respect to the total amount of the monomer components.
(4) The mass ratio (X / Y) of the mass (X) of the third monomer and the mass (Y) of the second monomer is 0.5 to 2.5, (1) to (3) The manufacturing method of a laminated body provided with the metal film in any one.
(5) The mass ratio (X / Z) of the mass (X) of the third monomer and the mass (Z) of the first monomer is 0.1 to 0.5, (1) to (4) The manufacturing method of a laminated body provided with the metal film in any one.

(6) The manufacturing method of a laminated body provided with the metal film in any one of (1)-(5) whose 1st monomer is a monofunctional monomer.
(7) Manufacturing method of laminated body provided with metal film in any one of (1)-(6) whose content of 2nd monomer is 1-20 mass% with respect to the whole quantity of a monomer component. .
(8) In any one of (1) to (7), the molar content of the polymerizable group of the second monomer is 0.4 to 2.0 mmol / g with respect to the total mass of the ink composition. The manufacturing method of a laminated body provided with the metal film of description.

(9) The polymerizable group of the second monomer is a group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinyloxy group, and an N-vinyl group, (1) to ( The manufacturing method of the laminated body which has a metal film in any one of 8).
(10) containing at least a monomer component and a polymerization initiator,
The monomer component is represented by the first monomer having a cyano group, the second monomer having a plurality of polymerizable groups, and the general formula (A), and the viscosity (25 ° C.) is 7.5 mPa · s or less. And at least a monofunctional third monomer,
The content of the monomer component is 85% by mass or more based on the total amount of the ink composition,
The content of the third monomer is 5 to 25% by mass with respect to the total amount of the monomer components, and the ink composition.

(11) The ink composition according to (10), wherein the log P value is 0 to 2.6.
(12) The mass ratio (X / Y) of the mass (X) of the third monomer and the mass (Y) of the second monomer is 0.5 to 2.5, (10) or (11) The ink composition as described.
(13) The mass ratio (X / Z) of the mass (X) of the third monomer and the mass (Z) of the first monomer is 0.1 to 0.5, (10) to (12) The ink composition according to any one of the above.

According to the present invention, it is possible to produce a metal film having excellent adhesion to a polycarbonate substrate, and it is excellent even when ejection of the ink composition is stopped and left for a certain period of time, and then ejection is resumed. It is possible to provide a method for manufacturing a laminate having a metal film that exhibits discharge stability and excellent productivity.
Moreover, according to this invention, the ink composition used with the manufacturing method of this laminated body can also be provided.

(A)-(D) are typical sectional drawings which show in order each manufacturing process in the manufacturing method of the laminated body which has a metal film of this invention, respectively.

Below, the manufacturing method of the laminated body which has a metal film of this invention is demonstrated.
First, the feature point compared with the prior art of this invention is explained in full detail.
A feature of the present invention is that a third monomer having a group exhibiting a predetermined log P and exhibiting a predetermined viscosity is used. As described above, in the prior art, the adhesion between a polycarbonate substrate (hereinafter also referred to as a PC substrate) and a cured film formed on the substrate was not sufficient. On the other hand, in the present invention, the third monomer contained in the ink composition used exhibits excellent permeability to the PC substrate. When the third monomer is cured while penetrating from the substrate surface to a predetermined depth, the formed cured film exhibits an excellent anchoring effect on the PC substrate, and as a result, the metal formed on the cured film. The adhesion of the film to the substrate is also improved.

The manufacturing method of the laminated body provided with the metal film of the present invention includes an ink discharging step of discharging a predetermined ink composition onto a PC substrate by an inkjet method, a cured film forming step of curing the discharged ink composition, and a curing A catalyst applying step for applying a plating catalyst or a precursor thereof to the film and a plating step for performing a plating treatment are provided.
Below, with reference to drawings, the material used at each process and the procedure of a process are demonstrated.

<Ink ejection process>
The ink discharge step is a step of discharging an ink composition containing at least a monomer component and a polymerization initiator onto a PC substrate by an inkjet method. More specifically, in this step, first, the PC board 10 shown in FIG. 1A is prepared, and then the ink is placed at a predetermined position on the PC board 10 as shown in FIG. 1B. The composition 12 is discharged.
First, materials (PC substrate, ink composition, etc.) used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.

[Polycarbonate substrate (PC substrate)]
As the polycarbonate substrate used in this step, a substrate formed from a known polycarbonate (a polymer having a carbonate group (—O— (C═O) —O—)) can be used.
The shape of the substrate is not particularly limited, and known shapes such as a flat plate shape and a lens shape can be applied. Further, a material obtained by molding polycarbonate into an arbitrary shape by injection molding or the like may be used as the PC substrate.

[Ink composition]
The ink composition used in this step contains at least a monomer component and a polymerization initiator. In the method for producing a laminate of the present invention, the ink composition is discharged onto a PC substrate and subjected to a curing process. Thereafter, the obtained cured film is subjected to a plating treatment to form a metal film on the cured film.
The monomer component contained in the ink composition includes a first monomer having a cyano group, a second monomer having a plurality of polymerizable groups, a general formula (A) described later, and a viscosity (25 ° C. ) Of 7.5 mPa · s or less, and a monofunctional third monomer.
Below, the detail of each component is demonstrated.

(Monomer component: first monomer)
The first monomer is a monomer having a cyano group. A cyano group in the monomer interacts with a plating catalyst or a precursor thereof described later, so that a metal film (plating film) having a sufficient thickness and sufficient adhesion can be obtained during the plating process.
The number of cyano groups (—CN group) in the monomer is not particularly limited, and a plurality of (for example, 2 to 3) cyano groups may be contained in the monomer. Especially, it is preferable that it is one piece at the point which can form a plating film stably in the case of a plating process.
The number of polymerizable groups in the monomer is not limited, but is preferably a monofunctional monomer having one polymerizable group from the viewpoint that the effects of the present invention are more excellent.

  The kind of the polymerizable group in the first monomer is not particularly limited, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Of these, a radical polymerizable group is preferable from the viewpoint of reactivity. Examples of the polymerizable group include an ethylenically unsaturated double bond group such as an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinyloxy group, or an N-vinyl group.

  A preferred embodiment of the first monomer includes a monomer having a cyano group represented by the following general formula (1). By using the monomer, a metal film (plating film) having a sufficient thickness can be obtained during the plating process.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, etc.).
L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, and a propylene group), a divalent aromatic hydrocarbon group ( preferably having 6 to 12 such as carbon, a phenylene group), - O -, - S -, - SO 2 -, - N (R) - (R:. alkyl), - CO -, - NH -, - COO -, -CONH-, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.) and the like.
In addition, -COO-La- group is preferable as L < ¹ > at the point which the effect of this invention is more excellent. La represents an alkylene group.

  Specific examples of the first monomer include acrylonitrile, cyanoethyl acrylate, cyanopropyl acrylate, and the like.

(Monomer component: second monomer)
The second monomer is a monomer having a plurality of polymerizable groups (polyfunctional monomer). By using the monomer, the film strength of the obtained cured film is improved, and as a result, the adhesion of the metal film is improved.
The definition of a polymeric group is synonymous with the polymeric group of the said 1st monomer, and its suitable aspect is also the same.
The number of polymerizable groups in the second monomer is 2 or more, preferably 2 to 8, and more preferably 2 to 4. If it is in the said range, the film | membrane intensity | strength of the cured film obtained will improve and the adhesiveness of a metal film will also improve.

As a suitable aspect of the second monomer, a second monomer having an alkylene oxide group (—La—O—) can be mentioned. La represents an alkylene group.
If it is this monomer, it is excellent in compatibility with another monomer and PC board, and as a result, the adhesiveness of a metal film also improves.

Specific examples of the second monomer include, for example, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonane. Diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythri Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, Dimethylol tricyclodecane di (meth) acrylate, modified glycerin tri (meth) acrylate, modified bisphenol A di (meth) acrylate, PO adduct di (meth) acrylate of bisphenol A, EO adduct di (meth) of bisphenol A Examples include acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Among these, an acyclic polyfunctional monomer having no cyclic structure is preferable.
Among these, polypropylene di (meth) acrylate-based and polyethylene glycol di (meth) acrylate-based polyfunctional monomers are preferable. Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and the like.

(Monomer component: third monomer)
The third monomer is a monofunctional monomer represented by the general formula (A) and having a viscosity (25 ° C.) of 7.5 mPa · s or less. The monomer exhibits excellent affinity for the PC substrate and exhibits excellent permeability. In other words, it can be used as a permeable monomer for a PC substrate. When the monomer penetrates into the PC substrate, the adhesion of the formed cured film to the PC substrate is improved, and as a result, the adhesion of the metal film is improved.
The third monomer is a monofunctional monomer and contains only one polymerizable group (such as a vinyl group, acryloyloxy group, methacryloyloxy group, acrylamide group, or methacrylamide group, which will be described later).
Note that the third monomer does not include a cyano group. That is, the first monomer is not included in the third monomer.

In the general formula (A), X represents an N-vinyl group (CH ₂ ═CH—), an acryloyloxy group (CH ₂ ═CHCOO—), a methacryloyloxy group (CH ₂ ═C (CH ₃ ) COO—), It represents an acrylamide group (CH ₂ ═CHCONH—) or a methacrylamide group (CH ₂ ═C (CH ₃ ) CONH—). Among these, an N-vinyl group, an acryloyloxy group, or a methacryloyloxy group is preferable from the viewpoint that the adhesion and leaving recovery properties of the metal film are more excellent.
N-vinyl group means a vinyl group bonded to a nitrogen atom.

Y represents an organic group having a log P of −0.2 to 2.7. Preferably it is 0-2.6, More preferably, it is 0.2-1.5. If it is in the said range, it is excellent in the adhesiveness of a metal film.
When log P is out of the above range, the adhesion of the metal film is inferior.
The structure of the organic group is not particularly limited as long as it is within the range of logP described above, and is composed of, for example, a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom, or a phosphorus atom. More specifically, for example, an alkyl group (linear, branched, or cyclic), an alkoxy group, an aryloxy group, an aralkyloxy group, a cycloalkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, List alkylthio groups, arylthio groups, acyl groups, acylamino groups, alkenyloxy groups, arylcarbonyloxy groups, alkylcarbonyloxy groups, alkylaminocarbonyl groups, alkylcarbonylamino groups, alkylsilyloxy groups, or combinations thereof. Can do. A plurality of these organic groups may be linked by a single bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a urea bond, or the like.

In addition, logP means the common logarithm of the distribution coefficient P (Partition Coefficient), and is an parameter | index showing the grade of distribution of the chemical substance between an octanol phase and a water phase.
The higher the value of logP, the higher the hydrophobicity of the chemical substance or organic group, and the lower the value of logP, the higher the hydrophilicity of the chemical substance or organic group. For example, a chemical substance having a log P value of 0 or less is more easily dissolved in the aqueous phase than the octanol phase, and a chemical substance having a log P value of 1 is less soluble in the octanol phase than the solubility in the aqueous phase. It can be said that it has 10 times the solubility.

The log P values of many compounds and organic groups have been reported, and many values are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., and can be referred to. When there is no measured log P value, it is most convenient to calculate with the program “CLOGP” available from Daylight CIS. This program outputs the value of “calculated logP (ClogP)” calculated by the fragment approach of Hansch and Leo together with the measured logP value, if any.
In the present invention, if there is an actual measured value of logP, the ClogP value calculated by the program attached to ChemDraw Pro Ver12.0 is used when there is no measured value.

The viscosity (25 ° C.) of the third monomer is 7.5 mPa · s or less, preferably 1 to 7.2 mPa · s, more preferably 3 to 7.1 mPa · s. If it is in the said range, the outstanding permeability with respect to the PC substrate of a 3rd monomer will be shown. As a result, the adhesion of the metal film is improved.
When the viscosity is out of the above range, the adhesion of the metal film is inferior.
The viscosity is a value measured at 25 ° C. by using a commonly used E-type viscometer (for example, an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.).

As the third monomer, a monomer having an absolute value of swelling degree determined by the following swelling degree measuring method of 10% or more is preferable, a monomer of 15% or more is more preferable, and a monomer of 17% or more is particularly preferable. preferable. When the degree of swelling of the third monomer is within the above range, the permeability of the third monomer to the PC substrate is better, and as a result, the adhesion of the metal film is better.
The upper limit of the absolute value of the degree of swelling is not particularly limited, but is preferably 80% or less, more preferably 75% or less, and more preferably 70% or less, from the viewpoint that the handleability of the monomer and the characteristics of the PC substrate are maintained. Further preferred is 60% or less.

As a method for measuring the degree of swelling of the monomer, first, a PC substrate (length: 2 cm, width: 2 cm, thickness: 0.5 mm) is immersed in a 10-fold mass ratio of the monomer solution at 25 ° C. for 1 hour. . After the immersion treatment, the degree of swelling (%) is obtained by the following formula for calculating the degree of swelling using the mass (W ₁ ) of the PC substrate taken out and the mass (W ₀ ) of the PC substrate before immersion.
Swelling degree (%) = [{mass of PC substrate plate after immersion (W ₁ ) −mass of PC substrate before immersion (W ₀ )} / mass of PC substrate before immersion (W ₀ )] × 100

  As a preferred embodiment of the third monomer, the molecular weight of Y in the general formula (A) is preferably 400 or less, preferably 300 or less, and preferably 200 or less. If it is the said range, the adhesiveness of the metal film obtained will be more excellent. The lower limit is not particularly limited, but it is often 50 or more in terms of monomer synthesis.

As another preferable embodiment of the third monomer, Y in the general formula (A) may have an —O—, —CO—, —N <, or an aliphatic hydrocarbon which may have a combination thereof. The aspect which is group, aromatic hydrocarbon group, or group which combined these is mentioned.
As an aliphatic hydrocarbon group, C1-C20 is preferable and C3-C10 is preferable from the point which the adhesiveness of the metal film obtained is more excellent. The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the aliphatic hydrocarbon group includes —O— (ether group), —CO— (carbonyl group), —N <(tertiary nitrogen atom), or a combination thereof (for example, —CO—N < ).
As an aromatic hydrocarbon group, C6-C20 is preferable and C7-C15 is preferable from the point which the adhesiveness of the metal film obtained is more excellent.
Examples of the group obtained by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group include a benzyl group.

As a further preferred embodiment of the third monomer, an aliphatic hydrocarbon group in which Y in the general formula (A) has a group of —O—, —CO—, —N <or a combination thereof can be mentioned. For example, an alkyl group or alkenyl group having an oxygen atom (for example, a cyclic ether group (glycidyl group, cyclohexene oxide group, oxetane group, etc.)), an alkylene group having an oxygen atom (for example, an alkylene oxide group) and the like can be mentioned. .
Among these groups, a linear aliphatic hydrocarbon group having —O— and a cyclic aliphatic hydrocarbon group having —CO—N <are mentioned because the adhesion of the resulting metal film is more excellent. It is done.

  Examples of the third monomer include benzyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, dimethylaminoethyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, and polytetrahydrofurfuryl acrylate. , N, N-dimethylacrylamide and the like.

(Monomer component: other monomer)
As the monomer component, a monomer other than the first to third monomers (hereinafter also referred to as a fourth monomer as appropriate) may be used as necessary.
The kind of the fourth monomer is not particularly limited as long as the effect of the present invention is not impaired. Examples thereof include phenoxyethyl acrylate.

  The molecular weight of the monomer component in the ink composition is not particularly limited, but is preferably less than 1500 in terms of better standing recovery properties. When a monomer having a molecular weight of 1500 or more is used, the content of the monomer in the ink composition is preferably 2.5% by mass or less from the standpoint of better standing recovery. Although a minimum in particular is not restrict | limited, 0 mass% is preferable.

(Monomer component content)
The content of the first monomer in the ink composition is not particularly limited, but is 20 to 75% by mass with respect to the total amount of the ink composition in that a sufficiently thick metal film (plating film) can be obtained. Is preferable, 25-65 mass% is more preferable, and 30-50 mass% is further more preferable.

  The content of the second monomer in the ink composition is not particularly limited, but is preferably 1 to 50% by mass, and preferably 4 to 25% by mass with respect to the total amount of the ink composition in that the strength of the metal film is more excellent. More preferred.

  The content of the third monomer in the ink composition is not particularly limited, but is preferably 5 to 24% by mass, and 7 to 17% by mass with respect to the total amount of the ink composition in that the strength of the metal film is more excellent. More preferred.

The content of the third monomer in the monomer component is 5 to 25% by mass with respect to the total amount of the monomer component (total amount of the monomer component), and 7 to 17 in that the adhesion of the metal film is more excellent. Mass% is preferred.
When the content of the third monomer is outside the above range, the adhesion of the metal film is inferior.

  The mass ratio (X / Y) of the mass (X) of the third monomer in the ink composition and the mass (Y) of the second monomer in the ink composition is that the adhesion of the metal film is more excellent. 0.5 to 2.5 is preferable, and 0.7 to 1.8 is more preferable.

  The mass ratio (X / Z) between the mass (X) of the third monomer in the ink composition and the mass (Z) of the first monomer in the ink composition is such that the adhesion of the metal film is more excellent. 0.1 to 0.5 is preferable, and 0.15 to 0.3 is more preferable.

The molar content of the polymerizable group of the second monomer is not particularly limited, but is preferably 0.4 to 2.0 mmol / g with respect to the total mass of the ink composition in terms of better adhesion of the metal film. 0.6 to 1.6 mmοl / g is more preferable, and 0.8 to 1.2 mmοl / g is particularly preferable.
The molar content of the polymerizable group is calculated by multiplying the number of moles of the second monomer contained in 1 g of the ink composition by the number of polymerizable groups contained in the structure of the second monomer. I can do it.

The content of the monomer component in the ink composition (total amount of monomers used) is 85% by mass or more, preferably 87% by mass or more, more preferably 90%, based on the total amount of the ink composition. There is more than mass%. The upper limit is not particularly limited, but 100% is the upper limit and is often about 95% by mass. When the content of the monomer component is in the above range, the storage stability is excellent.
When the content of the monomer component is out of the above range (less than 85% by mass), it is inferior in standing recovery.

(Polymerization initiator)
The ink composition contains a polymerization initiator. When the ink composition contains a polymerization initiator, curing proceeds sufficiently in a cured film forming step described later, and a cured film having sufficient film strength is obtained.
The polymerization initiator can be appropriately selected from known polymerization initiators (such as a thermal polymerization initiator or a photopolymerization initiator). The polymerization initiator is preferably a compound that generates a radical that is a polymerization initiating species by active energy rays, and examples of the active energy rays include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.

  As the polymerization initiator, known compounds can be used. Preferred polymerization initiators that can be used in the present invention include (a) aromatic ketones, (b) acylphosphine oxide compounds, and (c) aromatic onium salts. Compound, (d) organic peroxide, (e) thio compound, (f) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound , (K) an active ester compound, (l) a compound having a carbon halogen bond, or (m) an alkylamine compound. As the polymerization initiator, the above compounds (a) to (m) may be used alone or in combination.

Among these, in the present invention, it is preferable to use aromatic ketones and acylphosphine oxide compounds as polymerization initiators, such as 1-cyclohexyl phenyl ketone, p-phenylbenzophenone (manufactured by Wako Pure Chemical Industries, Ltd.), bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819: manufactured by Ciba Specialty Chemicals), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4 , 6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO: Ciba Japan, Lucirin TPO: BASF) is preferable.

  The total content of the polymerization initiator in the ink composition is not particularly limited, but from the viewpoints of handleability and curability of the ink composition, it is preferably 1 to 15% by mass, more preferably based on the total amount of the ink composition. Is 1 to 10% by mass, more preferably 1 to 5% by mass.

(Other components in the ink composition)
The ink composition may contain other components as long as the effects of the present invention are not impaired. Hereinafter, other components will be described.

  The ink composition may further contain an extremely small amount of water. In view of improving storage stability, the ink composition is preferably a non-aqueous ink composition that does not substantially contain water. Specifically, the water content is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less with respect to the total amount of the ink composition.

The ink composition may further contain a very small amount of a non-curable organic solvent for the purpose of adjusting the ink viscosity.
Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and cyclohexanone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, chloroform, and methylene chloride. Chlorine solvents such as benzene, aromatic solvents such as toluene, ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and propylene carbonate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ethylene glycol monomethyl ether, And glycol ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether.
The content of the organic solvent is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.1 to 3% by mass with respect to the entire ink composition.

The ink composition may further contain a surfactant. When a surfactant is included, it is preferable in terms of inkjet discharge stability and leveling properties upon landing.
As the surfactant, known surfactants can be used. For example, nonionic surfactants, amphoteric surfactants, anionic surfactants (for example, surfactants having ammonium ions as counterions), cationic interfaces An activator (for example, a surfactant having an organic acid anion as a counter ion) can be used.
Examples of nonionic surfactants include polyethylene glycol derivatives and polypropylene glycol derivatives. Examples of amphoteric surfactants include long-chain alkyl betaines. Examples of the anionic surfactant having an ammonium ion as a counter ion include, for example, a long-chain alkyl sulfate ammonium salt, an alkyl aryl sulfate ammonium salt, an alkyl aryl sulfonate ammonium salt, an alkyl phosphate ammonium salt, and an ammonium salt of a polycarboxylic acid polymer. Etc.

  Although content of surfactant in an ink composition is not specifically limited, 0-5 mass% is preferable with respect to the whole quantity of an ink composition, and 0.01-2 mass% is more preferable. Within the above range, a preferable surface tension can be obtained without impairing other physical properties of the ink.

  In addition to the above, the ink composition may contain a polymerization inhibitor, waxes, dyes, pigments, and the like, if necessary, as long as the effects of the present invention are not impaired.

[Procedure for ink ejection process]
The ink jet method ejects a liquid in picoliter order corresponding to a recording signal (digital data) from a liquid ejection hole toward a substrate, and a fine pattern can be formed by applying ink in a pattern.
The ink jet method used in this step is not particularly limited, a method in which a charged ink composition is continuously ejected and controlled by an electric field, a method in which ink jet ink is intermittently ejected using a piezoelectric element, and ink jet ink is heated. And various conventionally well-known methods, such as the method of injecting intermittently using the foaming, are employable. That is, drawing by the ink jet method may be performed by any conventionally known method such as a piezo ink jet method or a thermal ink jet method. In addition to a normal inkjet drawing apparatus, a drawing apparatus equipped with a heater or the like can be used.

  As an inkjet head to be used, various types of inkjet heads (ejection heads) such as a continuous type or an on-demand type piezo system, a thermal system, a solid system, and an electrostatic suction system can be used. Further, the ejection units (nozzles) of the inkjet head are not limited to a single row arrangement, and may be arranged in a plurality of rows or in a staggered pattern.

By the inkjet method, the ink composition is discharged to a place where a metal film on the PC substrate is to be formed. At this time, the ink composition may be applied to the entire surface of the PC substrate or may be applied in a desired pattern. That is, if it is applied to the entire surface of the PC substrate, a laminate (metal film material) having a metal film on the entire surface is obtained, and a desired pattern can be obtained by selectively applying the ink composition by discharging it in a pattern. A laminate having a metal film in the shape can be obtained.
In addition, after discharging an ink composition on a PC board | substrate, you may perform a drying process as needed. Such a drying process can be performed by lamp annealing in addition to a process using a hot plate, an electric furnace, or the like.

<Curing film formation process>
The cured film forming process is a process of forming a cured film by curing the ink composition ejected on the PC substrate by the ink ejecting process by an exposure process or a heating process. More specifically, as shown in FIG. 1C, the cured film 14 is formed on the PC substrate 10 by performing this step.
When energy application such as exposure or heat treatment is performed on the ink composition, a polymerization reaction of the monomer component occurs in a region where the ink composition is applied, and a cured film is formed. The formed cured film exhibits excellent adhesion to the PC substrate.
Below, the procedure of a cured film formation process is explained in full detail.

In the cured film forming step, either exposure processing or heat treatment may be performed, but exposure processing is preferable from the viewpoint of easy formation of a pattern image.
In the exposure treatment, irradiation with active energy rays (ultraviolet rays, γ rays, β rays, electron beams, visible rays, infrared rays, or the like) can be used. As the light source, for example, an ultraviolet irradiation lamp, a halogen lamp, a high-pressure mercury lamp, a laser, an LED, an electron beam irradiation device, or the like can be employed.
The wavelength of the active energy ray is preferably from 200 to 600 nm, more preferably from 300 to 450 nm, and even more preferably from 350 to 420 nm in that the reactivity of the monomer in the ink composition is more excellent.
The integrated irradiation dose of the active energy ray, in that the film strength of the cured film is excellent, preferably 5000 mJ / cm ² or less, more preferably 10~4000mJ / cm ^2, more preferably 20~3000mJ / cm ^2.

  In the case of heat treatment, an air dryer, an oven, an infrared dryer, a heating drum, or the like can be used. Although temperature conditions are not specifically limited, Usually, it is performed on the heating conditions for 5 to 120 minutes at 100-300 degreeC.

  Although the thickness of the cured film to be formed is not particularly limited, 0.1 to 10 μm is preferable and 0.3 to 5 μm is more preferable from the viewpoint of better adhesion with a metal film described later. The thickness of the cured film can be adjusted by appropriately setting the amount of the ink composition applied in the ink ejection process.

In addition, since the etching resistance of the formed cured film can be further improved, the cured film forming step is performed in an environment where the oxygen concentration is 10% or less, more preferably the oxygen concentration is 8% or less, and further preferably 5% or less. It is preferable to carry out with.
In order to control the oxygen concentration in the cured film forming step, for example, a nitrogen purge type UV irradiation apparatus (for example, CSN2-40 manufactured by GS Yuasa Co., Ltd.) is used. The oxygen concentration can be measured by an oxygen concentration meter such as Cosmo Protector XP-3180 (manufactured by Shin Cosmos Electric Co., Ltd.).

<Catalyst application step>
A catalyst provision process is a process of providing a plating catalyst or its precursor to the formed cured film after the said cured film formation process.
In this step, the cyano group in the cured film adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. That is, the cured film is used as a plating receptive layer (layer to be plated). The adsorbed plating catalyst or its precursor acts as a plating nucleus in the plating process described later.
First, materials (plating catalyst or its precursor etc.) used at this process are explained in full detail, and the procedure of this process is explained in full detail after that.

(Plating catalyst)
The plating catalyst or its precursor functions as a catalyst or electrode for plating treatment in the plating step described later. For this reason, the type of plating catalyst or precursor thereof used is appropriately determined depending on the type of plating.
In addition, it is preferable that the plating catalyst used in this process or its precursor is an electroless plating catalyst or its precursor. Especially, it is preferable that a plating catalyst or its precursor is a compound containing Pd, Ag, or Cu from the point of a reduction potential.
Hereinafter, mainly electroless plating or a precursor thereof will be described in detail.

As the electroless plating catalyst, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal having a catalytic ability for autocatalytic reduction reaction (which tends to be more ionized than Ni). And those known as metals capable of low electroless plating). More specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, etc. are mentioned. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
As the electroless plating catalyst, metal colloid (metal particles) may be used. Generally, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent.

  Any electroless plating catalyst precursor can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the metals mentioned as the electroless plating catalyst are mainly 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 cured film and before being immersed in the electroless plating solution by changing it to a zero-valent metal by a reduction reaction. The electroplating catalyst precursor may be immersed in an electroless plating solution and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating solution.

The metal ion that is the electroless plating catalyst precursor is preferably applied to the cured film using a metal salt. The metal salt 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 said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. In view of the number of types of groups and catalytic ability, Ag ions and Pd ions are preferred.

  In this step, zero-valent metals other than those described above can also be used as a catalyst used for direct electroplating without electroless plating.

The plating catalyst or a precursor thereof is preferably used in the form of a dispersion or solution in which these are dispersed or dissolved in a solvent (hereinafter also referred to as a plating catalyst solution as appropriate). That is, the plating catalyst solution contains a plating catalyst or a precursor thereof.
The plating catalyst solution usually contains a solvent, and an organic solvent and / or water is used as the type of solvent. Usually, water is used as the main component. When the plating catalyst solution contains an organic solvent, the permeability of the plating catalyst solution to the cured film is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the cyano group.

  The organic solvent used in the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the cured film. 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 can be used.

  The content of the plating catalyst or its precursor in the plating catalyst liquid is not particularly limited, but is 0.001 to 50 with respect to the total amount of the plating catalyst liquid in that it is easy to control the adhesion amount of the plating catalyst or its precursor. % By mass is preferable, and 0.005 to 30% by mass is more preferable.

(Procedure for applying catalyst)
The method for applying the plating catalyst or its precursor to the cured film is not particularly limited.
For example, the above plating catalyst solution (a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing metal ions dissolved in an appropriate solvent and dissociated metal ions) is prepared, and the plating catalyst solution is applied to the cured film. And a method of immersing a PC substrate on which a cured film is formed in a plating catalyst solution.
The contact time between the cured film and the plating catalyst solution is preferably about 30 seconds to 10 minutes, and more preferably about 3 minutes to 5 minutes.
The temperature of the plating catalyst solution at the time of contact is preferably about 20 to 60 ° C, more preferably about 30 to 50 ° C.

<Plating process>
The plating step is a step of forming a metal film on the cured film by performing a plating process on the cured film to which the plating catalyst or its precursor has been applied in the catalyst application step. More specifically, as shown in FIG. 1D, by performing this step, a metal film 16 is formed on the cured film 14, and a laminate 18 having the metal film is obtained.

Examples of the type of plating treatment performed in this step include electroless plating and electrolytic plating. In the above step, the plating treatment can be selected depending on the function of the plating catalyst applied to the cured film or its precursor.
Especially, it is preferable to perform electroless plating from the point of the adhesive improvement of a metal film. In addition, in order to obtain a metal film having a desired layer thickness, it is a more preferable aspect that electrolytic plating is further performed after electroless plating.
Hereinafter, the plating process suitably performed in this process will be described.

(Electroless plating)
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 this step is performed by, for example, washing the cured film provided with the electroless plating catalyst with water to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. As the electroless plating bath used, a known electroless plating bath can be used. In addition, as an electroless-plating bath, the case where an alkaline electroless-plating bath (pH is preferable about 9-14) is preferable from the point of availability.
In addition, when the cured film provided with the electroless plating catalyst precursor is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the insulating layer, the cured film is washed with water to remove the excess. After removing a 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 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 to 50% by mass. Preferably, 1-30 mass% is more preferable. As the reducing agent, known reducing agents (for example, boron-based reducing agents such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphorous acid, etc.) can be used.
When dipping, the concentration of the electroless plating catalyst or its precursor in the vicinity of the surface of the cured film with which the electroless plating catalyst or its precursor comes in contact may be immersed while stirring or shaking. preferable.

  As a composition of a general electroless plating bath, for example, in addition to a solvent (for example, water), 1. metal ions for plating; 2. reducing agent; An additive (stabilizer) for improving the stability of metal ions may be contained. 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 this respect, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.

  As the types of metals used in the electroless plating bath, for example, copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known. Among them, copper and gold are particularly preferable from the viewpoint of conductivity. preferable. Moreover, the optimal reducing agent and additive are selected according to the said metal.

The film thickness of the metal film obtained 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, but from the viewpoint of conductivity, it is 0. .1 μm or more is preferable, and 0.2 to 2 μm is more preferable.
However, when performing electroplating to be described later using a metal film formed by electroless plating as a conductive film, it is preferable that a film of at least 0.1 μm or more is uniformly applied.
Further, the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.

(Electrolytic plating (electroplating))
In this step, when the plating catalyst applied in the above step or a precursor thereof has a function as an electrode, electrolytic plating can be performed on the cured film provided with the catalyst or the precursor. .
Further, after the above-described electroless plating, the formed metal film may be used as an electrode, and further electrolytic plating may be performed. Thereby, a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the PC substrate. As described above, by performing electroplating after electroless plating, the metal film can be formed to a thickness according to the purpose, which is suitable for applying the metal film to various applications.

  As a method of electrolytic plating, a conventionally known method can be used. In addition, as a metal used for electrolytic plating, copper, chromium, lead, nickel, gold | metal | money, silver, tin, zinc etc. are mentioned, Copper, gold | metal | money, silver is preferable from a conductive viewpoint, and copper is more preferable.

Moreover, the film thickness of the metal film obtained by electrolytic plating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
In addition, when applying to general electric wiring etc., it is preferable that the layer thickness of a metal film is 0.5 micrometer or more from a viewpoint of electroconductivity, and 1-30 micrometers is more preferable.

<Laminated body with metal film (metal film material)>
By passing through the process mentioned above, the laminated body (metal film material) which has a metal film on the surface can be obtained. The laminate can be applied to various uses such as an electric wiring board (for example, a printed wiring board), an electromagnetic wave prevention film, a coating film, a two-layer CCL (Copper Clad Laminate) material, and a decoration material.
If the ink composition is selectively applied by discharging the ink composition in a desired pattern in the ink application process, a laminate (metal pattern material) having a patterned metal film is immediately obtained through the plating process. Can be obtained.

  On the other hand, the ink composition may be applied to the entire surface of the PC substrate to form a laminate having a metal film on the entire surface of the substrate, and a separate etching process may be provided to form the metal film in a desired pattern. Good. This etching process will be described in detail below.

(Etching process)
This step is a step of etching the metal film (plating film) formed in the plating treatment step into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the metal film formed on the PC substrate surface by etching.
Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.

With the subtractive method, a dry film resist layer is provided on the formed metal film, the same pattern as the metal pattern part is formed by pattern exposure and development, the metal film is removed with an etching solution using the dry film resist pattern as a mask, This is a method of forming a metal pattern.
Any material can be used as the dry film resist, and negative, positive, liquid, and film-like ones can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.

The semi-additive method is to provide a dry film resist layer on the formed metal film, form the same pattern as the non-metal pattern by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask. In this method, quick etching is performed after the dry film resist pattern is removed, and the metal film is removed in a pattern to form a metal pattern. The dry film resist, the etching solution, etc. can use the same material as the subtractive method. Moreover, the above-mentioned method can be used as the electroplating method.
Through the above etching process, a laminate having a desired patterned metal film can be formed.

  When the laminate according to the present invention is configured as a multilayer wiring board, an insulating resin layer (interlayer insulating film) may be further laminated on the surface of the metal film, and further wiring (metal pattern) may be formed on the surface. Alternatively, a solder resist may be formed on the surface of the metal film.

As the interlayer insulating film, a known interlayer insulating film can be used. For example, epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin, polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyphenylene sulfide resin Examples include ether ether ketone resins and liquid crystal resins.
Among these, it is preferable to contain an epoxy resin, a polyimide resin, or a liquid crystal resin from the viewpoints of adhesion to the above-described cured film, dimensional stability, heat resistance, electrical insulation, and the like.

  As a solder resist used for wiring protection on the surface of the metal film, a known material can be used, and is described in detail in, for example, Japanese Patent Application Laid-Open Nos. 10-204150 and 2003-222993. A commercially available solder resist may be used, and specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. Unless otherwise specified, “%” and “part” are based on mass.

(Synthesis Example 1: Synthesis of cyanopropyl acrylate)
In a 200 ml three-necked flask, dimethyl sulfoxide (33 g), water (33 g), potassium bicarbonate (14.8 g), 4-bromobutyronitrile (10 g), and 4-hydroxy TEMPO (4-hydroxy-2,2, 6,6-tetramethylpiperidine-1-oxyl free radical) (10 mg) was added. Thereafter, 9.8 g of acrylic acid was added dropwise. Then, it heated to 80 degreeC and stirred for 4 hours, Then, the reaction solution was cooled to room temperature. The reaction solution was washed with water and purified by column chromatography to obtain 3-cyanopropyl acrylate (9 g).

(Synthesis Example 2: Synthesis of Polymer P)
18 g of polyacrylic acid (average molecular weight 25,000) is dissolved in 300 g of DMAc (dimethylacetamide), and 0.41 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate are added thereto. , Reacted at 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. Polymer P having neutralized carboxyl group with 1 mol / l sodium hydroxide aqueous solution, precipitating polymer in addition to ethyl acetate, washing well, polymer having at least one hydrophilic group and at least one radical polymerizable unsaturated group Got.

<Manufacture of ink composition>
Each ink composition was prepared according to the composition ratio shown in Table 1 below. In Table 1,% represents mass%. Details of each material used for ink preparation are shown below.

(First monomer)
・ Cyanoethyl acrylate (2-Cyanoethyl Acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.)

(Second monomer)
・ Dipropylene glycol diacrylate (bifunctional) (SR508, manufactured by SARTOMER)
・ Diethylene glycol diacrylate (bifunctional) (SR230, manufactured by SARTOMER)
Pentaerythritol tetraacrylate (tetrafunctional) (V # 400, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(Third monomer)
2- (2-ethoxyethoxy) ethyl acrylate (EOEOEA) (manufactured by Sigma-Aldrich) (log P: 0.64, viscosity: 3.3 mPa · s, swelling degree: 67.6)
Tetrahydrofurfuryl acrylate (THFA) (SR285, manufactured by Nippon Kayaku Co., Ltd.) (log P: 0.72, viscosity: 4.1 mPa · s, swelling degree: 49.8)
Dimethylaminoethyl acrylate (DMAEA) (manufactured by Kojin Co., Ltd.) (log P: 0.58, viscosity: 1.5 mPa · s, swelling degree: 65.9)
N, N-dimethylacrylamide (DMAA) (manufactured by Kojin Co., Ltd.) (log P: -0.13, viscosity: 1.6 mPa · s, degree of swelling: 32.7)
N-vinyl-ε-caprolactam (NVC) (manufactured by Tokyo Chemical Industry Co., Ltd.) (log P: 1.33, viscosity: 7.1 mPa · s, degree of swelling: −17.2)
Benzyl acrylate (FA-BZA) (manufactured by Hitachi Chemical Co., Ltd.) (log P: 2.52, viscosity: 3.9 mPa · s, swelling degree: 74.5)

(Other monofunctional monomer (fourth monomer))
Phenoxyethyl acrylate (SR339, manufactured by SARTOMER) (log P: 2.3, viscosity: 12.7 mPa · s, degree of swelling: −9.2)
Isobornyl acrylate (IBOA) (manufactured by Tokyo Chemical Industry Co., Ltd.) (log P: 3.5, viscosity: 9.2 mPa · s, swelling degree: 0.1)
Γ-butyrolactone acrylate (GBLA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (log P: −0.47, viscosity: 29.0 mPa · s, swelling degree: −0.3)
Isodecyl acrylate (IDA) (manufactured by BASF) (log P: 3.7, viscosity: 6.2 mPa · s, swelling degree: 0.2)

The swelling degree of each monomer was measured by the following method.
First, a PC substrate (length: 2 cm, width: 2 cm, thickness: 0.5 mm) was immersed in each monomer solution having a mass ratio of 10 times at 25 ° C. for 1 hour. After the immersion treatment, the degree of swelling (%) was determined by the following formula for calculating the degree of swelling using the mass (W ₁ ) of the PC substrate taken out and the mass (W ₀ ) of the PC substrate before immersion.
Swelling degree (%) = [{mass of PC substrate after immersion (W ₁ ) −mass of PC substrate before immersion (W ₀ )} / mass of PC substrate before immersion (W ₀ )] × 100

(Polymerization initiator)
1-hydroxy-cyclohexyl phenyl ketone (IRGACURE 184, manufactured by BASF)
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) (Lucirin TPO, manufactured by BASF)

(Surfactant)
・ Silicone surfactant (BYK-307, manufactured by BYK Chemie)
・ Silicone surfactant (BYK-323, manufactured by BYK Chemie)
-Fluorosurfactant (F-781F, manufactured by DIC Corporation)

(solvent)
・ Cyclohexane (Sumitomo Chemical Co., Ltd.)
・ Acetone (manufactured by Sankyo Chemical Co., Ltd.)
-Acetonitrile (manufactured by Asahi Kasei Chemicals Corporation)
・ Propylene carbonate (Maruzen Petrochemical Co., Ltd.)

<Evaluation: Restoration recoverability (ejection stability when the ejection of the ink composition is stopped on the inkjet recording apparatus and left for a certain period of time, and then ejection is resumed)>
Using the ink composition prepared above, the standing recovery property was evaluated according to the following method.
Using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatix, each ink composition was ejected at a frequency of 4 kHz using 10 nozzles, ejection properties were confirmed, ejection was stopped, and the mixture was allowed to stand for 60 minutes. Thereafter, pressure purging and head cleaning were performed, and discharging was performed again under the same conditions, and the stand-by recovery property was evaluated.
“A” indicates that ejection is normal with all 10 nozzles, “B” indicates that no ejection or flight bending occurs in 1 to 2 nozzles, and ejection failure or flight bending occurs in 3 to 5 nozzles. The case where the discharge was not ejected or the flight curve occurred at 6 nozzles or more, or the case where the ejection start itself was impossible with all the nozzles was evaluated as “D”. The results are shown in Table 1.

<Manufacture of laminate (Pattern 1)>
(Ink ejection process and cured film formation process)
A cured film was produced according to the following method using the ink composition prepared above.
Using a Fujifilm Dimatix inkjet printer DMP-2831 on a PC substrate (PC-1151, manufactured by Teijin Chemicals Ltd., length: 10 cm, width: 10 cm, thickness: 0.5 mm), a line width of 100 μm, A straight line pattern having a length of 5 cm was drawn and an exposure process was performed to form a cured film (thickness: 0.8 μm) composed of a line pattern.
In the exposure step, a metal halide light source exposure machine: U-0272 (manufactured by GS Yuasa Co., Ltd.) was used for exposure with a total light amount of 2000 mJ / cm ^{2 over} the entire emission wavelength.

(Catalyst application process)
In a mixed solution of water: acetone = 80: 20 (mass ratio), 0.5% by mass of palladium nitrate is dissolved with respect to the total amount of the solution, and undissolved material is removed with a filter paper. A PC substrate (to-be-plated body) having a cured film was immersed for 15 minutes.
Thereafter, the PC substrate having the line-shaped cured film was immersed and washed in a mixed solution of water: acetone = 80: 20 (mass ratio) for 15 minutes.

(Plating process (electroless plating process))
Next, an electroless plating bath having the following composition was prepared using Sulcup PGT (A solution, B solution, C solution) which is a plating bath manufactured by Uemura Kogyo Co., Ltd.
Thereafter, the temperature of the electroless plating bath is adjusted to 30 ° C., the pH is adjusted to 13.0 with sodium hydroxide and sulfuric acid, and the electroless plating is applied to a PC substrate having a cured film provided with a plating catalyst. Went. The immersion time in the plating bath was 60 minutes, whereby a line-shaped metal film having a film thickness of 3 μm was obtained.

(Composition of electroless plating bath)
-Distilled water: 79.2% by mass
-PGT-A liquid: 9.0 mass%
-PGT-B liquid: 6.0 mass%
-PGT-C liquid: 3.5 mass%
Formaldehyde (Wako Pure Chemical Industries, Ltd.): 2.3% by mass

  When the obtained metal film was visually observed, a uniform film was formed, and a good line-shaped metal film was obtained.

<Manufacture of laminate (Pattern 2)>
Under the same conditions as pattern 1 above, a solid pattern was drawn in a 50 mm × 50 mm square using a Fujifilm Dimatix inkjet printer DMP-2831, and an exposure process was performed.
Moreover, the catalyst provision process mentioned above and the electroless-plating process were implemented after that. Further, after the electroless plating treatment, the following electrolytic plating treatment was performed to obtain a solid metal film (film thickness: 10 μm).

(Electrolytic plating process)
Electroless plating was performed for 15 minutes under the condition of 3 A / dm ² using an electroless copper plating film formed by electroless plating treatment as a power feeding layer and using an electrolytic copper plating bath having the following composition.

(Composition of electrolytic plating bath)
-Copper sulfate (Wako Pure Chemical Industries, Ltd.) 38g
・ 95 g of sulfuric acid (Wako Pure Chemical Industries, Ltd.)
-Hydrochloric acid (Wako Pure Chemical Industries, Ltd.) 1mL
・ Copper Greeme PCM (Meltex) 3mL
・ Water 500g

<Evaluation: Metal film adhesion>
Adhesion evaluation was performed using the metal film after the electrolytic plating obtained in the production of the laminate (pattern 2). Using a cross-cut guide, a cutter knife was applied so that the cutter knife was perpendicular to the metal film, and 6 vertical and 6 horizontal grid cuts were made at 1 mm intervals. Thereafter, the adhesive surface of the transparent adhesive tape was pressure-bonded to the cut surface so that no bubbles remained with finger pressure of 50 mm or more. After 10 seconds, the tape was quickly peeled off in the direction perpendicular to the metal film surface, and the state of the peeled metal film surface was observed and evaluated according to the following criteria.
“AA”: The cut edge is smooth, and no peeling is observed in any lattice eye.
“A”: The edge of the cut is smooth, and the small peeling of the coating film at the intersection of the cut is less than 5% of the lattice plane.
“B”: peeling of the film is observed along the cut surface, but the peeling is 5% or more and less than 15% of the lattice surface.
"C": Film peeling occurs overall, and peeling is seen at 15% or more.

“-” In Table 1 means that the evaluation has not been performed.
In Table 1,% represents mass%. A blank represents no addition. In addition, from the first monomer to the solvent column represents mass% of each component in the ink composition.

As shown in Table 1 above, in the production method of the present invention, the metal film in the obtained laminate exhibited excellent adhesion and was also excellent in storage recovery.
In particular, as can be seen by comparing the case where the ink 13 and the ink 14 are used with the case where the other ink is used, the content of the third monomer with respect to the total amount of the monomer components is in the range of 7 to 17% by mass. In this case, it was confirmed that the adhesion of the metal film was more excellent. Further, as can be seen by comparing the case of ink 17 with the case of using another ink, when the third monomer having a log P in the range of 0 to 2.6 is used, the adhesion of the resulting metal film It was confirmed that it was excellent in performance.

On the other hand, as shown in Table 1, as shown in Comparative Inks 1 to 3, when the content of the monomer component in the ink composition is not within the predetermined range, it is confirmed that the standing recovery property and the adhesion of the metal film are inferior. It was done.
Further, as shown in comparative inks 4 and 5, it was confirmed that the adhesion of the metal film was inferior when the content of the third ink was not within the predetermined range.
In addition, as shown in comparative inks 6 to 9, it is confirmed that the adhesion of the metal film is inferior when the viscosity of the third monomer or the monomer whose Y logP in the formula is not within the predetermined range is used. It was done.
In addition, as shown in Comparative Ink 9, it was confirmed that when the ink composition specifically shown in paragraph [0095] of Patent Document 1 was used, it was poor in storage stability.

10: Polycarbonate substrate (PC substrate)
12: Ink composition 14: Cured film 16: Metal film 18: Laminate having metal film

Claims (13)

An ink discharge step of discharging an ink composition containing at least a monomer component and a polymerization initiator onto a polycarbonate substrate by an inkjet method;
A cured film forming step of curing the ink composition ejected on the polycarbonate substrate by exposure treatment or heat treatment to form a cured film;
A catalyst application step of applying a plating catalyst or a precursor thereof to the cured film;
A method for producing a laminate including a metal film, comprising a plating step of performing a plating process on the cured film to which the plating catalyst or a precursor thereof is applied, and forming a metal film on the cured film,
The monomer component is represented by the first monomer having a cyano group, the second monomer having a plurality of polymerizable groups, and the general formula (A), and the viscosity (25 ° C.) is 7.5 mPa · s or less. Including at least a monofunctional third monomer;
The content of the monomer component is 85% by mass or more based on the total amount of the ink composition,
The manufacturing method of a laminated body provided with a metal film whose content of a said 3rd monomer is 5-25 mass% with respect to the whole quantity of the said monomer component.
(In the general formula (A), X represents an N-vinyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, or a methacrylamide group. Y has a log P of -0.2 to 2.7. Represents an organic group.)   The manufacturing method of a laminated body provided with the metal film of Claim 1 whose said logP value is 0-2.6.   The manufacturing method of a laminated body provided with the metal film of Claim 1 or 2 whose content of a said 3rd monomer is 7-17 mass% with respect to the whole quantity of the said monomer component.   The mass ratio (X / Y) of the mass (X) of the third monomer and the mass (Y) of the second monomer is 0.5 to 2.5. The manufacturing method of a laminated body provided with the metal film of description.   The mass ratio (X / Z) of the mass (X) of the third monomer and the mass (Z) of the first monomer is 0.1 to 0.5. The manufacturing method of a laminated body provided with the metal film of description.   The manufacturing method of a laminated body provided with the metal film in any one of Claims 1-5 whose said 1st monomer is a monofunctional monomer.   The manufacturing method of a laminated body provided with the metal film in any one of Claims 1-6 whose content of a said 2nd monomer is 1-20 mass% with respect to the whole quantity of the said monomer component.   The metal according to claim 1, wherein the molar content of the polymerizable group of the second monomer is 0.4 to 2.0 mmol / g with respect to the total mass of the ink composition. The manufacturing method of a laminated body provided with a film | membrane.   The polymerizable group of the second monomer is a group selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a vinyloxy group, and an N-vinyl group. A method for producing a laminate having the metal film according to claim 1. Containing at least a monomer component and a polymerization initiator,
The monomer component is represented by the first monomer having a cyano group, the second monomer having a plurality of polymerizable groups, and the general formula (A), and the viscosity (25 ° C.) is 7.5 mPa · s or less. Including at least a monofunctional third monomer;
The content of the monomer component is 85% by mass or more based on the total amount of the ink composition,
The ink composition has a content of the third monomer of 5 to 25% by mass with respect to the total amount of the monomer components.
(In the general formula (A), X represents an N-vinyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, or a methacrylamide group. Y has a log P of -0.2 to 2.7. Represents an organic group.)   The ink composition according to claim 10, wherein the log P value is 0 to 2.6.   The ink according to claim 10 or 11, wherein a mass ratio (X / Y) of a mass (X) of the third monomer and a mass (Y) of the second monomer is 0.5 to 2.5. Composition.   The mass ratio (X / Z) of the mass (X) of the third monomer and the mass (Z) of the first monomer is 0.1 to 0.5. The ink composition as described.