JP6799267B2 - Method of forming laminated wiring - Google Patents

Description

The present invention relates to a method for forming laminated wiring.

The photolithography method is widely used for forming wirings, electrodes, and the like used in semiconductor elements, electronic circuits, and the like. However, the photolithography method requires expensive equipment and the process is complicated, so that the manufacturing cost is high. On the other hand, as a technique for forming wiring and the like at low cost, printed electronics that directly print wiring is attracting attention.

Each printing method such as inkjet printing, screen printing, and gravure printing used in printed electronics is considered to be a simple and low-cost method because a desired pattern of wiring can be formed directly on a substrate. However, in the formation of wiring by the printing method, as a result of the ink material used flowing, these wet spreads and bleeding occur, so that there is a limit in forming a fine wiring pattern. Further, in the conventional general printing method, it is not possible to form the laminated wiring in which the wirings of the layer structure are connected by vias.

Under these circumstances, a method of forming laminated wiring by a printing method using a material whose surface energy changes by applying energy has been proposed (see JP-A-2015-15378). In this method, laminated wiring is formed by the following steps. First, a wettability changing layer is formed on a substrate on which the first wiring is formed on the surface by a material whose surface energy changes by applying energy. This wettability changing layer serves as an insulating film between the layers. Next, a region having high wettability is formed by irradiating a part of the surface of the wettability changing layer with a laser. This highly wettable region serves as a wiring pattern. Next, a hole for via is formed by further irradiating a part of the formed highly wettable region with a laser. After that, by applying the conductive ink on the highly wettable region, it is said that the second wiring and the via can be formed at the same time.

However, the above method is to irradiate a high-energy laser to form a highly wettable region which is a wiring pattern, and it cannot be said that the efficiency is good. When a laser is used, for example, as the wiring pattern becomes complicated, the scanning path becomes complicated and the working time becomes long. Further, as a specific material whose surface energy changes by applying energy in the above method, a polymer containing polyimide in the main chain and having a side chain capable of generating a hydrophilic group by irradiation with ultraviolet rays is used. Only.

JP-A-2015-15378

The present invention has been made based on the above circumstances, and an object of the present invention is to provide a method for forming a laminated wiring capable of efficiently forming a laminated wiring.

The invention made to solve the above problems is a step of preparing a base material having a first conductive layer as the outermost layer, and an insulation having a liquid-repellent surface region and a liquid-based surface region on the surface of the base material. A step of forming a film and a step of forming a second conductive layer to be laminated on a liquid-based surface region of the insulating film by contacting a material for forming a second conductive layer with the surface of the insulating film are provided. The step of forming an insulating film is a step of forming an insulating coating film having a liquid-repellent surface with a composition for forming an insulating film containing a first polymer having an acid dissociative group and a first acid generator, and the above. This is a method for forming a laminated wiring including a step of forming the liquid-based surface region on a part of the surface region of the insulating coating.

In the forming method, a composition for forming an insulating film containing a first polymer having an acid dissociative group and a first acid generator is used for forming the insulating film. Therefore, for example, in the region of the insulating coating that has been heated or irradiated, an acid is generated, and the acid dissociation group of the first polymer is dissociated by the generation of this acid, so that the wettability changes. To do. Since such heating and irradiation can be performed without using a laser, the laminated wiring can be efficiently formed according to the forming method.

The present invention can provide a method for forming a laminated wiring capable of efficiently forming a laminated wiring.

FIG. 1A is an explanatory diagram of a step (A-1) in the method for forming a laminated wiring according to an embodiment of the present invention, and FIG. 1B is an explanatory diagram of a step (A-2). Yes, FIG. 1 (c) is an explanatory diagram of the process (A-3), FIG. 1 (d) is an explanatory diagram of the process (A-4), and FIG. 1 (e) is a process (A). It is explanatory drawing of -5). FIG. 2A is an explanatory diagram of step (B-1), FIG. 2B is an explanatory diagram of step (B-2), and FIG. 2C is a process (B-3). )-(B-4). FIG. 3 is an explanatory diagram of step (C). FIG. 4 is an image showing the substrate on which the first conductive layer is formed in the embodiment. FIG. 5 is an image showing a substrate on which a repellent pattern is formed on the second layer in the embodiment. FIG. 6 is an image showing the substrate on which the second conductive layer is formed in the embodiment. FIG. 7 is an enlarged image of the substrate on which the second conductive layer of FIG. 6 is formed. FIG. 8 is an image showing a substrate on which the second conductive layer and the via conductor are formed in the embodiment. FIG. 9 is an SEM image showing the substrate on which the second conductive layer and the via conductor are formed in the embodiment.

Hereinafter, a method for forming a laminated wiring and a laminated wiring according to an embodiment of the present invention will be described in detail with reference to the drawings as appropriate.

<Method of forming laminated wiring>
The method for forming the laminated wiring according to the embodiment of the present invention is
Step (A) of preparing a base material having a first conductive layer as the outermost layer,
A step of forming an insulating film on the surface of the base material (B) and a step of forming a second conductive layer (C).
With
The insulating film forming step (B)
A step of forming an insulating coating film (B-1) and a step of forming a liquid-based surface region (B-2).
To be equipped.

The insulating film forming step (B) in the forming method is described in.
Step of forming a hole for via (B-3)
It is preferable to have
Step of heating the insulating coating film irradiated with radiation (B-4)
It is also preferable to provide.

In addition, the preparation process (A)
Step of forming the undercoat film (A-1),
Step of forming a liquid-friendly surface region (A-2) and step of forming a first conductive layer (A-4))
It is preferable to provide.

Further, the preparation step (A) in the forming method is
Before the first conductive layer forming step (A-4),
Step of heating the base coating film irradiated with radiation (A-3)
It is preferable to provide.

In addition, the preparation step (A) in the forming method is
After the first conductive layer forming step (A-4),
Step of irradiating the entire surface of the surface on which the first conductive layer is formed (A-5)
It is preferable to provide.

Hereinafter, the forming method will be described in detail in order. The order of the steps is not limited to the following order, and as long as the same laminated wiring can be formed, the order of the steps may be different, and a plurality of steps may be performed at the same time.

<Preparation process (A)>
The preparation step (A) is a step of preparing a base material having the first conductive layer as the outermost layer. The preparation step (A) is preferably composed of the following steps (A-1) to (A-5).

<Undercoat film forming step (A-1)>
The undercoat film forming step (A-1) is a step of forming an undercoat film having a liquid-repellent surface with the undercoat film forming composition. The composition for forming an undercoat film contains a polymer having an acid dissociative group (second polymer) and an acid generator (second acid generator). The acid dissociable group refers to a group in which a hydrogen atom is substituted in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, and refers to a group that dissociates in the presence of an acid. The composition for forming the base film will be described in detail later. Specifically, in the step (A-1), as shown in FIG. 1A, the undercoat film 11 is formed by applying the undercoat film forming composition to the surface of the substrate 10. The undercoat film 11 finally becomes the undercoat film 15 (see FIG. 1E).

Examples of the material of the substrate 10 include glass, quartz, silicon, resin and the like. Examples of the resin include polyethylene terefralate, polybutylene terephthalate, polyethylene naphthalate, polyether sulfone, polycarbonate, polyimide, and a ring-opening polymer of cyclic olefin (ROMP polymer).

As the substrate 10, resin substrates, glass substrates, and semiconductor substrates conventionally used in electronic circuits are preferable. By using such a substrate, the obtained laminated wiring can be used as it is for an electronic circuit or the like.

If necessary, the surface of the substrate 10 may be pretreated before the composition for forming the base film is applied to the substrate 10. Examples of the pretreatment include cleaning and roughening treatment.

The coating method of the composition for forming the base film is not particularly limited, and the coating method using a brush or a brush, the dipping method, the spray method, the roll coating method, the rotary coating method (spin coating method), the slit die coating method, etc. Known methods such as bar coating method, flexographic printing, offset printing, inkjet printing, and dispensing method can be mentioned.

After applying the undercoat film forming composition, the undercoat film 11 is preferably heated (prebaked). The heating conditions vary depending on the composition of the base film forming composition and the like, but are, for example, 60 ° C. or higher and 120 ° C. or lower, and 1 minute or longer and 10 minutes or shorter.

The average thickness of the obtained base coating film 11 can be appropriately adjusted according to the intended use, etc., but the lower limit thereof is preferably 0.05 μm, more preferably 0.1 μm. On the other hand, the upper limit is preferably 20 μm, more preferably 10 μm.

<Proximity surface region forming step (A-2)>
In the lipophilic surface region forming step (A-2), as shown in FIG. 1 (b), for example, by irradiating (exposure) a part of the surface region of the undercoat film 11 with radiation (hν), the parent coating film 11 is parented. This is a step of forming the liquid surface region 12. The surface of the undercoat film 11 obtained from the undercoat film forming composition has a liquid-repellent property, and the region irradiated with radiation becomes the liquid-based surface region 12. On the other hand, the region not irradiated with radiation is the liquid-repellent surface region 13. Here, liquid repellency and lipophilicity are relative concepts.

The reason why the lipophilic surface region 12 is formed by irradiation with radiation is as follows. Upon irradiation with radiation, an acid is generated from the radiation-sensitive acid generator in the composition for forming the base film, whereby the acid dissociative group of the polymer is dissociated. The dissociation of the acid dissociative group changes the surface energy of the irradiated area and enhances wettability. In particular, when the acid dissociative group has a fluorine atom, the expression of this liquid repellency becomes remarkable. Since the component derived from the dissociated acid dissociative group is preferably volatilized, the wicked surface region 12 becomes a recess (concave pattern). Since the lipophilic surface region 12 becomes a concave portion, the concave portion (lipidic surface region 12) can be filled with the conductive layer forming material without oozing out, as will be described later.

Radiation irradiation (exposure) can be performed through a photomask having a predetermined pattern so that a lyophilic surface region 12 having a shape similar to the shape of the wiring to be formed is formed. By performing exposure through a photomask, irradiation can be performed efficiently even when a complicated pattern is formed. In addition, a predetermined pattern can be drawn and exposed using a direct drawing exposure machine or the like.

Visible light, ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays and the like can be used as the radiation to be irradiated in this step (A-2). Among these, radiation having a wavelength in the range of 190 nm or more and 450 nm or less is preferable, and radiation containing ultraviolet rays having a wavelength of 365 nm is more preferable.

The amount of radiation exposure in this step (A-2) may be appropriately set within a range in which a sufficient change in wettability and formation of recesses can be formed. The lower limit of the exposure amount, as the intensity at a wavelength 365nm radiation, preferably ^{10mJ / cm 2, 20mJ / cm} 2 is more preferable. On the other hand, as the upper limit, 1000 mJ / cm ² is preferable, and 500 mJ / cm ² is more preferable.

The size and shape of the arsenic surface region 12 formed corresponds to the desired size and shape of the wiring, and can be linear, for example, having a width of 10 μm or more and 300 μm or less.

<Heating step (A-3)>
The heating step (A-3) is a step of heating the base coating film 11 irradiated with radiation. By this heating, the dissociated components can be further volatilized in the irradiated region (parental liquid surface region 12). As a result, the lipophilic surface region 12 (recess) becomes deeper (see FIG. 1C). In addition, the volatilization of the dissociated components further enhances the wettability of the lipophilic surface region 12.

The depth of the lipophilic surface region 12 (recess) can be, for example, 0.1 μm or more and 1 μm or less. Further, the lower limit of the depth of the liquid-based surface region 12 (recess) with respect to the average thickness of the liquid-repellent surface region 13 in the undercoat film 11 is preferably 5%, more preferably 10%. On the other hand, as the upper limit, 70% is preferable, and 50% is more preferable. By forming the wicked surface region 12 having such a depth, the conductive layer forming material can be effectively filled in the wicked surface region 12. As a result, fine wiring can be formed with high accuracy.

The heating method in this step is not particularly limited, and examples thereof include a method of heating using a hot plate, an oven, a dryer, or the like. Alternatively, it may be heated by vacuum baking. The heating conditions are also appropriately set depending on the composition and film thickness of the base film forming composition, but are preferably 60 ° C. or higher and 150 ° C. or lower, and preferably 3 minutes or longer and 30 minutes or shorter.

Difference in contact angle between the liquid-repellent surface region 12 and the liquid-repellent surface region 13 formed in this manner with respect to tetradecane (contact angle in the liquid-repellent surface region 13-contact angle in the liquid-repellent surface region 12). As the lower limit, 30 ° is preferable, 40 ° is more preferable, and 50 ° is even more preferable. The upper limit of this contact angle difference is, for example, 70 °. Further, the lower limit of the contact angle difference between the liquid-repellent surface region 12 and the liquid-repellent surface region 13 with respect to water (contact angle in the liquid-repellent surface region 13-contact angle in the liquid-repellent surface region 12) is 20. ° is preferred, more preferably 25 °. The upper limit of this contact angle difference is, for example, 60 °. As described above, since the contact angle difference with respect to tetradecane or water is large, the conductive layer forming material in contact with the liquid-repellent surface region 13 can easily move to the liquid-friendly surface region 12, and is liquid-friendly. Wiring along the surface region 12 can be preferably formed.

<First conductive layer forming step (A-4)>
The first conductive layer forming step (A-4) is a step of forming the first conductive layer 14 by contacting the surface of the base coating film 11 irradiated with radiation with the material for forming the first conductive layer (FIG. 1). (D)).

The material for forming the first conductive layer is not particularly limited. For example, any conductive material that can form wiring may be used, and examples thereof include a conductive film forming ink and a conductive film forming paste.

Specific preferred materials for forming the first conductive layer include an ink or paste in which metal particles are dispersed, an ink or paste containing a metal salt and a reducing agent, and metal oxide particles that can be metallized by heating in a reducing atmosphere. Examples thereof include an ink or paste in which the above is dispersed, an ink or paste which is a dispersion or solution of a conductive polymer, and an ink or paste in which nanocarbons such as carbon nanotubes and graphene are dispersed. Among these, inks and pastes in which metal particles such as silver particles are dispersed, and inks and pastes containing a metal salt and a reducing agent are particularly preferable from the viewpoint of conductivity and coatability. These inks or pastes can form a coating film by various printing methods and coating methods. Further, the coating film of such a material for forming the first conductive layer is heated to become the first conductive layer 14 (wiring).

The contact of the material for forming the first conductive layer with the surface of the undercoat film 11 can be performed by a known method such as coating. Specifically, coating method using a brush or brush, dipping method, spray method, roll coating method, rotary coating method (spin coating method), slit die coating method, bar coating method, flexographic printing, offset printing, inkjet Known methods such as printing and dispensing method can be mentioned. Among these, the dipping method, the spray method, the spin coating method, the slit die coating method, the offset printing method, the inkjet method and the dispensing method are preferable.

A liquid-soluble surface region 12 and a liquid-repellent surface region 13 are formed on the surface of the undercoat film 11. Therefore, when the material for forming the first conductive layer is brought into contact with the surface of the base coating film 11, the material for forming the first conductive layer is repelled in the liquid-repellent surface region 13, and is preferably a recess. It flows into the surface area 12. As a result, the first conductive layer forming material is disposed along the recessed liquid-friendly surface region 12.

<Irradiation step (A-5)>
The radiation irradiation step (A-5) is a step of irradiating the entire surface of the surface on which the material for forming the first conductive layer is applied, that is, the side on which the first conductive layer 14 is formed, with radiation (hν). By irradiating the entire surface of the exposed base coating film 11 with radiation in this way, the entire surface of the liquid-repellent surface region 13 becomes lipophilic. As a result, the applicability of the insulating film forming composition to the surface of the base film 15 in the post-process described later is improved.

Specific examples and preferable examples of the radiation to be irradiated in this step are the same as those in the positivity surface region forming step (A-2). Further, the amount of radiation exposure in this step can be the same as in the step of forming a liquid-based surface region (A-2).

After irradiating the entire surface with radiation, it is preferable to heat the undercoat film 11 and the like. By this heating, the components derived from the acid dissociative group dissociated in the exposed portion (exposed portion) are volatilized, the exposed portion becomes thinner, and the liquidity becomes higher. Further, by this heating, the material for forming the first conductive layer (first conductive layer 14) is sufficiently cured. Through such a step, the undercoat film 11 becomes the undercoat film 15, and the base material 16 having the first conductive layer 14 (wiring) on the outermost layer can be obtained (see FIG. 1 (e)).

The heating method is not particularly limited, and examples thereof include a method of heating using a hot plate, an oven, a dryer, or the like. Alternatively, it may be heated by vacuum baking. The heating conditions are not particularly limited, but can be, for example, 50 ° C. or higher and 200 ° C. or lower, and 1 minute or longer and 120 minutes or shorter. However, since it is not necessary to thin the undercoat film 15 (undercoat film 11), the heating conditions may be milder than those in the heating step (A-3).

<Insulating film forming step (B)>
In the insulating film forming step (B), for example, an insulating film 23 having a liquid-repellent surface region 19 and a liquid-based surface region 18 provided with via holes 20 is formed on the surface of the base material 16. This is a process (see FIG. 2C). In addition, in FIG. 2C and the like, the via hole 20 is formed in the liquid-based surface region 18 of the insulating film 23, but the via hole 20 may not be formed.

<Insulating coating film forming step (B-1)>
The insulating coating film forming step (B-1) is a step of forming an insulating coating film 17 having a liquid-repellent surface with the insulating film forming composition. The composition for forming an insulating film contains a polymer having an acid dissociative group (first polymer) and an acid generator (first acid generator). The composition for forming an insulating film will be described in detail later. In the step (B-1), specifically, as shown in FIG. 2A, a composition for forming an insulating film on the surface of the base material 16 on the side on which the first conductive layer 14 is formed. By coating, an insulating coating film 17 is formed. The insulating coating film 17 finally becomes the insulating film 23.

The method for applying the insulating film-forming composition is the same as the method for applying the undercoat film-forming composition in the above-mentioned step (A-1).

After applying the insulating film-forming composition, the insulating coating film 17 is preferably heated (prebaked). The heating conditions vary depending on the composition of the insulating film forming composition and the like, but are, for example, 60 ° C. or higher and 120 ° C. or lower, and 1 minute or longer and 10 minutes or shorter.

The average thickness of the obtained insulating coating film 17 can be appropriately adjusted according to the intended use, etc., but the lower limit thereof is preferably 0.05 μm, more preferably 0.1 μm. On the other hand, the upper limit is preferably 20 μm, more preferably 10 μm.

<Proximity surface region forming step (B-2)>
The wicked surface region forming step (B-2) is a step of forming a wicked surface region by irradiating a part of the surface region of the insulating coating film 17 with radiation (hν) (FIG. 2 (b). )reference). Similar to the undercoat film 11 obtained from the undercoat film forming composition, the surface of the insulating coating film 17 has a liquid-repellent property, and the region irradiated with radiation becomes the parental liquid surface region 18. On the other hand, the region not irradiated with radiation is the liquid-repellent surface region 19. Further, similarly to the undercoat film 11, the liquid-based surface region 18 becomes a concave portion (concave pattern).

The radiation irradiation (exposure) method, the type of radiation, specific examples of the exposure amount, and preferable examples in this step (B-2) are the same as those in the liquid-based surface region forming step (A-2). That is, the irradiation of radiation is preferably performed by exposure through a photomask. Further, the shape and the like of the wicked surface region 18 formed can be the same as that of the wicked surface region 12 formed in the step (A-2).

<Via hole forming step (B-3)>
The via hole forming step (B-3) is a step of forming the via hole 20 (see FIG. 2C). The method for forming the via holes 20 is not particularly limited, but it can be preferably performed by irradiating a part of the positivity surface region 18 of the insulating coating film 17 with a laser. By such laser ablation, a via hole 20 for connecting the first conductive layer 14 and the second conductive layer 21 (see FIG. 3) is formed. The via hole 20 penetrates the insulating coating film 17. The via holes 20 can also be formed by a method other than laser ablation. For example, the via hole 20 may be formed by irradiating a photomask with a sufficient amount of radiation.

The wavelength of the laser used in this step (B-3) is not particularly limited, but it is preferable to use radiation (ultraviolet rays) in the range of 190 nm or more and 450 nm or less. Specifically, the YAG laser's 3rd harmonic (355nm), 4th harmonic (266nm), 5th harmonic (215nm), excimer laser XeF laser (351nm), XeCl laser (308nm), KrF (248nm). ), ArF (193 nm) and the like. Among these, it is preferable to use the 4th harmonic (266 nm) of the YAG laser.

The size of the via holes 20 to be formed is not particularly limited, but is usually narrower than the width of the linear lyophilized surface region 18. The specific size of the via hole 20 can be, for example, about 1 μm or more and 100 μm or less. The size of the via hole 20 means the diameter of the via hole 20 when it is circular, and the length of one side (long side) when it is square.

<Heating step (B-4)>
The heating step (B-4) is a step of heating the insulating coating film 17 irradiated with radiation. By this heating, the dissociated components can be further volatilized in the area irradiated with radiation (parental surface area 18). As a result, the lipophilic surface region 18 (recess) becomes deeper. In addition, the volatilization of the dissociated components further enhances the wettability of the lipophilic surface region 18.

The shape of the liquid-based surface region 18 in the insulating film 23 obtained through this heating step (B-4), the relationship between the contact angle difference between the liquid-based surface region 18 and the liquid-repellent surface region 19, the heating method, etc. , The same as the description in the heating step (A-3).

The heating step (B-4) may be performed before the via hole forming step (B-3) as long as it is after the lipophilic surface region forming step (B-2). It may be performed after the hole forming step (B-3). However, it is preferable to perform the heating step (B-4) before the via hole forming step (B-3). The via holes 20 can be efficiently and accurately formed by performing laser ablation after thinning the liquid-forming surface region 18 through the heating step (B-4).

<Second conductive layer forming step (C)>
In the second conductive layer forming step (C), the second conductive layer 21 (wiring) is laminated on the liquid-liquid surface region 18 of the insulating film 23 by contacting the material for forming the second conductive layer with the surface of the insulating film 23. ) Is the process of forming. At this time, the material for forming the second conductive layer forms a via conductor 22 that connects the first conductive layer 14 and the second conductive layer 21 together with the second conductive layer 21. Specific examples and preferable examples of the material for forming the second conductive layer are the same as those for the material for forming the first conductive layer described above.

The method of contacting the second conductive layer forming material with the insulating film 23 surface is the same as that of the first conductive layer forming material in the first conductive layer forming step (A-4). When the material for forming the second conductive layer is brought into contact with the surface of the insulating film 23, the material for forming the second conductive layer is repelled in the liquid-repellent surface region 19, preferably in the liquid-friendly surface region 18 which is a recess. It flows in. As a result, the second conductive layer forming material is arranged along the liquid-based surface region 18. Further, the material for forming the second conductive layer that has flowed into the wicked surface region 18 is filled into the via holes 20 formed in the wicked surface region 18.

After the contact (coating) of the material for forming the second conductive layer, the material for forming the second conductive layer is heated together with the substrate 10 and the like. By this heating, the material for forming the second conductive layer is cured, and the second conductive layer 21 and the via conductor 22 are formed. Examples of this heating method include heating using a hot plate, an oven, a dryer, and the like, vacuum baking, and the like. The heating conditions are not particularly limited, but can be, for example, 50 ° C. or higher and 200 ° C. or lower, and 1 minute or longer and 120 minutes or shorter.

Through such a step, a laminated wiring 24 which is a laminated body of wiring including the first conductive layer 14 and the second conductive layer 21 can be obtained. According to the forming method, the wettability pattern (parental liquid surface region 12 and liquidar liquid surface region 18) can be formed by exposure through a photomask or the like without using a laser. , The laminated wiring 24 can be efficiently formed.

<Composition for film formation>
Hereinafter, the composition for forming an undercoat film and the composition for forming an insulating film (hereinafter, both compositions are collectively referred to as a “composition for forming a film”) will be described in detail. The composition for forming the undercoat film and the composition for forming the insulating film may have different compositions or the same composition, but the same composition is preferable. Since these are the same composition, laminated wiring can be efficiently manufactured.

As described above, the film-forming composition includes a polymer having an acid dissociative group (hereinafter, also referred to as “polymer (A)”) and an acid generator (hereinafter, “acid generator (B)”). Also referred to as). The film-forming composition usually contains a solvent (C), and other suitable components include a sensitizer (D), a quencher (E), a polymerizable compound (F), and radiation-sensitive polymerization initiation. The agent (G) can be contained.

<Polymer (A)>
The polymer (A) is not particularly limited as long as it is a polymer having an acid dissociative group, but is usually a polymer having a structural unit (I) having this acid dissociative group. The structural unit (I) preferably has a structure containing either an acetal bond or a hemiacetal ester bond. The structural unit (I) containing an acid dissociative group more preferably contains a group represented by the following formula (5-1) or (5-2).

In the formula (5-1) and (5-2), ^{R 4} and ^{R 5} are each independently hydrogen atom or a methyl group. Rf is an independently organic group having a fluorine atom. * Represents the binding site.

-C (R ¹ ) (R ² ) ORf in the formulas (5-1) and (5-2) serves as an acid dissociative group. By using the polymer (A) having such a group, the acid dissociative group is efficiently dissociated in the exposed portion of the coating film, and the surface energy is increased. Further, when the acid dissociative group contains a fluorine atom as described above, the surface energy of the film before and after the dissociation of the acid dissociative group, that is, the change in wettability becomes large, which is preferable.

As Rf, a hydrocarbon group in which one or more hydrogen atoms are substituted with a fluorine atom, and a group having an oxygen atom between carbon-carbon bonds of such a hydrocarbon group are preferable. More preferred groups of Rf, equation (1) to (4) to be described later ^- can be a group represented by ^{_{(R 2 -O) n -R 3}} .

The structural unit (I) is preferably a structural unit represented by any of the following formulas (1) to (4). The structural unit (I) may consist of only one type of structural unit, or may include a plurality of types of structural units.

In formulas (1) to (4), R ¹ is independently a hydrogen atom or a methyl group. R ² independently has a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and 4 to 12 carbon atoms. A divalent alicyclic hydrocarbon group of the above, or a group in which one or more hydrogen atoms of these groups are substituted with a substituent. R ³ is a hydrocarbon group in which one or more hydrogen atoms are substituted with fluorine atoms, respectively. m is 0 or 1 independently of each other. n is an integer of 0 to 12 independently of each other.

Examples of the alkylene group having 2 to 12 carbon atoms represented by R ² include an ethylene group, a propylene group, and a butylene group.

Examples of the alkenylene group having 2 to 12 carbon atoms represented by R ² include a vinylene group and an ethene-1,2-diyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R ² include a phenylene group, a trilene group, a naphthylene group, and a biphenylene group.

Examples of the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ² include a cyclobutane diyl group and a cyclohexane diyl group.

Examples of the substituent that replaces the hydrogen atom contained in these groups include a halogen atom such as a fluorine atom and a hydroxy group.

The R ^2, methylene group, preferably an alkylene group and the aromatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group and a biphenylene group are more preferable.

Examples of the hydrocarbon group in which one or more hydrogen atoms represented by R ³ are substituted with a fluorine atom (fluorine-substituted hydrocarbon group) include a fluorine-substituted aliphatic hydrocarbon group and a fluorine-substituted aromatic hydrocarbon group. However, fluorine-substituted aliphatic hydrocarbon groups are preferable. The lower limit of the number of carbon atoms of this fluorine-substituted hydrocarbon group is preferably 3 and more preferably 4. On the other hand, the upper limit is preferably 30, more preferably 20, and even more preferably 15. As the lower limit of the number of fluorines of this fluorine-substituted hydrocarbon group, 5 is preferable, and 10 is more preferable. On the other hand, the upper limit can be, for example, 30. By using R ³ as such a group, the change in surface energy can be made larger, and the volatility of the dissociated component can be increased.

Specific examples of the fluorine-substituted hydrocarbon group represented by R ³ include groups represented by the following formulas (Rf-1) to (Rf-33).

n is an integer of 0 to 12, but as the upper limit thereof, 8 is preferable, 4 is more preferable, and 2 is more preferable. As n, 0 is particularly preferable.

Specific examples of the structural unit (I) represented by the above formulas (1) to (4) include the following.

The lower limit of the content of the structural unit (I) with respect to all the structural units of the polymer (A) is preferably 20% by mass, more preferably 35% by mass. Further, this lower limit may be 50% by mass or 70% by mass. On the other hand, the upper limit may be 100% by mass and may be 80% by mass.

The polymer (A) can have a structural unit other than the structural unit (I). Other structural units are specifically (meth) acrylic acid chain alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated aromatic compounds, conjugated diene, and tetrahydro, which will be described later. Examples thereof include structural units derived from unsaturated compounds having a skeleton, maleimides, other monomers and the like.

The polymer (A) is a method obtained by reacting (1) a polymer having a hydroxyl group or a carboxy group as a precursor with a compound (a) represented by the following formula (a), and (2) a compound (a). It can be obtained by a method of polymerizing the monomer obtained by using the above.

Wherein ^(a), R 1 to R ³ and n have the same meanings as ^R 1 to R ³ and n in the above formula (1) to (4).

(1) Method of reacting compound (a) with a polymer as a precursor In this method, a polymer having a hydroxyl group or a carboxy group is obtained by polymerizing a monomer having a hydroxyl group or a carboxy group, and this polymer is used. The compound (a) is reacted to obtain the polymer (A).

Examples of the monomer having a hydroxyl group include a (meth) acrylic acid ester having a hydroxyl group. Specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate. , 2-Acryloyloxyethyl-2-hydroxylethylphthalic acid, dipropylene glycol methacrylate, dipropylene glycol acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, cyclohexanedimethanol monoacrylate, cyclohexanedimethanol monomethacrylate, ethyl α- (Hydroxymethyl) acrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, glycerin monomethacrylate, glycerin monoacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, poly (ethylene glycol-propylene glycol) monomethacrylate, poly (ethylene) Glycol-propylene glycol) monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, poly (ethylene glycol-tetramethylene glycol) monomethacrylate, poly (ethylene glycol-tetramethylene glycol) monoacrylate, poly (poly) Propropylene glycol-tetramethylene glycol) monomethacrylate, poly (propylene glycol-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monomethacrylate, propylene glycol polybutylene glycol monoacrylate, p-hydroxyphenyl methacrylate, parahydroxyphenyl acrylate, etc. Can be mentioned.

Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, and 2-acryloyloxy. Ethyltetrahydrophthalic acid, 2-methacryloyloxyethyltetrahydrophthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyloxypropylphthalic acid, Examples thereof include 2-acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydrophthalic acid, 2-methacryloyloxypropylhexahydrophthalic acid and the like.

The polymer having a hydroxyl group or a carboxy group can be obtained by using only the monomer having a hydroxyl group or a carboxy group, and other than the monomer having a hydroxyl group or a carboxy group and the monomer having a hydroxyl group or a carboxy group. It can be obtained by copolymerizing with a monomer. Examples of the monomer other than the monomer having a hydroxyl group or a carboxy group include (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, and tetrahydrofuran. Examples thereof include unsaturated compounds containing a skeleton, maleimide, and other monomers.

Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and methacrylic. N-lauryl acid acid, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate , N-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, isobornyl methacrylate, and cyclohexyl acrylate. , 2-Methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, isobornyl acrylate and the like.

Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, benzyl acrylate and the like.

Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and the like.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of unsaturated compounds containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydrofuran-2-one and the like. ..

Examples of maleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-tolylmaleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, and N-benzylmaleimide.

Examples of other monomers include (meth) acrylic acid esters having an epoxy group (cyclic ether group). Specifically, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3- Ethyloxetane, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yloxyethyl, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, etc. be able to.

Examples of the solvent used in the polymerization reaction for synthesizing a polymer having a hydroxyl group or a carboxy group include glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, and propylene glycol mono. Examples thereof include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate and the like. Further, other alcohols, ethers, ketones, esters and the like can also be used.

In the polymerization reaction for obtaining a polymer having a hydroxyl group or a carboxy group, a molecular weight adjusting agent can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; dimethyl. Xanthogens such as xanthogen sulfide and diisopropyl xanthogen disulfide; turpinolene, α-methylstyrene dimer and the like can be mentioned.

The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the polymer having a hydroxyl group or a carboxy group by gel permeation chromatography (GPC) is preferably 1000, more preferably 5000. On the other hand, as the upper limit, 50,000 is preferable, and 30,000 is more preferable. By setting the Mw of the polymer having a hydroxyl group or a carboxy group in the above range, the sensitivity of the film-forming composition containing the polymer (A) can be increased.

Next, the compound (a) is reacted with the hydroxyl group or carboxy group of the obtained polymer having a hydroxyl group or carboxyl. An example of these reactions is represented by the following reaction formula.

An acetal bond is formed by the hydroxyl group of the polymer having a hydroxyl group and the vinyl ether group of the compound (a), and by the carboxy group of the polymer having a carboxy group and the vinyl ether group of the compound (a). A hemiacetal ester bond is formed to form the polymer (A).

As a specific reaction method, first, a polymer having a hydroxyl group or a carboxy group is dissolved in an organic solvent, and then an equimolar or excess amount of the compound (a) is added to the hydroxyl group or the carboxy group of the polymer. .. After cooling the obtained reaction mixture from 0 ° C. to about room temperature, an acid (for example, oxalic acid) dissolved in the same solvent as the above organic solvent is added dropwise as a catalyst, and the mixture is stirred at room temperature for about 1 to 24 hours. React. After completion of the reaction, the desired polymer (A) can be obtained by removing the organic solvent.

(2) Method of Polymerizing a Monomer Obtained Using Compound (a) In this method, a desired monomer is obtained by reacting the above compound (a) with a hydroxyl group or carboxy group of a polymerizable compound having a hydroxyl group or a carboxy group. Then, the polymer (A) is obtained by polymerizing this monomer. As a method for producing such a polymer (A), a known method can be referred to.

In the above method, specifically, an acetal bond is formed by the hydroxyl group of the polymerizable compound having a hydroxyl group and the vinyl ether group of the vinyl ether compound (compound (a)), or the carboxy of the polymerizable compound having a carboxy group. A hemiacetal ester bond is formed by the group and the vinyl ether group of the vinyl ether compound (compound (a)) to obtain a desired monomer. Then, the polymer (A) can be obtained by polymerizing the obtained monomer in the same manner as in the above-mentioned method for producing a polymer having a hydroxyl group or a carboxy group.

<Acid generator (B)>
The acid generator (B) has, for example, a function of generating an acid in response to heating, radiation, or the like. The acid generator (B) is preferably a radiation-sensitive acid generator. The acid generator (B) may be contained as a so-called acid generator in the form of a compound, or may be incorporated in a part of a polymer such as the polymer (A). When the film-forming composition contains the acid generator (B), the acid dissociative group can be eliminated from the polymer (A).

Examples of the acid generator which is a radiation-sensitive acid generator include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carboxylic acid ester compound. it can. The acid generator may be used alone or in combination of two or more. These radiation-sensitive acid generators may function as heat-sensitive acid generators.

[Oxime sulfonate compound]
As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (6) is preferable.

In the above formula (6), R ¹¹ is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, and an aryl having 6 to 20 carbon atoms. A group, or a group in which some or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups and aryl groups are substituted with substituents.

Examples of the substituent that the alkyl group, alicyclic hydrocarbon group and aryl group may have include an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom and the like.

Examples of the compound containing the oxime sulfonate group represented by the above formula (6) include oxime sulfonate compounds represented by the following formulas (6-1) to (6-3).

In the above formula (6-1) ~ ^{(6-3), R 11} has the same meaning as ^{R 11} in the formula (6). R ¹⁵ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms. X is an alkyl group, an alkoxy group or a halogen atom. m is an integer from 0 to 3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

Examples of the oxime sulfonate compound represented by the above formula (6-3) include compounds represented by the following formulas (6-3-1) to (6-3-5).

The compounds represented by the above formulas (6-3-1) to (6-3-5) are, in order, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile. (5-Octylsulfonyloxyimino-5H-thiophen-2-iriden)-(2-methylphenyl) acetonitrile, (Phenylsulfonyloxyimino-5H-thiophen-2-iriden)-(2-methylphenyl) acetonitrile, (5) -P-Toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, and (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile.

Examples of the other compound containing the oxime sulfonate group represented by the above formula (6) include (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile and the like.

[Onium salt]
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt and the like. it can.

Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, and diphenyl. Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Nate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis ( 4-t-butylphenyl) iodonium camphorsulfonic acid and the like can be mentioned.

Examples of the triphenyl sulfonium salt include triphenyl sulfonium trifluoromethane sulfonate, triphenyl sulfonium camphor sulfonic acid, triphenyl sulfonium tetrafluoroborate, triphenyl sulfonium trifluoroacetate, triphenyl sulfonium-p-toluene sulfonate, and triphenyl. Examples thereof include sulfonium butyltris (2,6-difluorophenyl) borate and the like.

Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, and dimethyl-4. -(Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned.

Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxy. Phenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxy Examples thereof include phenylmethylsulfonium hexafluorophosphate.

Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenyl. Sulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl -4-Hydroxyphenylsulfonium hexafluorophosphate and the like can be mentioned.

Examples of the substituted benzyl sulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenyl. Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3 −Chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate and the like can be mentioned.

Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxy). Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate and the like can be mentioned.

Examples of the tetrahydrothiophenium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium trifluo. Lomethanesulfonate, 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium-1, 1,2,2-Tetrafluoro-2- (norbornane-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxy) Bicyclo [2.2.1] heptane-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalene-1-yl) tetrahydrothiophenium-2- ( 6-t-butoxycarbonyloxybicyclo [2.2.1] heptane-2-yl) -1,1,2,2-tetrafluoroethanesulfonate and the like can be mentioned.

[Sulfone imide compound]
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (kanfasulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, and N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (kanfasulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (kanfasulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-tri) Fluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (trifluo) Lomethanesulfonyloxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboxyimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-en-2 , 3-Dicarboxyimide, N- (kanfasulfonyloxy) bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (kanfasulfonyloxy) -7-oxabicyclo [2] .2.1] Hept-5-en-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-en-2,3- Dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxa Bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) Bisi Clos [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5- En-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyl sulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboxyimide, N- (kanfasulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (4-methylphenylsulfonyl) Oxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,5 6-Oxy-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (tri) Fluoromethylsulfonyloxy) naphthyldicarboxyimide, N- (kanfasulfonyloxy) naphthyldicarboxyimide, N- (4-methylphenylsulfonyloxy) naphthyldicarboxyimide, N- (phenylsulfonyloxy) naphthyldicarboxyimide, N -(2-Trifluoromethylphenylsulfonyloxy) naphthyldicarboxyimide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboxyimide, N- (pentafluoroethylsulfonyloxy) naphthyldicarboxyimide, N- (heptafluoro) Propylsulfonyloxy) naphthyldicarboxyimide, N- (nonafluorobutylsulfonyloxy) naphthyldicarboxyimide, N- (ethylsulfonyloxy) naphthyldicarboxyimide, N- (propylsulfonyloxy) naphthyldicarboxyimide, N- ( Butylsulfonyloxy) naphthyldicarboxyimide, N- (pentylsulfonyloxy) naphthyldicarboxyimide, N- (hexylsulfonyloxy) naphthyldicarboxyimide, N- (heptylsulfonyloxy) naphthyldical Examples thereof include boxyimide, N- (octylsulfonyloxy) naphthyldicarboxyimide, and N- (nonylsulfonyloxy) naphthyldicarboxyimide.

[Halogen-containing compound]
Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound.

[Diazomethane compound]
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-kisilylsulfonyl) diazomethane. , Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane And so on.

[Sulfone compound]
Examples of the sulfone compound include β-ketosulfone compound, β-sulfonylsulfone compound, diaryldisulfone compound and the like.

[Sulfonic acid ester compound]
Examples of the sulfonic acid ester compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate and the like.

[Carboxylate ester compound]
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

Examples of the acid generator that is a heat-sensitive acid generator include onium salts such as diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt, phosphonium salt, and tetrahydrothiophenium salt, and sulfonimide. Examples include compounds. These heat-sensitive acid generators may function as radiation-sensitive acid generators.

As the acid generator (B), an oxime sulfonate compound, an onium salt and a sulfonic acid ester compound are preferable, and an oxime sulfonate compound is more preferable. By using the acid generator (B) as these compounds, the film-forming composition can further improve the sensitivity, and can also improve the solubility.

When the acid generator (B) is an acid generator, the lower limit of the content of the acid generator is preferably 0.1 part by mass and more preferably 1 part by mass with respect to 100 parts by mass of the polymer (A). preferable. On the other hand, as the upper limit, 10 parts by mass is preferable, and 5 parts by mass is more preferable. By setting the content of the acid generator in the above range, the sensitivity can be optimized and a better laminated wiring can be formed.

<Solvent (C)>
The solvent (C) is not particularly limited, but a solvent capable of uniformly dissolving or dispersing the polymer (A), the acid generator (B) and other components is preferable.

Examples of the solvent (C) include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons, and aromatics. Examples thereof include group hydrocarbons, ketones, esters and the like.

Examples of the alcohols include long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, and 1,8-octanediol;
Aromatic alcohols such as benzyl alcohol;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
Examples thereof include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether.

Examples of the ethers include tetrahydrofuran, hexylmethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, 1,4-dioxane and the like.

Examples of the diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

Examples of the ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like.

Examples of the propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate. be able to.

Examples of the aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane, and decalin. it can.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, chlorobenzene, dichlorobenzene and the like.

Examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone and the like.

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methylpropion. Ethyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3- Butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate , Ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Examples thereof include butyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate.

As the solvent (C), one type may be used alone, or two or more types may be mixed and used.
As the lower limit of the content of the solvent (C), 200 parts by mass is preferable, and 400 parts by mass is more preferable with respect to 100 parts by mass of the components other than the solvent (C) of the film forming composition. On the other hand, as the upper limit, 1600 parts by mass is preferable, and 1000 parts by mass is more preferable. By setting the content of the solvent (C) in the above range, the coating property is improved, the occurrence of coating unevenness (streak unevenness, pin mark unevenness, moy unevenness, etc.) is suppressed, and the coating film with improved film thickness uniformity. Can be obtained.

<Sensitizer (D)>
The sensitizer (D) has a function of improving the radiosensitivity of the film-forming composition. The sensitizer (D) is preferably a compound that absorbs radiation and enters an electron-excited state. The sensitizer (D) in the electron-excited state comes into contact with the acid generator (B) to generate electron transfer, energy transfer, heat generation, etc., which causes the acid generator (B) to undergo a chemical change. Decomposes to produce acid.

Examples of the sensitizer (D) include compounds belonging to the following compounds and having an absorption wavelength in the range of 350 nm to 450 nm.

Examples of the sensitizer (D) include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene and the like. Polynuclear aromatics;
Xanthenes such as fluoressein, eosin, erythrosine, rhodamine B, rose bengal;
Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone (2,4-diethylthioxanthene-9-one, etc.), isopropylthioxanthone (2-isopropylthioxanthone, etc.);
Cyanines such as thiacarbocyanine and oxacarbocyanine;
Merocyanines such as merocyanine and carbomerocyanine;
Rhoda cyanines;
Oxonors;
Thiazines such as thionin, methylene blue, toluidine blue;
Acridines such as acridine orange, chloroflavin, and acriflavine;
Acridones such as 10-butyl-2-chloroacridone;
Anthraquinones such as anthraquinones;
Squaliums such as squalium;
Styrils;
Base styryls such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole;
7-diethylamino4-methylcoumarin, 7-hydroxy4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizidine- Examples thereof include coumarins such as 11-non.

Among these sensitizers (D), polynuclear aromatics, acridones, styryls, base styryls, coumarins and xanthones are preferable, and xanthones are more preferable. As the sensitizer (D), one type may be used alone, or two or more types may be mixed and used.

As the lower limit of the content of the sensitizer (D), 0.1 part by mass is preferable, and 0.3 part by mass is more preferable with respect to 100 parts by mass of the polymer (A). On the other hand, as the upper limit, 8 parts by mass is preferable, and 4 parts by mass is more preferable. By setting the content of the sensitizer (D) in the above range, the sensitivity of the film-forming composition can be optimized, and a high-resolution pattern (wiring) can be formed.

<Quencher (E)>
The quencher (E) has a function of controlling the diffusion of the acid from the acid generator (B). Examples of the quencher (E) include amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds and the like.

Examples of amine compounds include mono (cyclo) alkylamines; di (cyclo) alkylamines; tri (cyclo) alkylamines; substituted alkylaniline or derivatives thereof; ethylenediamine, N, N, N', N'-tetra. Methylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4) -Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-amino Phenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis (1- (4-aminophenyl) -1-methylethyl) benzene, 1,3-bis (1- (4-aminophenyl)- 1-Methylethyl) benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N , N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N', N''N''-pentamethyldiethylenetriamine and the like.

Examples of the amide group-containing compound include N-t-butoxycarbonyl group-containing amino compounds, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, and the like. Examples thereof include benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, tris isocyanurate (2-hydroxyethyl) and the like.

Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea and the like. Can be mentioned.

Examples of the nitrogen-containing heterocyclic compound include imidazoles such as 2-phenylbenzoimidazole; pyridines such as 4- (dimethylamino) pyridine; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol. , 3-Piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholin, 3- (N-morpholino) -1,2-propanediol, 1, Examples thereof include 4-dimethylpiperazine and 1,4-diazabicyclo [2.2.2] octane.

Further, as the quencher (E), a photodisintegrating base can be used. Examples of the photodisintegrating base include sulfonium salt compounds and onium salt compounds such as iodonium salt compounds.

As the quencher (E), a nitrogen-containing heterocyclic compound is preferable, and imidazoles and pyridines are more preferable. As the quencher (E), one type may be used alone, or two or more types may be mixed and used.

The lower limit of the content of the quencher (E) is preferably 0.001 part by mass and more preferably 0.01 part by mass with respect to 100 parts by mass of the polymer (A). On the other hand, as the upper limit, 3 parts by mass is preferable, and 1 part by mass is more preferable. By setting the content of the quencher (E) in the above range, the reactivity of the film-forming composition can be optimized, and a high-resolution pattern (wiring) can be formed.

<Polymerizable compound (F)>
By containing the polymerizable compound (F) in the film-forming composition, the curability can be enhanced. The polymerizable compound (F) is usually a polymerizable compound having an ethylenically unsaturated bond.

As the polymerizable compound (F), a monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid ester is preferable from the viewpoint of good polymerizable property and improvement in the strength of the obtained film. The monofunctional compound means a compound having one (meth) acryloyl group, and the bifunctional or trifunctional or higher compound is a compound having two or three or more (meth) acryloyl groups, respectively. It means that.

Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, and (2-acryloyloxyethyl) (2-hydroxypropyl). Examples thereof include phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ω-carboxypolycaprolactone monoacrylate.

Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol. Examples thereof include dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate.

Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropantriacrylate, trimethylpropantrimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol. Pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, tri (2-acryloyloxy) Examples thereof include ethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and tris (acryloxyethyl) isocyanurate.

As the polymerizable compound (F), a bifunctional or trifunctional or higher (meth) acrylic acid ester is preferable, and 1,9-nonanediol dimethacrylate, trimethylpropantriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol Pentaacrylate and polyfunctional urethane acrylate-based compounds are more preferable. As the polymerizable compound (F), one type may be used alone, or two or more types may be mixed and used.

As the lower limit of the content of the polymerizable compound (F), 1 part by mass is preferable, 3 parts by mass is more preferable, and 5 parts by mass is further preferable with respect to 100 parts by mass of the polymer (A). On the other hand, as the upper limit, 100 parts by mass is preferable, 50 parts by mass is more preferable, 20 parts by mass is further preferable, and 10 parts by mass is particularly preferable. By setting the content of the polymerizable compound (F) in the above range, the hardness of the obtained film can be increased.

<Radiation-sensitive polymerization initiator (G)>
The radiation-sensitive polymerization initiator (G) is a compound that initiates or promotes the polymerization of the polymerizable compound (F) by being irradiated with radiation. Therefore, when the film-forming composition contains the polymerizable compound (F), it is preferable to use the radiation-sensitive polymerization initiator (G).

Examples of the radiation-sensitive polymerization initiator (G) include an O-acyloxime compound, an acetophenone compound, and a biimidazole compound.

Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and 1- [9. -Ethyl-6-benzoyl-9. H. -Carbazole-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, ethane-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl) } -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.

Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

Examples of the aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4). -Molphorin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and the like can be mentioned.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. , 4- (2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2. '-Bis (2-chlorophenyl) -4,4', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5 , 5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'- Biimidazole and the like can be mentioned.

When a biimidazole compound is used as the radiation-sensitive polymerization initiator (G), an aliphatic or aromatic compound having a dialkylamino group can be used in combination to sensitize the biimidazole compound. Examples of the aliphatic or aromatic compound having such a dialkylamino group include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.

As the radiation-sensitive polymerization initiator (G), an O-acyloxime compound and an acetophenone compound are preferable. As the acetophenone compound, an aminoketone compound is preferable. As the radiation-sensitive polymerization initiator (G), one type may be used alone, or two or more types may be mixed and used.

The lower limit of the content of the radiation-sensitive polymerization initiator (G) is preferably 0.05 parts by mass, more preferably 0.1 parts by mass, based on 100 parts by mass of the polymer (A). On the other hand, as the upper limit, 10 parts by mass is preferable, and 2 parts by mass is more preferable. By setting the content of the radiation-sensitive polymerization initiator (G) in the above range, the film-forming composition can sufficiently cure the coating film with high radiation sensitivity even at a low exposure amount.

<Other optional ingredients>
The film-forming composition may further contain other optional components as long as the effects of the present invention are not impaired. Examples of other optional components include surfactants, storage stabilizers, adhesive aids, heat resistance improvers and the like. As for the other optional components, one type may be used alone, or two or more types may be mixed and used.

<Laminated wiring>
The laminated wiring according to an embodiment of the present invention is a laminated wiring obtained by the above-mentioned method for forming a laminated wiring. Since the laminated wiring is obtained by the above-mentioned forming method, it can be excellent in productivity and can reduce the cost.

The laminated wiring can be suitably used for semiconductor elements and electronic circuits. Further, the semiconductor element and the electronic circuit can be suitably used for an electronic device and the like. The electronic device using the laminated wiring can be miniaturized, thinned, and highly functional. Examples of the electronic device include a liquid crystal display, a portable information device, a digital camera, an organic display, an organic EL lighting, a sensor, a wearable device, and the like.

<Other Embodiments>
The method for forming the laminated wiring and the laminated wiring of the present invention are not limited to the above-described embodiment. For example, in the method for forming the laminated wiring, it is possible to form a multilayer laminated wiring having three or more conductive layers (wiring). In this case, for example, by repeating the step (B) and the step (C) a plurality of times, a multi-layer laminated wiring can be formed. On the other hand, as a step (A) of preparing a base material having the first conductive layer as the outermost layer, instead of forming the first conductive layer using a composition for forming a base film or the like, an existing substrate with a conductive layer is prepared. You can also use it as it is. The method for forming the laminated wiring is a method capable of obtaining a pattern after irradiation with radiation without going through a developing step using a developing solution. However, in the forming method, for example, a developing process or a cleaning process can be performed instead of or in combination with heating after irradiation.

Further, as the acid generator contained in the insulating film forming composition or the base film forming composition, a heat-sensitive acid generator or the like can be used. In this case, instead of irradiation, an acid can be generated by heating a part of the surface region to form a lyophilized surface region. A part of the surface region can be heated by, for example, a laser. In addition, a part of the surface region may be heated by irradiation with radiation.

Further, the insulating film does not have to be provided with holes for vias. In this case, it is possible to form a laminated wiring in which the first conductive layer and the second conductive layer are not conducting (insulated).

Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not construed as being limited to this Example. The measurement method used in this example is shown below.

[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The polystyrene-equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymers obtained in the following synthetic examples were measured under the following conditions.
-Measurement method: Gel permeation chromatography (GPC) method-Standard substance: Polystyrene conversion-Device: Tosoh's "HLC-8220"
-Column: Tosoh's guard columns "H _XL- H", "TSK gel G7000H _XL ", two "TSK gel GMH _XL ", and "TSK gel G2000H _XL " are connected in sequence.-Solvent: tetrahydrofuran-Sample concentration : 0.7% by mass
・ Injection amount: 70 μL
・ Flow velocity: 1 mL / min

[ ¹ Measurement of ¹ H-NMR]
¹ H-NMR was measured under the condition of a temperature of 25 ° C. using CDCl ₃ as a solvent and a nuclear magnetic resonance apparatus (“AVANCE III AV400N” manufactured by Bruker).

<Synthesis of polymer>
[Synthesis Example 1]
In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol. 200 parts by mass of dimethyl ether was charged. Subsequently, 42 parts by mass of 2-hydroxyethyl methacrylate and 58 parts by mass of benzyl methacrylate are charged, and the temperature of the solution is raised to 80 ° C. while gently stirring in a nitrogen atmosphere, and this temperature is maintained for 4 hours for polymerization. As a result, a solution containing the copolymer (A-1) was obtained (solid content concentration = 34.6% by mass). The solid content concentration means the ratio of the copolymer mass to the total mass of the copolymer solution. The obtained solution was added dropwise to a large excess of hexane, and the precipitate was dried to obtain a white solid polymer (A-1) (Mw = 26000, Mw / Mn = 2.2).

Next, 10 parts by mass of the solution containing the obtained polymer (A-1), 13 parts by mass of diethylene glycol dimethyl ether, and 3,3,4,4,5,5,6,6,7,7,8,8 , 8-Tridecafluoro-1-vinyloxyoctane (4.8 parts by mass) was added, and the mixture was sufficiently stirred. Then, 0.27 parts by mass of trifluoroacetic acid was added, and the mixture was reacted at 80 ° C. for 9 hours under a nitrogen atmosphere. Subsequently, the reaction solution was cooled to room temperature, 0.3 parts by mass of pyridine was added, and the reaction was quenched. Reprecipitation purification was performed by dropping the obtained reaction solution into a large excess of methanol. Subsequently, the precipitate was dissolved in 10 parts by mass of diethylene glycol dimethyl ether, then reprecipitated by dropping it in a large excess of hexane, and the precipitate was dried to form a polymer as a white solid copolymer. (P-1) 6.8 parts by mass was obtained. The obtained polymer (P-1) was analyzed by ¹ H-NMR, and it was confirmed that acetalization was proceeding (chemical shift: 4.80 ppm, acetal group CH).

[Synthesis Example 2]
In a flask equipped with a condenser and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol dimethyl ether. 200 parts by mass was charged. Subsequently, 42 parts by mass of 2-hydroxyethyl methacrylate, 37 parts by mass of N-cyclohexylmaleimide, and 21 parts by mass of styrene were charged, substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring to reach this temperature. Was held for 4 hours for polymerization to obtain a solution containing the polymer (A-2) which is a copolymer. The obtained solution was added dropwise to a large excess of hexane, and the precipitate was dried to obtain a white solid polymer (A-2) (Mw = 20100, Mw / Mn = 2.1).

Next, 10 parts by mass of the polymer (A-2) was dissolved in 45 parts by mass of tetrahydrofuran, and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-. 13.8 parts by mass of 1-vinyloxyoctane was added, and after sufficient stirring, 0.77 parts by mass of trifluoroacetic acid was added, and the mixture was reacted at 60 ° C. for 8 hours under a nitrogen atmosphere. Subsequently, the reaction solution was cooled to room temperature, 1.0 part by mass of pyridine was added, and the reaction was quenched. Reprecipitation purification was performed by dropping the obtained reaction solution into an excess amount of methanol. Subsequently, the precipitate was dissolved again in 30 parts by mass of tetrahydrofuran, then reprecipitated and purified by dropping it in hexane, and the precipitate was dried to form a polymer (P-2) as a white solid copolymer. ) 16.5 parts by mass was obtained. The obtained polymer (P-2) was analyzed by ¹ H-NMR, and it was confirmed that acetalization was proceeding (chemical shift: 4.80 ppm, acetal group CH).

[Synthesis Example 3]
8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and propylene glycol in a flask equipped with a cooling tube and a stirrer. 200 parts by mass of monomethyl ether acetate was charged. Subsequently, 30 parts by mass of methacrylic acid and 70 parts by mass of benzyl methacrylate were charged, substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was maintained for 4 hours for polymerization. A solution containing a polymer (A-3), which is a copolymer, was obtained. The obtained solution was added dropwise to a large excess of hexane, and the precipitate was dried to obtain a white solid polymer (A-3) (Mw = 24000, Mw / Mn = 2.2).

Next, 5 parts by mass of the polymer (A-3) was dissolved in 34 parts by mass of diethylene glycol dimethyl ether, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10 , 10,10-Heptadecafluoro-1-vinyloxydecane 9.4 parts by mass was added, and after sufficient stirring, 0.09 parts by mass of pyridinium paratoluenesulfonate was added and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere. I let you. Subsequently, the reaction solution was cooled to room temperature, 0.04 part by mass of pyridine was added, and the reaction was quenched. Reprecipitation purification was performed by dropping the obtained reaction solution into an excess amount of methanol. Subsequently, the precipitate was dissolved again in 15 parts by mass of diethylene glycol dimethyl ether, then reprecipitated by dropping it in hexane, and the precipitate was dried to form a polymer (P-) as a white solid copolymer. 3) 10.9 parts by mass was obtained. The obtained polymer (P-3) was analyzed by ¹ H-NMR, and it was confirmed that acetalization was proceeding (chemical shift: 5.74 ppm, acetal group CH).

[Synthesis Example 4]
In a flask equipped with a condenser and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol dimethyl ether. 200 parts by mass was charged. Subsequently, 56 parts by mass of p-hydroxyphenyl methacrylate, 28 parts by mass of N-cyclohexyl maleimide, and 16 parts by mass of styrene were charged, replaced with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring to raise this temperature. By holding and polymerizing for 4 hours, a solution containing a polymer (A-4) which is a copolymer was obtained. The obtained solution was added dropwise to a large excess of hexane, and the precipitate was dried to obtain a white solid polymer (A-4) (Mw = 20500, Mw / Mn = 2.0).

Next, 10 parts by mass of the polymer (A-4) was dissolved in 45 parts by mass of tetrahydrofuran, and 3,3,4,5,5,6,6,7,7,8,8,8-tridecafluoro-. 13.5 parts by mass of 1-vinyloxyoctane was added, and after sufficient stirring, 0.079 parts by mass of trifluoroacetic acid was added, and the mixture was reacted at 60 ° C. for 8 hours under a nitrogen atmosphere. Subsequently, the reaction solution was cooled to room temperature, 1.1 parts by mass of pyridine was added, and the reaction was quenched. Reprecipitation purification was performed by dropping the obtained reaction solution into an excess amount of methanol. Subsequently, the precipitate was dissolved again in 30 parts by mass of tetrahydrofuran, then reprecipitated and purified by dropping it in hexane, and the precipitate was dried to form a polymer (P-4) as a white solid copolymer. ) 17.5 parts by mass was obtained. The obtained polymer (P-4) was analyzed by ¹ H-NMR, and it was confirmed that acetalization was proceeding (chemical shift: 5.50 ppm, acetal group CH).

[Synthesis Example 5]
To a flask equipped with a cooling tube and a stirrer, 5 parts by mass of polyvinylphenol (“Marukalinker S-4P” manufactured by Maruzen Petrochemical Co., Ltd.) was added and dissolved in 50 parts by mass of tetrahydrofuran to 3, 3, 4, 4, 5,. Add 16 parts by mass of 5,6,6,7,7,8,8,8-tridecafluoro-1-vinyloxyoctane, and after sufficient stirring, add 0.50 parts by mass of trifluoroacetic acid under a nitrogen atmosphere. , 60 ° C. for 9 hours. Subsequently, the reaction solution was cooled to room temperature, 0.5 part by mass of pyridine was added, and the reaction was quenched. Reprecipitation purification was performed by dropping the obtained reaction solution into an excess amount of methanol. Subsequently, the precipitate was dissolved again in 30 parts by mass of tetrahydrofuran, then reprecipitated and purified by dropping it in hexane, and the precipitate was dried to form a polymer (P-5) as a white solid copolymer. ) Was obtained. The obtained polymer (P-5) was analyzed by ¹ H-NMR, and it was confirmed that acetalization was proceeding (chemical shift: 5.48 ppm, acetal group CH).

[Synthesis Example 6]
To a flask equipped with a cooling tube and a stirrer, 5 parts by mass of a phenol novolac resin (“P-200” manufactured by Arakawa Chemical Industry Co., Ltd.) represented by the following formula was added and dissolved in 60 parts by mass of tetrahydrofuran to 3, 3, 4, Add 20 parts by mass of 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-vinyloxydecane, stir well and then trifluoro 0.50 parts by mass of acetic acid was added, and the mixture was reacted at 60 ° C. for 9 hours under a nitrogen atmosphere. Subsequently, the reaction solution was cooled to room temperature, 0.5 part by mass of pyridine was added, and the reaction was quenched. Reprecipitation purification was performed by dropping the obtained reaction solution into an excess amount of methanol. Subsequently, the precipitate was dissolved again in 30 parts by mass of tetrahydrofuran, then reprecipitated by dropping it in hexane, and the precipitate was dried to form a polymer (P-6) as a white solid copolymer. ) 12.1 parts by mass was obtained. The obtained polymer (P-6) was analyzed by ¹ H-NMR, and it was confirmed that acetalization was proceeding (chemical shift: 5.49 ppm, acetal group CH).

[Synthesis Example 7]
In a flask equipped with a condenser and a stirrer, 25 parts by mass of 2-hydroxyethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro 101 parts by mass of -1-vinyloxy-octane, 2.0 parts by mass of trifluoroacetic acid (TFA) and 200 parts by mass of tetrahydrofuran (THF) were charged and kept at 60 ° C. for 9 hours under a nitrogen atmosphere for reaction. After cooling, 2.1 parts by mass of pyridine was added to the reaction solution and quenched. The obtained reaction solution was washed with water, separated, the solvent was removed with a rotary evaporator, and the unreacted components were removed by vacuum distillation to obtain the following acetal product (M-1).

Next, in a flask equipped with a cooling tube and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 2 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), and 200 parts by mass of propylene glycol monomethyl ether was charged. Subsequently, 70 parts by mass of the above-mentioned acetalized product (M-1) and 30 parts by mass of benzyl methacrylate were charged, substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring to reach this temperature. Was held for 4 hours and polymerized to obtain a solution containing the copolymer (P-7) (Mw = 22200, Mw / Mn = 2.3, ¹ H-NMR chemical shift: 4.80 ppm, acetal group CH).

[Synthesis Example 8]
In a flask equipped with a cooling tube and a stirrer, 25 parts by mass of hydroxyphenyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1- 82 parts by mass of vinyloxy-octane, 1.6 parts by mass of trifluoroacetic acid (TFA), and 200 parts by mass of tetrahydrofuran (THF) were charged and kept at 60 ° C. for 9 hours under a nitrogen atmosphere for reaction. After cooling, 1.7 parts by mass of pyridine was added to the reaction solution and quenched. The obtained reaction solution was washed with water, separated, the solvent was removed with a rotary evaporator, and the unreacted components were removed by vacuum distillation to obtain the following acetal product (M-2).

Next, in a flask equipped with a cooling tube and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 2 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), and 200 parts by mass of propylene glycol monomethyl ether was charged. Next, 75 parts by mass of the obtained acetalized product (M-2) and 25 parts by mass of benzyl methacrylate were charged, substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. By holding this temperature for 4 hours and polymerizing, a solution containing a polymer (P-8) which is a copolymer was obtained (Mw = 23200, Mw / Mn = 2.2, ^{1 1} H-NMR chemistry). Shift: 5.50 ppm, acetal group CH).

[Synthesis Example 9]
In a flask equipped with a cooling tube and a stirrer, 25 parts by mass of 2- (2-vinyloxyethoxy) ethyl methacrylate (“VEEM” of Nippon Catalyst Co., Ltd.), 3,3,4,4,5,5,6 Add 45 parts by mass of 6,7,7,8,8,8-tridecafluorooctanol, 1.6 parts by mass of pyridinium paratoluenesulfonate (PPTSA), and 200 parts by mass of tetrahydrofuran (THF) at room temperature in a nitrogen atmosphere. It was held for 8 hours and reacted. After completion of the reaction, 0.7 parts by mass of pyridine was added to the reaction solution for quenching. The obtained reaction solution was washed with water, separated, the solvent was removed with a rotary evaporator, and the unreacted components were removed by vacuum distillation to obtain the following acetal product (M-3).

Next, in a flask equipped with a cooling tube and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and 2 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), and 200 parts by mass of propylene glycol monomethyl ether was charged. Next, 75 parts by mass of the obtained acetalized product (M-3) and 25 parts by mass of benzyl methacrylate were charged, substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. Polymerization was carried out at a temperature of 4 hours to obtain a solution containing the copolymer (P-9) (Mw = 24200, Mw / Mn = 2.1, chemical shift: 4.80 ppm). , Acetal group CH).

<Preparation of film-forming composition>
Details of each component used in Examples and Comparative Examples are shown below.
<Polymer (A)>
P-1: Polymer synthesized in Synthesis Example 1 (P-1)
P-2: Polymer synthesized in Synthesis Example 2 (P-2)
P-3: Polymer synthesized in Synthesis Example 3 (P-3)
P-4: Polymer synthesized in Synthesis Example 4 (P-4)
P-5: Polymer synthesized in Synthesis Example 5 (P-5)
P-6: Polymer synthesized in Synthesis Example 6 (P-6)
P-7: Polymer synthesized in Synthesis Example 7 (P-7)
P-8: Polymer synthesized in Synthesis Example 8 (P-8)
P-9: Polymer synthesized in Synthesis Example 9 (P-9)
A-1: Polymer (A-1) synthesized in Synthesis Example 1
A-3: Polymer synthesized in Synthesis Example 3 (A-3)
<Acid generator (B)>
C-1: N-Hydroxynaphthalimide-trifluoromethanesulfonic acid ester C-2: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate C-3: (5-octylsulfonyloxyimino) )-(4-Methoxyphenyl) acetonitrile (BASF's "CGI725")
<Sensitizer (D)>
D-1: 2-isopropylthioxanthone D-2: 2,4-diethylthioxanthene-9-one <quencher (E)>
E-1: 2-Phenylbenzimidazole E-2: 4- (dimethylamino) pyridine <Polymerizable compound (F)>
F-1: Dipentaerythritol hexaacrylate F-2: 1,9-nonanediol diacrylate <Radiation-sensitive polymerization initiator (G)>
G-1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (BASF's "Irgacure® 907")
G-2: 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one (BASF's "Irgacure® 379" )
G-3: Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) (BASF's "Irgacure® OXE02" ”)

[Preparation Examples 1 to 9 and Comparative Preparation Examples 1 to 2]
Each component of the type and content shown in Table 1 was mixed, and propylene glycol monomethyl ether acetate was added as the solvent (B) so that the solid content concentration was 10% by mass. Then, each film-forming composition was prepared by filtering with a membrane filter having a pore size of 0.5 μm. In addition, "-" in Table 1 indicates that the corresponding component was not used.

<Formation and evaluation of laminated wiring>
Laminated wiring was formed using each film-forming composition prepared in Preparation Examples 1 to 9 and Comparative Preparation Examples, and the following evaluation was carried out. The results are shown in Table 2. Examples 1 to 9 are those using the film-forming compositions of Preparation Examples 1 to 9, respectively, and Comparative Examples 1 and 2 are those using the film-forming compositions of Comparative Preparation Examples 1 and 2, respectively. ..

[Formation of wiring of the first layer (first conductive layer)]
The film-forming compositions prepared in Preparation Examples 1 to 9 or Comparative Preparation Examples 1 and 2 are each applied on a glass substrate (“EAGLE-XG” manufactured by Corning Inc.) with a spinner, and then placed in a clean oven at 90 ° C. A 0.2 μm thick coating film was formed by prebaking for 5 minutes. Next, a high-pressure mercury lamp (“MA-1400” manufactured by Dainippon Kaken Co., Ltd.) was used for the obtained coating film, and the exposure amount was 250 mJ / cm via a quartz mask (L / S = 50 μm / 450 μm, contact). Irradiation was performed as ² . Then, by baking at 110 ° C. for 15 minutes using a hot plate, a parent-repellent patterning substrate (a substrate having a base film having a liquid-repellent surface region and a liquid-repellent surface region) was formed.

By immersing the patterning surface of the repellent patterning substrate in silver nanoink ("NPS-JL" of Harima Chemicals, Inc.), immediately pulling it up and holding the substrate at an angle of 45 ° or more for 1 minute, the silver nanoink can be obtained. A patterned substrate was obtained. After that, a high-pressure mercury lamp (“MA-1400” manufactured by Dainippon Kaken Co., Ltd.) was used to irradiate the entire surface of the substrate on which silver nanoink was patterned with an exposure amount of 250 mJ / cm ² , and then a hot plate at 120 ° C./30. Bake for a minute. As a result, the liquid-repellent portion was removed, and a substrate (a substrate having the first conductive layer on the outermost surface) was obtained in which silver wiring as a linear first conductive layer was formed at L / S = 50 μm / 450 μm. An image of the "base material on which the first conductive layer is formed" of Example 1 is shown in FIG.

[Applicability of the second layer film-forming composition]
The film-forming compositions prepared in Preparation Examples 1 to 9 or Comparative Preparation Examples 1 and 2 are respectively applied to the substrate on which the first conductive layer obtained in the above step is formed with a spinner, and then at 90 ° C. By prebaking on a hot plate for 2 minutes, a second layer coating film having a thickness of 1.0 μm was formed. If the coating film at this time had no coating unevenness, it was visually confirmed as good (A), and if there was remarkable coating unevenness, it was visually confirmed as defective (B).

[Contact angle of the coating film formed on the second layer]
A high-pressure mercury lamp (“MA-1400” from Dainippon Kaken Co., Ltd.) was used for the coating film formed by the above “coatability of the film forming composition for the second layer”, and a quartz mask (contact) was applied. Irradiation was performed with an exposure amount of 250 mJ / cm ² . Then, by baking at 110 ° C. for 15 minutes using a hot plate, a liquid-soluble surface area (exposed area) and a liquid-repellent surface area (non-exposed area) were formed.

After that, using a contact angle meter (“CA-X” manufactured by Kyowa Interface Science Co., Ltd.), the contact angles of water and tetradecane on the coating film surface of the exposed part and the coating film surface of the unexposed part were measured, and the contact angle was measured. I confirmed the performance. In Table 2, the contact angle of water on the surface of the exposed portion is referred to as "parent liquid portion water", and the contact angle of water on the surface of the non-exposed portion is indicated as "liquid repellent portion water". The same applies to the contact angle of tetradecane.

[Confirmation of concave patterning property of the coating film formed on the second layer]
In the coating film formed by the above-mentioned "coatability of the film-forming composition for the second layer", a quartz mask (L / S = 50 μm) was used using a high-pressure mercury lamp (“MA-1400” manufactured by Dainippon Kaken Co., Ltd.). Irradiation was performed with an exposure amount of 250 mJ / cm ² via (/ 450 μm, contact). Then, by baking at 110 ° C. for 15 minutes using a hot plate, a substrate having a repellent pattern was formed in the second layer. After that, the film thickness of the exposed portion (concave portion) which is the liquid-repellent surface region and the non-exposed portion (convex portion) which is the liquid-repellent surface region are measured with a contact type film thickness meter (Keyence's "Alpha Step IQ"). Then, the depth of the recess was determined. An image of "a substrate on which a repellent pattern is formed on the second layer" of Example 1 is shown in FIG. In FIG. 5, a second layer repellent pattern is formed in the left-right direction.

[Confirmation of laminated wiring formability]
Immerse the patterning surface of the substrate having the repellent pattern in the second layer obtained in the above "confirmation of concave patterning property of the coating film formed in the second layer" in silver nanoink ("NPS-JL" of Harima Kasei Co., Ltd.). Then, the substrate was immediately pulled up and held at an angle of 45 ° or more for 1 minute to form a substrate on which the second layer of silver nanoink was patterned. After that, the entire surface of the substrate on which the silver nanoink was patterned was formed. Using a high-pressure mercury lamp (“MA-1400” manufactured by Dainippon Kaken Co., Ltd.), irradiation was performed with an exposure amount of 250 mJ / cm ² , and then baked on a hot plate at 120 ° C./30 minutes. The liquid-repellent portion was removed to obtain a substrate on which silver wiring of L / S = 50 μm / 450 μm was formed. At this time, it is good if the silver wiring of L / S = 50 μm / 450 μm is formed with good patterning property ( A), if there was a patterning defect, it was confirmed as a defect (B) by visual inspection and an optical microscope (Nikon's "Eclipse L200D"). Note that the "second layer silver wiring (second conductive layer)" of Example 1 was confirmed. ) Is formed in the substrate, which is shown in FIGS. 6 and 7.

<Three-dimensional continuity evaluation by laser processing>
The film-forming compositions prepared in Preparation Examples 1 to 9 and Comparative Preparation Examples 1 and 2 were used to form a film on an ITO substrate, and the following evaluations were carried out. The results are shown in Table 2.

[Hole formation]
The film-forming compositions prepared in Preparation Examples 1 to 9 or Comparative Preparation Examples 1 and 2 are each applied with a spinner onto a glass substrate on which ITO is formed, and then prebaked in a clean oven at 90 ° C. for 5 minutes. As a result, a coating film having a thickness of 0.2 μm was formed. Next, a high-pressure mercury lamp (“MA-1400” manufactured by Dainippon Kaken Co., Ltd.) was used for the obtained coating film, and the exposure amount was 250 mJ / cm ² via a quartz mask (L / S = 50 μm / 450 μm, contact). Irradiation was performed as. Then, the parent-repellent patterning substrate was formed by baking at 110 ° C. for 15 minutes using a hot plate.

A 20 μm square hole was formed in the parent liquid portion (parent liquid surface region) of the obtained parent-repellent patterning substrate by a YAG laser thin film processing device (“VL-C” of TNS Systems GK, oscillation wavelength: 266 nm). .. The observation was carried out with an optical microscope (“Eclipse L200D” manufactured by Nikon Corporation), and evaluation was made as good (A) if holes could be formed, and poor (B) if residues remained in the holes. In Comparative Examples 1 and 2, since patterning could not be performed, holes were not formed.

[3D continuity confirmation]
An inkjet device (Fujifilm's "Dimatic DMP-2831") is used for the parent liquid portion of the repellent pattern substrate having holes obtained by the above "concave pattern formation on the ITO substrate and hole formation by laser processing". Silver nano ink (“NPS-JL” manufactured by Harima Kasei Co., Ltd.) was applied to form a silver nano ink pattern only on the parent liquid part. Then, it was baked on a hot plate at 120 ° C./30 minutes to obtain a substrate on which silver wiring having a width of 50 μm was formed. It was confirmed by SEM observation that the holes formed by the laser processing were filled with silver generated from the silver nanoink. The images of "the substrate on which the silver wiring (second conductive layer and via conductor) are formed" of Example 1 are shown in FIGS. 8 and 9. FIG. 8 is a plan view image, and FIG. 9 is an SEM image.

A Keithley 2000-inch digital multimeter was used to measure the resistance between the silver wiring and the ITO on the substrate surface. If the continuity was confirmed, it was evaluated as good (A) because it means that the three-dimensional conduction was performed through the hole filled with silver, and if the continuity was not obtained, it was evaluated as a three-dimensional conduction failure (B). In Comparative Examples 1 and 2, since patterning could not be performed, holes were not formed.

According to Examples 1 to 9 using the film-forming compositions of Preparation Examples 1 to 9 as shown in Table 2, a good repellent pattern (wetability pattern) can be formed, and a good repellent pattern (wetability pattern) can be formed between the conductive layers. It can be seen that a laminated wiring having good conductivity can be obtained.

The method for forming a laminated wiring of the present invention can efficiently form a three-dimensional wiring pattern and can be used for printed electronics and the like. Further, the laminated wiring obtained by the method for forming the laminated wiring of the present invention is suitable for electronic circuits provided in electronic devices such as liquid crystal displays, portable information devices, digital cameras, organic displays, organic EL lighting, sensors, and wearable devices. It can be used.

10 Substrate 11 Base coating film 12 Hydrophilic surface area 13 Liquid-repellent surface area 14 First conductive layer 15 Base film 16 Base film 17 Insulation coating film 18 Hydrophilic surface area 19 Liquid-repellent surface area 20 Via holes 21 Second conductive layer 22 Via conductor 23 Insulating film 24 Laminated wiring hν Radiation

Claims (6)

Step (A) of preparing a base material having the first conductive layer as the outermost layer,
By the step (B) of forming an insulating film having a liquid-repellent surface region and a liquid-based surface region on the surface of the base material, and by contacting the surface of the insulating film with the material for forming the second conductive layer. Step (C) of Forming a Second Conductive Layer Laminated on the Hydrophilic Surface Region of the Insulating Film
With
The insulating film forming step (B)
A liquid-repellent surface is provided by a composition for forming an insulating film containing a first polymer containing a structural unit having an acid dissociating group containing a fluorine atom and a first acid generator which is a radiation-sensitive acid generator. Step (Bi) of forming an insulating coating having
By irradiating a part of the surface area of the insulating coating film with radiation, the step of forming the positivity surface region on a part of the surface area of the insulating coating film (B-ii) and the radiation were irradiated. Step of heating the insulating coating film (B-iii)
With
The structural units, Ri least one Der structural unit represented by the following formulas from the following equation (1) (4),
The above preparation step (A)
A step of forming a base coating film having a liquid-repellent surface by a composition for forming a base film containing a second polymer having an acid dissociative group and a second acid generator which is a radiation-sensitive acid generator. (Ai),
A step (A-ii) of forming a liquor-friendly surface region on a part of the surface region of the base coating film by irradiating a part of the surface region of the base coating film with radiation.
A step (A-iii) of applying the first conductive layer forming material to the surface of the base coating film on which the lipophilic surface region is formed.
The step (A-iv) of irradiating the entire surface of the surface coated with the first conductive layer forming material with radiation, and
Step of heating the base material coated with the material for forming the first conductive layer (Av)
With
The step (Av) of heating the base material coated with the material for forming the first conductive layer is performed after the step (Av) of irradiating the entire surface with radiation.
A method for forming a laminated wiring in which a liquid-forming surface region formed on the undercoat film is a recess and the depth of the recess is 0.1 μm or more .

(In formulas (1) to (4), R ¹ is an independent hydrogen atom or a methyl group, and R ² is an independent methylene group, an alkylene group having 2 to 12 carbon atoms, and a carbon. An alkenylene group having a number of 2 to 12, a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or one or more hydrogens contained in these groups. A group in which an atom is substituted with a substituent. R ³ is a hydrocarbon group in which one or more hydrogen atoms are substituted with a fluorine atom, respectively. M is 0 or 0 or each independently. 1. n is an independently integer from 0 to 12.) The insulating film forming step (B)
Further provided with a step of forming holes for vias by irradiating a part of the wicking surface region of the insulating coating film with a laser.
The first aspect of the present invention, wherein in the second conductive layer forming step, a via conductor connecting the first conductive layer and the second conductive layer is formed together with the second conductive layer by the material for forming the second conductive layer. How to form laminated wiring. The method for forming a laminated wiring according to claim 1 or 2, wherein a part of the surface area of the insulating coating film is irradiated with radiation by exposure through a photomask. The method for forming a laminated wiring according to any one of claims 1 to 3, wherein the wicking surface region formed on the insulating film is a recess. The preparation step (A) is performed before the step (A-iii) of applying the first conductive layer forming material .
The method for forming a laminated wiring according to any one of claims 1 to 4, further comprising a step of heating the base coating film irradiated with radiation. Method for forming a multilayer wiring according to any one of claims 1 to 5 and the composition for forming an insulating film and the underlying film-forming composition is the same composition.

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