JP2016090639A - Method for manufacturing base material including metal wire, polarization element, and electrode substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a base material including a metal wire capable of suppressing wet spreading and oozing of composition for forming a metal wire and capable of forming a high-definition metal wire on the base material, and to provide a polarization element and an electrode substrate.SOLUTION: A method for manufacturing a base material including a metal wire includes the steps of: (i) forming a coating film of a composition for forming a film that contains an acid-generating agent and a polymer having an acid-dissociable group on a substrate 1; (ii) irradiating a prescribed portion of the coating film with radioactive rays; (iii) providing a layer of a composition for forming a metal wire having a line width of 0.1 μm to 20 μm on the coating film that is irradiated with radioactive rays; and (iv) heating the layer of the composition for forming a metal wire to form a pattern 6 to become a metal wire. A polarization element and an electrode substrate are manufactured according to the method for manufacturing a base material including a metal wire.SELECTED DRAWING: Figure 5

Description

  The present invention relates to a method for producing a base material having a metal wire, a polarizing element and an electrode substrate, and more particularly to a method for producing a base material having a metal wire and a polarizing element and an electrode substrate produced using the method.

  2. Description of the Related Art In recent years, development of a technique for manufacturing an electrode substrate for a polarizing element and a display element by arranging extremely thin metal wires called nanowires on a base material in a lattice shape has been actively promoted.

  For example, the polarizing element described in Patent Document 1 is called a wire grid type, and a plurality of extremely thin metal wires are arranged in a lattice shape on a substrate, and the interval between the metal wires is considerably smaller than the wavelength of visible light. Can be manufactured. Since this wire grid type polarization element can be polarized by utilizing reflection of light, it is also desirable from the viewpoint of effective use of light.

  Moreover, an electrode substrate can be manufactured by providing a very thin metal wire having a line width of about 100 nm in a lattice shape on a light-transmitting substrate serving as a base material. In such an electrode substrate, the line width of the metal line is extremely narrow, and an opening is formed between adjacent metal lines, thereby realizing a high aperture ratio. Therefore, it is excellent in light transmittance and can be used for manufacturing a display element for a transmissive display element. An electrode substrate having an extremely thin metal wire as an electrode is expected to be an alternative to an electrode substrate with ITO using ITO as an electrode, which is feared to be depleted of raw materials.

  In order to realize the polarizing element and the electrode substrate as described above, as described above, for example, a plurality of metal lines having a line width of about 100 nm are formed on a substrate serving as a base material, and they are arranged in a lattice pattern. Technology is required. However, it is difficult to form such an extremely thin metal wire on a substrate simply and with high throughput by a well-known conventional photolithography method.

  Therefore, printed electronics technology that can directly print a pattern capable of forming a grid-like metal line has attracted attention. This technique can omit a multi-step process including development of an exposed pattern and a vacuum process such as a vapor deposition method, which are included in a normal photolithography method, and is expected to greatly simplify the process.

  Printing methods such as inkjet, screen printing, gravure printing, and gravure offset printing can be used as a simple and low-cost process because a metal line having a desired shape can be formed directly on a substrate. However, in forming a metal wire, the liquid or ink-like metal wire forming material used for printing flows, and as a result, these wetting spread and bleeding occur, and the metal wire is formed as a fine pattern with excellent linearity. There was a limit.

  Moreover, although the metal wire formation composition used as a metal wire formation material is patterned by printing, and the technique which forms a metal wire by thermal baking or light baking is actively examined (for example, refer patent document 2). In addition to the problem of material spreading and bleeding during printing, there was a problem in the adhesion of the resulting wiring to the substrate.

  In view of this, a technique for solving the above-described problems to enable high-definition printing and providing a layer (underlayer) serving as a base of wiring for forming a high-definition metal line has been studied. The base treatment for providing the base layer is often performed for the purpose of suppressing wet spread, bleeding, etc. of the metal line forming composition applied on the substrate and improving printability.

  For example, a technique of grafting an epoxy group on a substrate that is a base material is known (see, for example, Patent Document 3 and Patent Document 4). Moreover, the technique of apply | coating a photocatalyst on a board | substrate is known (for example, refer patent document 5 and patent document 6). Furthermore, a technique for applying an acrylic copolymer on a substrate is known (see, for example, Patent Document 7 and Patent Document 8).

JP 2006-84776 A JP 2011-241309 A JP 2003-114525 A JP 2006-58797 A JP 2003-209340 A JP 2004-98351 A JP 2012-232434 A JP 2012-218318 A

  However, in the base treatment for providing a conventional base layer, after the metal wire forming composition, which is a metal wire forming material, is printed, the wetting, spreading and bleeding are not sufficiently suppressed. Therefore, for example, it is difficult to form a high-definition metal line having a line width of 0.1 μm to 20 μm, that is, 0.1 μm to 20 μm. From a metal line having a line width of 0.1 μm to 20 μm It was difficult to dispose a metal grid having a period greater than 0.1 μm and not greater than 200 μm. For example, in the conventional ground treatment, the properties of the ground layer surface to which the metal line forming composition is applied are uniform. For this reason, when the metal line forming composition was printed in a predetermined pattern, it was not possible to sufficiently suppress the composition from spreading immediately after printing.

  The present invention has been made based on the above findings. That is, an object of the present invention is to form a high-definition metal wire having a line width of 0.1 μm to 20 μm on a substrate while suppressing the wetting and spreading of the metal wire forming composition for forming the metal wire. It is providing the manufacturing method of the base material which has a metal wire.

  Another object of the present invention is to manufacture a substrate having a metal wire as described above, and to have a metal lattice made of a metal wire on the substrate, and the period of the metal lattice is from 0.1 μm. The object is to provide a polarizing element having a size of 200 μm or less.

  Another object of the present invention is to provide an electrode substrate that is manufactured using the above-described method for manufacturing a base material having a metal wire, and that has a high-definition metal lattice made of metal wires on the base material substrate. It is in.

  Other objects and advantages of the present invention will become apparent from the following description.

1st aspect of this invention is related with the manufacturing method of the base material which has a metal wire characterized by having the process of following (i)-(iv).
(I) The process of forming the coating film of the film forming composition containing the polymer which has an acid dissociable group, and an acid generator on a base material (ii) The process of irradiating a predetermined part of the said coating film with radiation (iii) ) A step of providing a layer of a metal line forming composition having a line width of 0.1 μm to 20 μm on the coating film irradiated with the radiation. (Iv) A step of heating the layer of the metal line forming composition.

  1st aspect of this invention WHEREIN: It is preferable that the process of (ii) includes the process of heating the coating film after the said radiation irradiation.

  In the first aspect of the present invention, the acid dissociable group preferably contains a fluorine atom.

  In the first aspect of the present invention, the acid dissociable group is preferably a group containing at least one structural unit selected from the group of an acetal bond and a hemiacetal ester bond.

  In the first aspect of the present invention, when the acid dissociable group is a group containing at least one structural unit selected from the group of an acetal bond and a hemiacetal ester bond, the group of the acetal bond and the hemiacetal ester bond It is preferable that the group containing at least one structural unit selected from has at least one selected from the group of structural units represented by the following formula (1-1) and the following formula (1-2).

（式（１−１）および（１−２）中、Ｒ^１およびＲ^２はそれぞれ独立して、水素原子またはメチル基を示し、Ｒｆは独立して、フッ素原子を有する有機基を示す。＊は結合部位を示す。）

(In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rf independently represents an organic group having a fluorine atom. Indicates a binding site.)

  1st aspect of this invention WHEREIN: It is preferable that the said film formation composition contains the polymeric compound which has an ethylenically unsaturated bond.

  1st aspect of this invention WHEREIN: It is preferable that the said film formation composition has at least 1 chosen from the group of the structural unit shown by following formula (2)-following formula (5).

（式（２）〜（５）中、Ｒ^３は独立して、水素原子またはメチル基を示す。Ｒ^４は独立して、メチレン基、炭素数２〜１２のアルキレン基、炭素数２〜１２のアルケニレン基、炭素数６〜１２の置換または非置換の芳香族炭化水素基、炭素数４〜１２の置換または非置換の脂環式炭化水素基、または、これらの基の１つ以上の水素原子がフッ素原子で置換された基を示す。Ｒ^５は独立して、１つ以上の水素原子がフッ素原子で置換された炭化水素基を示す。ｍは０または１を示す。ｎは独立して、０〜１２を示す。）

(In formulas (2) to (5), R ³ independently represents a hydrogen atom or a methyl group. R ⁴ independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. An alkenylene group, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or one or more hydrogens of these groups A group in which an atom is substituted with a fluorine atom, R ⁵ independently represents a hydrocarbon group in which one or more hydrogen atoms have been substituted with a fluorine atom, m represents 0 or 1, and n represents independently. 0-12 are shown.)

  A second aspect of the present invention is manufactured by using the method for manufacturing a base material having a metal wire according to the first aspect of the present invention, wherein a period of a metal lattice made of the metal wire is greater than 0.1 μm and less than or equal to 200 μm. The present invention relates to a polarizing element.

  A third aspect of the present invention relates to an electrode substrate manufactured using the method for manufacturing a base material having a metal wire according to the first aspect of the present invention.

  According to the first aspect of the present invention, a high-definition metal line having a line width of 0.1 μm to 20 μm is suppressed on a substrate while suppressing spreading and spreading of the metal line-forming composition for forming a metal line. A method for producing a substrate having a metal wire to be formed is provided.

  According to the second aspect of the present invention, there is provided a polarizing element having a metal grid made of a metal wire on a substrate, and the period of the metal grid being greater than 0.1 μm and not greater than 200 μm.

  According to the 3rd aspect of this invention, the electrode substrate which has a high-definition metal lattice which consists of a metal wire on the board | substrate used as a base material is provided.

It is sectional drawing which shows typically the coating film of the radiation sensitive composition of embodiment of this invention formed on the board | substrate. It is sectional drawing which illustrates typically exposure of the coating film of the radiation sensitive composition of embodiment of this invention on a board | substrate. It is sectional drawing which illustrates typically the heating of the coating film of the radiation sensitive composition of embodiment of this invention in which one part was exposed. It is sectional drawing which illustrates typically formation of the layer of the metal wire formation material in the manufacturing method of the base material which has a metal wire of embodiment of this invention. It is sectional drawing which shows typically the pattern of embodiment of this invention formed on the board | substrate. It is a top view which shows typically the structure of the polarizing element of embodiment of this invention. It is a figure which shows typically the cross-section of the polarizing element of embodiment of this invention. It is a top view which shows typically the structure of the electrode substrate of embodiment of this invention. It is a figure which shows typically the cross-sectional structure of the electrode substrate of embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate.

[Method for producing substrate having metal wire]
The manufacturing method of the base material which has a metal wire of embodiment of this invention is comprised including the process of following (i)-(iv). And the manufacturing method of the base material which has a metal wire of embodiment of this invention has the characteristics that the image development process required by the conventional photolithography method is not included.
(I) The process of forming the coating film of the film forming composition containing the polymer which has an acid dissociable group, and an acid generator on a base material (ii) The process of irradiating a predetermined part of the said coating film with radiation (iii) ) A step of providing a layer of a metal line forming composition having a line width of 0.1 μm to 20 μm on the coating film irradiated with the radiation. (Iv) A step of heating the layer of the metal line forming composition.

  The development steps that are conventionally required for patterning are used in the steps (i) to (iv) described above (hereinafter also referred to as steps (i), (ii), (iii), and (iv)). A metal wire having a line width of 0.1 μm to 20 μm can be formed on the substrate without any problem, and a substrate having a metal wire can be produced.

  Hereinafter, each process which the manufacturing method of the base material which has a metal wire of embodiment of this invention has is demonstrated.

[Step (i)]
FIG. 1 is a cross-sectional view schematically showing a coating film of a radiation-sensitive composition according to an embodiment of the present invention formed on a substrate.

  In this step (i), after a film-forming composition containing an acid-dissociable group-containing compound and an acid generator is applied on the substrate 1 which is an example of a base material, the coated surface is preferably heated (pre-baked). In this step, the coating film 2 is formed on the substrate 1. Here, the film-forming composition described above preferably includes a compound having an acid dissociable group and an acid generator and has radiation sensitivity. Hereinafter, the film-forming composition according to the embodiment having radiation sensitivity is also referred to as a radiation-sensitive composition.

In step (i), by using the above-mentioned radiation-sensitive composition, a recess for forming a metal wire later is formed on the substrate 1 without performing a development step in each step described below. Can do.
The radiation sensitive composition will be specifically described later.

  Examples of the material of the substrate 1 that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether sulfone, polycarbonate, polyimide, cyclic olefin ring-opening polymer (ROMP polymer), and hydrogenated products thereof.

  In addition, as the substrate 1, it is possible to provide an electrode substrate that can be used for a wire grid type polarizing element, a display element, and the like by the method for manufacturing a base material having a metal wire according to an embodiment of the present invention. A resin substrate and a glass substrate having light transmittance suitable for the structure are preferable.

  In addition, before apply | coating a radiation sensitive composition to the board | substrate 1, you may perform pretreatments, such as washing | cleaning, roughening, and giving a fine uneven surface, as needed.

  The application method of the radiation-sensitive composition is not particularly limited, and is a coating method using a brush or brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar An appropriate method such as a coating method, flexographic printing, offset printing, ink jet printing, or dispensing method can be employed. Among these coating methods, a slit die coating method or a spin coating method is particularly preferable.

  The thickness of the coating film 2 formed in the step (i) may be appropriately adjusted according to a desired application, but is preferably 0.01 μm to 5 μm, more preferably 0.05 μm to 3 μm.

  The pre-baking conditions vary depending on the composition of the radiation-sensitive composition used, but are preferably about 60 to 120 ° C. for 1 to 10 minutes.

[Step (ii)]
Step (ii) is a step of performing exposure by irradiating at least a part of the coating film 2 formed in step (i) with radiation.

  FIG. 2 is a cross-sectional view schematically illustrating exposure of a coating film of the radiation-sensitive composition of the embodiment of the present invention on a substrate.

  In step (ii), as shown in FIG. 2, a part of the coating film 2 on the substrate 1 is irradiated with radiation, and a coating film 2a having a radiation irradiation part 3 and a radiation non-irradiation part 3-2 is formed. The

  In the step (ii), a predetermined pattern is used through a photomask having a predetermined pattern or using a direct drawing type exposure apparatus so that the radiation irradiation section 3 having the same shape as the shape of the metal wire to be formed is formed. A pattern can be drawn and exposed.

  At this time, the line width of the radiation irradiating part 3 of the coating film 2a is a metal line forming composition having a line width of 0.1 μm to 20 μm on the coating film in the step (iii) described later, that is, a line width of 0.1 μm to 20 μm. It is preferably 0.1 μm or more and 20 μm or less, that is, 0.1 μm to 20 μm so as to be suitable for providing an object layer. And when providing the polarizing element of embodiment of this invention which uses the manufacturing method of the base material which has a metal wire of this embodiment, and the period of the metal grating | lattice which consists of metal wires is larger than 0.1 micrometer and is 200 micrometers or less. The radiation irradiating portions 3 having a line width of 0.1 μm to 20 μm are preferably arranged in a lattice pattern with a period greater than 0.1 μm and not greater than 200 μm. In particular, in a base material having a metal wire to be manufactured, the line width of the metal wire and the distance between the adjacent metal wires are formed to be equal, and the period of the arrangement of the metal wires is set to twice the line width of the metal wires. In this case, it is preferable that the radiation irradiation part 3 of the coating film 2a has a line width of 0.1 μm to 20 μm and is arranged in a lattice pattern with a period of 0.2 μm to 40 μm.

  In this step (ii), as the radiation used for exposure, ultraviolet rays, far ultraviolet rays, charged particle beams, X-rays, or the like can be used so that a predetermined pattern having a line width of 0.1 μm to 20 μm can be drawn and exposed.

  By the step (ii), the acid dissociable group present in the coating film 2 in FIG. 1 is eliminated and volatilized by the effect of the acid generator. As a result, as shown in FIG. 2, the film thickness of the radiation irradiation part 3 becomes thinner than the film thickness of the radiation non-irradiation part 3-2, and a concave pattern consisting of concave parts is formed. At this time, if the acid dissociable group has a fluorine atom, the coating film 2 and the radiation non-irradiated part 3-2 obtained in the step (i) exhibit liquid repellency, but the radiation irradiated part 3 is an acid. Along with disappearance of the dissociable group, it becomes lyophilic as compared with the radiation non-irradiated part 3-2.

  Therefore, in step (i), when the radiation-sensitive composition to be used contains a polymer having an acid-dissociable group containing a fluorine atom, liquid repellent property is formed on the substrate 1 by step (ii). The coating film which has the radiation non-irradiation part 3-2 and the radiation irradiation part 3 which is a lyophilic recessed part from the radiation non-irradiation part 3-2 is formed.

  FIG. 3 is a cross-sectional view schematically illustrating heating of the coating film of the radiation-sensitive composition according to the embodiment of the present invention that is partially exposed.

  In the step (ii), a heating step shown in FIG. 3 can be provided after the exposure shown in FIG.

  In the step (ii), by heating the coating film after exposure, the concave portion 13 corresponding to the portion that was the radiation irradiated portion in the step (ii) and the portion that was the radiation non-irradiated portion in the step (ii) A coating film having the corresponding convex portion 12 can be formed.

  By this heating step, the component generated in the radiation irradiation section 3 after the exposure shown in FIG. 2 and from which the acid dissociable group is eliminated due to the effect of the acid generator can be further volatilized. As a result, the concave depression in the radiation irradiation section 3 of FIG. 2 is further deepened (the film thickness of the recess 13 is further reduced), and the film thickness of the recess 13 is 10% or more thinner than the film thickness of the protrusion 12. A coating film having a shape can be formed.

  In the step (i), when the radiation-sensitive composition to be used contains a polymer having an acid-dissociable group containing a fluorine atom, a liquid repellency is formed on the substrate by the heating step in the step (ii). The coating film which has the convex part 12 and the lyophilic concave part 13 from this part is formed. And when a layer of a liquid metal wire forming material is formed on such a coating film, since the film thickness difference between the convex portion 12 and the concave portion 13 is large, the metal wire forming material is formed on the concave portion 13 by the unevenness of the coating film surface. Becomes easier to gather. In addition, not only the effect of the surface shape of the coating film but also the lyophilic / liquid repellency of the surface makes it easy for the metal wire forming material to collect on the recess 13, and the desired shape of the metal wire forming composition. It becomes easy to form a layer, specifically, a layer of a high-definition metal wire forming composition.

  In the step (i), when the radiation-sensitive composition to be used includes a polymer having an acid-dissociable group containing a fluorine atom, the group having a fluorine atom is exposed by the above-described exposure by irradiation with radiation. Detach. Since this leaving group is relatively easily volatilized, a coating film having a large film thickness difference between the convex portion 12 and the concave portion 13 can be easily formed by the heating step of step (ii).

  As a method of heating the coating film in the heating step of step (ii), for example, a method of heating the substrate 1 with the coating film using a hot plate, a batch type oven or a conveyor type oven, a dryer or the like is used. And hot air drying and vacuum baking.

  The heating conditions in the heating step vary depending on the composition of the radiation-sensitive composition used in step (i), the thickness of the coating film in step (ii), etc., but are preferably 3 at 60 ° C to 150 ° C. About 30 minutes.

  In the heating step of step (ii), the thickness of the concave portion 13 is preferably 10% or more thinner, more preferably 11% or thinner, more preferably 12% to 70% thinner than the thickness of the convex portion. It is desirable to form a coating film having a shape. When the obtained coating film has such a shape, when the metal wire forming material layer is formed in the recess 13, the metal wire forming material overflows from the recess 13 due to unevenness on the surface of the coating film. Since the metal wire forming material is less likely to remain in places other than the recess 13, a high-definition metal wire forming composition layer can be formed using a large amount of the metal wire forming composition. A high-definition metal wire can be obtained even if the metal wire forming composition is used.

  In addition, although the film thickness of the recessed part 13 obtained by the heating process of process (ii) should just be adjusted suitably according to a desired use, Preferably it is 0.01 micrometer-18 micrometers, More preferably, it is 0.05 micrometer-15 micrometers. .

  The contact angle difference between the surface of the concave portion 13 and the surface of the convex portion 12 with respect to tetradecane (contact angle of the surface of the convex portion 12−contact angle of the surface of the concave portion 13) is preferably 30 ° or more, more preferably 40 ° or more, and still more preferably. Is 50 ° or more. When the contact angle difference is in the above range, even in the case where a layer of a liquid metal wire forming material is formed on the surface of the convex portion 12 in the step (iii) described later, the convex portion 12 that is a liquid repellent portion. In this case, the metal line forming material is repelled and the metal line forming material easily moves to the recess 13 which is a lyophilic part, so that a layer of the metal line forming material along the recess 13 can be formed. After that, it is possible to form a metal line along the recess 13.

  Note that the surface of the concave portion 13 and the surface of the convex portion 12 are surfaces on the side opposite to the side in contact with the substrate 1 of the coating film formed on the substrate 1, as shown in FIG.

  The resulting recesses 13 and protrusions 12 have a thickness of the recesses 13 that is 10% or more thinner than the thickness of the protrusions 12, and the contact angle difference between the surfaces of the recesses 13 and the protrusions 12 with respect to tetradecane is 30 °. When the above condition is satisfied, a large amount of metal wire forming material can be easily applied only to the recess 13 for the same reason as described above.

[Step (iii)]
FIG. 4 is a cross-sectional view schematically illustrating the formation of a metal wire-forming material layer in the method for producing a base material having a metal wire according to an embodiment of the present invention.

  In the step (iii), the layer 5 of the metal wire forming composition 4 is provided on the coating film irradiated with the radiation in the step (ii). At this time, as in the example shown in FIG. 4, the layer 5 of the metal wire forming material 4 is preferably formed on the recess 13 formed by the heating step of the step (ii).

  And the line | wire width of the radiation irradiation part 3 of the coating film 2a shown in FIG. 2 shall be 0.1 micrometer-20 micrometers. Therefore, in this step (iii), as in the example shown in FIG. 4, the layer 5 of the metal wire forming composition 4 having a line width of 0.1 μm to 20 μm is provided on the concave portion 13 of the coating film. And when providing the polarizing element of embodiment of this invention which uses the manufacturing method of the base material which has a metal wire of this embodiment, and the period of the metal grating | lattice which consists of metal wires is larger than 0.1 micrometer and is 200 micrometers or less. The layer 5 of the metal line forming composition 4 having a line width of 0.1 μm to 20 μm is preferably arranged in a stripe shape with a period of greater than 0.1 μm and not greater than 200 μm, that is, with a formation pitch of greater than 0.1 μm and not greater than 200 μm. . In particular, in a base material having a metal wire to be manufactured, the line width of the metal wire and the distance between the adjacent metal wires are formed to be equal, and the period of the arrangement of the metal wires is set to twice the line width of the metal wires. In this case, the layer 5 of the metal line-forming composition 4 preferably has a line width of 0.1 μm to 20 μm and is arranged in a lattice pattern with a period of 0.2 μm to 40 μm.

  The metal wire forming composition 4 will be specifically described later.

  In this step, the method for providing the layer 5 of the metal wire-forming composition 4 on the coating film irradiated with radiation is not particularly limited, and a known coating method can be used.

  The coating method is not particularly limited. For example, a coating method using a brush or brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method. Appropriate methods such as a method, a squeegee method, a flexographic printing, an offset printing, an ink jet printing, and a dispensing method can be employed. Among these, the dipping method, the spray method, the spin coating method, the slit die coating method, the offset printing, the ink jet printing, and the dispensing method are particularly preferable.

  Further, regardless of the above-described coating method, for example, if the liquid metal wire-forming composition 4 is supplied on the substrate 1 provided with the coating film having the recesses 13 by hanging or sprinkling, the metal wire-forming composition. Four layers 5 can be provided.

  The substrate 1 on which the coating film is formed by the above-described step (ii) has, for example, a liquid-repellent convex portion 12 and a lyophilic concave portion 13 so that a liquid metal wire is used in this step (iii). When the forming material 4 is used, the metal line forming material 4 is repelled in the convex portion 12 and easily gathers in the concave portion 13 regardless of which method is used. The layer 5 is formed.

[Step (iv)]
Step (iv) is a step of heating the substrate on which the layer of the metal line forming material obtained in step (iii) is formed.

  FIG. 5 is a cross-sectional view schematically showing a pattern of an embodiment of the present invention formed on a substrate.

  By this step (iv), the pattern 6 is formed from the layer of the metal wire forming material, and this becomes the metal wire. As a result, in this step (iv), a substrate having a metal wire is manufactured. At this time, the convex part 12 on the substrate 1 is formed of the radiation-sensitive composition as described above and can have light transmission, and a light-transmitting region can be formed on the substrate 1.

  The heating temperature is not particularly limited, but is preferably 190 ° C. or lower. Further, when a film having poor heat resistance such as polyethylene terephthalate is used as the substrate 1, it is preferably not higher than the heat resistant temperature of the film, specifically 150 ° C. or lower.

  The heating time is not particularly limited, but is preferably 1 minute to 120 minutes, more preferably 3 minutes to 60 minutes.

  Examples of the heating method include a method of heating using a hot plate, a batch type oven or a conveyor type oven, a method of drying with hot air using a dryer or the like, and a method of vacuum baking.

  The metal wire pattern 6 formed in this step (iv) is excellent in properties such as adhesion, and is effective in forming high-definition metal wires and electrodes. The metal line pattern 6 has a line width of, for example, 0.1 μm to 20 μm based on the line width of the layer 5 of the metal line forming composition 4 in the step (iii) shown in FIG. And when providing the polarizing element of embodiment of this invention which uses the manufacturing method of the base material which has a metal wire of this embodiment, and the period of the metal grating | lattice which consists of metal wires is larger than 0.1 micrometer and is 200 micrometers or less. The pattern 6 having a line width of 0.1 μm to 20 μm is preferably arranged in a stripe pattern with a period of greater than 0.1 μm and less than or equal to 200 μm, that is, a formation pitch greater than 0.1 μm and less than or equal to 200 μm. In particular, in a base material having a metal wire to be manufactured, the line width of the metal wire and the distance between the adjacent metal wires are formed to be equal, and the period of the arrangement of the metal wires is set to twice the line width of the metal wires. In this case, it is preferable that the pattern 6 has a line width of 0.1 μm to 20 μm and is arranged in a lattice pattern with a period of 0.2 μm to 40 μm.

  And the board | substrate which has a metal wire manufactured by the manufacturing method of the base material which has a metal wire of embodiment of this invention can be utilized for a display element etc. as a wire grid type polarizing element so that it may mention later. It can be used as an electrode substrate.

[Radiation sensitive composition]
As described above, the radiation-sensitive composition of the embodiment of the present invention is an example of a film-forming composition used in the method for producing a substrate having a metal wire of the embodiment of the present invention, and has a metal wire. It is used for providing a base material, and by extension, for providing a wire grid type polarizing element, an electrode substrate and the like.

  The radiation-sensitive composition of the embodiment of the present invention (hereinafter sometimes simply referred to as a radiation-sensitive composition) is a polymer having an acid-dissociable group of the embodiment of the present invention (hereinafter simply referred to as [ A] may be referred to as a polymer.

  The radiation-sensitive composition can contain a solvent in addition to the [A] polymer. Moreover, the radiation sensitive composition can contain an acid generator. Further, the radiation-sensitive composition can contain a polymerizable compound having an ethylenically unsaturated bond, and can contain a radiation-sensitive polymerization initiator.

  The radiation-sensitive composition exhibits a liquid state by containing a solvent (hereinafter sometimes referred to as [B] solvent), forms a coating film by coating, and is a so-called for easily forming a metal wire. An underlayer can be formed.

  In addition, the radiation-sensitive composition can have desired high-sensitivity radiation sensitivity by containing an acid generator (hereinafter sometimes referred to as [C] acid generator). Further, it may further contain a sensitizer (hereinafter sometimes referred to as [D] sensitizer) as an auxiliary material for the acid generator. Furthermore, a quencher (hereinafter sometimes referred to as [E] quencher) may be included as a material for suppressing the diffusion of acid from the acid generator.

Furthermore, the radiation-sensitive composition can contain a polymerizable compound having an ethylenically unsaturated bond (hereinafter sometimes referred to as [F] polymerizable compound). Furthermore, the radiation-sensitive composition can contain a radiation-sensitive polymerization initiator (hereinafter sometimes referred to as [G] radiation-sensitive polymerization initiator).
And a radiation sensitive composition can contain another arbitrary component, unless the effect of this invention is impaired.

The viscosity (temperature: 20 ° C., shear rate: 10 sec ⁻¹ ) of the radiation-sensitive composition may be adjusted depending on the desired coating method and the film thickness of the coating film to be formed. When a coating film having a film thickness of 0.5 μm to 2 μm is formed and the spin coating method is used as the coating method, preferably 5 cP (0.003 Pa · s) to 20 cP (0.02 Pa · s) can be exemplified. When the slit die coating method is used as the coating method, preferably 1 cP (0.001 Pa · s) to 20 cP (0.01 Pa · s) can be exemplified.

<[A] polymer>
[A] The polymer having an acid-dissociable group ([A] polymer), which is a component of the radiation-sensitive composition according to the embodiment of the present invention, is at least one selected from the group consisting of an acetal bond and a hemiacetal ester bond. It has a group containing a structural unit. More specifically, it preferably includes structural units represented by the following formulas (1-1) and (1-2).

（式（１−１）および式（１−２）中、Ｒ^１およびＲ^２はそれぞれ独立して、水素原子またはメチル基を示し、Ｒｆは独立して、フッ素原子で置換された有機基を示す。＊は、結合部位を示す。）

(In Formula (1-1) and Formula (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rf independently represents an organic group substituted with a fluorine atom. * Indicates a binding site.)

A compound containing an acetal bond can be obtained by reacting an alcohol with a compound having a group CH ₂ ═C (R ¹ ) —O—, and a compound containing a hemiacetal ester bond can be obtained by reacting a carboxylic acid with a group CH _2. It can be obtained by reacting with a compound having ═C (R ¹ ) —O—.

  Examples of Rf include organic groups having a fluorine atom.

  As Rf, groups represented by the following formulas (1-1-1) to (1-1-33) are preferable.

  [A] The polymer is a protecting group derived from a vinyl ether compound represented by the following formula (1) (hereinafter sometimes referred to as “compound (1)”) on the hydroxyl group of the precursor-containing compound having a hydroxyl group. It is preferable to have a structure in which is introduced. [A] The polymer may have a structure in which a protecting group derived from the compound (1) is introduced into the carboxyl group of the compound having a carboxyl group as a precursor.

  These compounds (hereinafter sometimes referred to as “compound (a)”), in particular compounds having a hydroxyl group as a precursor, have the property that the removal of the protecting group by heat hardly occurs, while radiation irradiation. It can be suitably used for forming the polymer [A] because it has the property that it can control the elimination of the protecting group by. Further, when the compound (a) forms the [A] polymer, it becomes possible to control the elimination of the protecting group with higher accuracy by irradiation with the combination with the [C] acid generator described later. Therefore, it is preferable.

In the above formula (1), R ⁰ represents a hydrogen atom or a methyl group.

In the above formula (1), R ^A is independently a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms. A group, a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom;

As the alkylene group having 2 to 12 carbon atoms in R ^A of the above formula (1), ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, And dodecylene group.

Examples of the alkenylene group having 2 to 12 carbon atoms in R ^A of the above formula (1) include vinylene group, ethene-1,2-diyl group, 2-butene-1,4-diyl and the like.

Examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms in R ^A of the above formula (1) include a phenylene group, a tolylene group, a mesitylene group, a naphthylene group, and a biphenylene group.

As the substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms in R ^A of the above formula (1), (cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bicyclohexyl group) Is mentioned.

In R ^A of the above formula (1), a methylene group, an alkylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, or a substituted or unsubstituted group having 4 to 12 carbon atoms. Examples of the group in which one or more hydrogen atoms of the alicyclic hydrocarbon group are substituted with fluorine atoms include groups in which one or more hydrogen atoms of the groups exemplified above are substituted with fluorine atoms.

R ^{A in the} above formula (1) is preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a vinylene group.

In the above formula (1), R ^B represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms.

In the formula (1), R ^B is, for example, a group represented by the formulas (1-1-1) to (1-1-33) in the Rf, a 2,2,2-trifluoroethyl group, 4, 4,5,5,6,6,6, -heptafluorohexyl group and 1,2,2-trifluorovinyl group, and 2,2,2-trifluoroethyl group, the above formula (1-1 -1) 3,3,3-trifluoropropyl group, formula (1-1-2) 4,4,4-trifluorobutyl group, formula (1-1-4) 3,3,4, 4,4-pentafluorobutyl group, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,6 of formula (1-1-8) , 6,7,7,8,8,8-tridecafluorooctyl group, 1,2,2-trifluorovinyl group, 2,3,4,5,6-pen of formula (1-1-29) A tafluorophenyl group is preferred.

  In said formula (1), x shows the integer of 0-12, the integer of 0-9 is preferable and 0 is more preferable.

  The coating film formed in step (i) of the method for producing a substrate having a metal wire according to the embodiment of the present invention described above exhibits characteristics based on [A] polymer, and is described above in the formation of [A] polymer. When the compound (a) is used, the compound (a) exhibits characteristics derived from the protecting group. Specifically, when a coating film is formed from the radiation-sensitive composition containing the [A] polymer, first, in the step (i), a liquid-repellent coating film is formed, and this coating film is irradiated with radiation. In the exposed part, the protecting group in the [A] polymer is eliminated, and in the part from which the protecting group is eliminated, a hydroxyl group or a carboxyl group remains, and the liquid repellency resulting from the protecting group is lost.

  Next, the method for obtaining the [A] polymer is demonstrated. [A] As a method for obtaining a polymer, two methods are possible: a method using a polymer as a precursor compound, and a method using a monomer as a precursor compound.

  In the method of using a polymer as the precursor compound, the precursor polymer contains a hydroxyl group or a carboxyl group in the molecule, and the compound (1) is reacted with the hydroxyl group of the precursor polymer. [A] A polymer can be obtained.

  In the method using a monomer as the precursor compound, the precursor monomer contains a hydroxyl group or a carboxyl group in the molecule, and the compound (1) is reacted with the hydroxyl group or carboxyl group of the precursor monomer. Then, the [A] polymer can be obtained by polymerizing the obtained monomer.

  Hereinafter, the two methods for obtaining the [A] polymer will be described more specifically.

(1) Method of using a polymer as a compound to be a precursor In this method, a monomer having a hydroxyl group or a carboxyl group is polymerized to obtain a polymer having a hydroxyl group or a carboxyl group (precursor), and then the precursor and The compound (1) is reacted with the hydroxyl group or carboxyl group of the resulting polymer to obtain the [A] polymer.

  As the above-mentioned monomer having a hydroxyl group, (meth) acrylic acid ester is preferable. For example, 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- (hydroxy Chill) 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 (pro (Pyrene 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 Examples include Plascel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FM3X, Plaxel FM4, Plaxel FM5, Plaxel FA1, Plaxel FA1DDM, Plaxel FA2D, Plaxel FA5L and Plaxel FA10L manufactured by Daicel Corporation it can.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2- Acryloyloxyethyltetrahydrophthalic acid, 2-methacryloyloxyethyltetrahydrophthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-methacryloyloxypropylphthalate Acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydrophthalate Acid, and 2-methacryloyloxy propyl hexahydrophthalic acid.

  [A] A polymer having a hydroxyl group or a carboxyl group, which is a precursor of the polymer, can be obtained using only the monomer having a hydroxyl group or a carboxyl group as described above; It can be obtained by copolymerizing with a monomer other than a monomer having a hydroxyl group or a carboxyl group. As monomers other than the monomer having a hydroxyl group or a carboxyl group, (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, tetrahydrofuran Examples thereof include unsaturated compounds containing a skeleton, maleimide, and other monomers.

  More specifically, examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methacrylic acid. 2-ethylhexyl acid, isodecyl methacrylate, n-lauryl methacrylate, 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, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacryl Examples include acid isobornyl, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and isobornyl acrylate.

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

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

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

  Examples of the unsaturated compound containing the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran-2-one. Can be mentioned.

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

As other monomers, for example, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) ) -3-ethyloxetane, tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl An acrylate is mentioned.

  [A] Examples of the solvent used in the polymerization reaction for synthesizing a polymer having a hydroxyl group or a carboxyl group, which serves as a polymer precursor, include alcohols, glycol ethers, ethylene glycol alkyl ether acetates, and diethylene glycol monoalkyl ethers. , Diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone and ester.

  [A] In the polymerization reaction for obtaining a polymer having a hydroxyl group or a carboxyl group, which is a precursor of the polymer, a molecular weight modifier 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; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

  The polystyrene-reduced weight average molecular weight (Mw) of the polymer having a hydroxyl group or a carboxyl group by gel permeation chromatography (GPC) is preferably 1000 to 30000, more preferably 5000 to 20000. By setting Mw of the polymer having a hydroxyl group or a carboxyl group within the above range, the sensitivity of the radiation-sensitive composition containing the [A] polymer can be increased.

  Next, the method of obtaining the polymer [A] by reacting the hydroxyl group or carboxyl group of a polymer having a hydroxyl group or a carboxyl group with the compound (1) is represented by the following formula. This can be done by adding a group.

  And the method of obtaining a [A] polymer can refer to a well-known method, for example, can refer to the method described in Unexamined-Japanese-Patent No. 2005-187609.

  Specifically, an acetal bond is formed by the hydroxyl group of the polymer having a hydroxyl group and the vinyl ether group of the compound (1), or a hexyl group is formed by the carboxyl group of the monomer having a carboxyl group and the vinyl ether group of the compound (1). An acetal ester bond is formed to form an adduct.

  For example, after dissolving a polymer having a hydroxyl group or a carboxyl group in an appropriate organic solvent, an equimolar or excess amount of the compound (1) is added to the hydroxyl group or carboxyl group of the polymer, and the resulting reaction is obtained. After cooling the mixture to a temperature of about 0 ° C. to room temperature (25 ° C.), an acid (for example, an oxalic acid solution) dissolved in the same solvent as the organic solvent described above is added dropwise as a catalyst. Stir for 1 to 24 hours to react. After completion of the reaction, the desired [A] polymer can be obtained by removing the organic solvent.

(2) Method of using a monomer as a precursor compound In this method, the compound (1) is reacted with a hydroxyl group or a carboxyl group of a monomer having a hydroxyl group or a carboxyl group to obtain an adduct and polymerize them. [A] A polymer is obtained. A known method can be referred to for obtaining such a polymer [A]. For example, as described in JP-A-2005-187609, an acetal bond is formed by a hydroxyl group of a monomer having a hydroxyl group and a vinyl ether group of a vinyl ether compound, or a carboxyl group of the monomer having a carboxyl group and the compound A hexacetal ester bond is formed by the vinyl ether group of (1) to form an adduct. Next, using the obtained monomer, the [A] polymer can be obtained in the same manner as in the method for producing a polymer having a hydroxyl group or a carboxyl group as described above.

  Preferred examples of the [A] polymer obtained as described above include polymers having at least one selected from the group consisting of structural units represented by the following formulas (2) to (5). .

（式（２）〜（５）中、Ｒ^３は独立して、水素原子またはメチル基を示す。Ｒ^４は独立して、メチレン基、炭素数２〜１２のアルキレン基、炭素数６〜１３の芳香族炭化水素基、炭素数４〜１２の置換または非置換の脂環式炭化水素基、または、これらの基の１つ以上の水素原子がフッ素原子で置換された基を示す。Ｒ^５は独立して、炭化水素基の１つ以上の水素原子がフッ素原子で置換された基を示す。ｍは０または１を示す。ｎは独立して０〜１２を示す。）

(In formulas (2) to (5), R ³ independently represents a hydrogen atom or a methyl group. R ⁴ independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or 6 to 13 carbon atoms. aromatic hydrocarbon group, .R ⁵ showing a substituted or unsubstituted alicyclic hydrocarbon group, or one or more hydrogen atoms are substituted with fluorine atoms in these groups, C4-12 Independently represents a group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a fluorine atom, m represents 0 or 1, and n independently represents 0 to 12.)

  And as a specific example of a polymer having at least one selected from the group consisting of structural units represented by the above formulas (2) to (5), which is a preferred example of the [A] polymer, Can be mentioned.

  [A] A polymer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

<[B] solvent>
[B] Although it does not specifically limit as a solvent, The solvent which can melt | dissolve or disperse | distribute each component, such as a [C] acid generator mentioned later and a [F] polymeric compound, in addition to a [A] polymer uniformly. preferable.

  Suitable [B] solvents include alcohol solvents, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons. , Aromatic hydrocarbons, ketones and esters.

Examples of the alcohol solvent include long-chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, 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, ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.
These alcohol solvents can be used alone or in combination of two or more.

  Among these alcohol solvents, benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether are particularly preferable from the viewpoint of improving coatability.

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

  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, and ethylene glycol monoethyl ether acetate.

  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. Can be mentioned.

  Examples of the above-mentioned aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, cyclohexane and decalin. Can do.

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

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

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

  [B] solvent mentioned above may be used individually by 1 type, and may mix and use 2 or more types.

  [B] The amount of the solvent used is preferably 200 parts by mass to 1600 parts by mass, more preferably 400 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the component excluding the solvent [B] of the radiation-sensitive composition. is there. [B] By making the amount of the solvent used within the above-mentioned range, the coating property of the radiation-sensitive composition on the glass substrate and the like is improved, and furthermore, uneven coating (such as streaky unevenness, uneven pin trace, and unevenness) occurs. And a coating film with improved film thickness uniformity can be obtained.

<[C] acid generator>
[C] The acid generator is a compound that generates an acid at least upon irradiation with radiation. When the radiation-sensitive composition contains the [C] acid generator, the acid-dissociable group can be eliminated from the [A] polymer.

[C] Examples of the acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds.
[C] The acid generators may be used alone or in combination of two or more.

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

In the 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, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

As the alkyl group represented by R ¹¹ described above, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2. -An alicyclic group containing a bridged cyclic alicyclic group such as an oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptylfluoropropyl group, and the like.

The alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ¹¹ described above may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, A halogen atom is mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹¹ is preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The above aryl group may be substituted by a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the compound containing an oxime sulfonate group represented by the formula (6) include an oxime sulfonate represented by the following formula (6-1), the following formula (6-2), and the following formula (6-3). Compounds.

In Formula (6-1), Formula (6-2), and Formula (6-3), R ¹¹ has the same meaning as Formula (6) described above. In the formula (6-1), the formula (6-2), and the formula (6-3), R ¹⁵ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.
In formula (6-3), X represents an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

  The alkyl group represented by X in the formula (6-3) is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As m, 0 or 1 is preferable. In the formula (6-3), a compound in which m is 1, X is a methyl group, and the substitution position of X is an ortho position is particularly preferable.

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

  The compounds represented by the formula (6-3-1) to the formula (6-3-5) are each represented by (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl). Acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, obtained as a commercial product it can.

[Onium salt]
[C] Preferred onium salts as acid generators include, for example, diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, tetrahydrothio Phenium salts are mentioned.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. , Diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexa Fluoroarsenate, bis (4-tert-butylphenyl) iodonium tri Fluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid Can be mentioned.

  Examples of the triphenylsulfonium salt described above include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, And triphenylsulfonium butyl tris (2,6-difluorophenyl) borate.

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

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4. -Methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4 -Hydroxyphenylmethylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4- Methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4- And methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4- Hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl -3-Chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt described above include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p -Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate.

  Examples of the tetrahydrothiophenium salt described above include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene. Nitrotrifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium- 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxy) Carbonyloxybicyclo [2.2.1] heptan-2-yl) 1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] Heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate.

[Sulfonimide compound]
[C] As a preferred sulfonimide compound as an acid generator, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-tri Fluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphor Sulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenyl) Sulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( Nonafluorobutanesulfonyloxy Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenol) Nylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane -5,6-oxy-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3- Carboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboximide, N- (camphorsulfonyloxy) naphthyl dicarboximide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboximide, N- (Phenylsulfonyloxy) naphthyl dicarboximide, N- (2-trifluoro) Romethylphenylsulfonyloxy) naphthyl dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboximide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboximide, N- (heptafluoropropylsulfonyloxy) naphthyl Dicarboximide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboximide, N- (ethylsulfonyloxy) naphthyl dicarboximide, N- (propylsulfonyloxy) naphthyl dicarboximide, N- (butylsulfonyloxy) naphthyl Dicarboximide, N- (pentylsulfonyloxy) naphthyl dicarboximide, N- (hexylsulfonyloxy) naphthyl dicarboximide, N- (heptylsulfo) Nyloxy) naphthyl dicarboximide, N- (octylsulfonyloxy) naphthyl dicarboximide, N- (nonylsulfonyloxy) naphthyl dicarboximide and the like.

[Halogen-containing compounds]
[C] Preferred halogen-containing compounds as acid generators include, for example, haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

[Diazomethane compounds]
[C] Preferred diazomethane compounds as acid generators include, for example, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2 , 4-Xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) Examples include diazomethane and phenylsulfonyl (benzoyl) diazomethane.

[Sulfone compound]
[C] Examples of the sulfone compound preferable as the acid generator include β-ketosulfone compounds, β-sulfonylsulfone compounds, and diaryldisulfone compounds.

[Sulfonic acid ester compounds]
[C] Preferred sulfonic acid ester compounds as acid generators include, for example, alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.

[Carboxylic ester compounds]
[C] Preferred examples of the carboxylic acid ester compound as the acid generator include carboxylic acid o-nitrobenzyl ester.

  [C] The acid generator is preferably an oxime sulfonate compound, an onium salt, or a sulfonic acid ester compound, and more preferably an oxime sulfonate compound. As the oxime sulfonate compound described above, a compound containing an oxime sulfonate group represented by the above formulas (6-3-1) to (6-3-5) is preferable, and is represented by the above formula (6-3-5). Are more preferred.

  Further, as the above-described onium salt, a tetrahydrothiophenium salt and a benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferable. As the sulfonic acid ester compound described above, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable. [C] By making an acid generator into the above-mentioned compound, the radiation sensitive composition of this embodiment can improve a sensitivity, and can further improve solubility.

  In the radiation sensitive composition, the content of the [C] acid generator is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymer [A], and 1 part by mass to 5 parts by mass. Is more preferable. [C] By making content of an acid generator into the above-mentioned range, the sensitivity of a radiation sensitive composition can be optimized.

<[D] sensitizer>
The radiation sensitive composition of embodiment of this invention can contain a [D] sensitizer.
The radiation sensitive composition of embodiment of this invention can further improve the radiation sensitivity of a radiation sensitive composition because it further contains a [D] sensitizer. [D] The sensitizer is preferably a compound that absorbs radiation and becomes an electronically excited state. When the [D] sensitizer in the electronically excited state is brought into contact with the [C] acid generator, electron transfer, energy transfer, heat generation, and the like occur, and the [C] acid generator undergoes a chemical change. Decomposes to produce acid.

  [D] Examples of the sensitizer include compounds belonging to the following compounds.

[D] Examples of the sensitizer include pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, and 9,10-dipropyloxyanthracene. Polynuclear aromatics such as;
Xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, rose bengal;
Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone;
Cyanines such as thiacarbocyanine, oxacarbocyanine;
Merocyanines such as merocyanine and carbomerocyanine;
Rhodocyanines;
Oxonols;
Thiazines such as thionine, methylene blue and toluidine blue;
Acridines such as acridine orange, chloroflavin, acriflavine;
Acridones such as acridone, 10-butyl-2-chloroacridone;
Anthraquinones such as anthraquinone;
Squariums such as squalium;
Styryls;
Base styryls such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole;
7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolidine- Coumarins, such as 11-non, etc. are mentioned.

  Among these [D] sensitizers, polynuclear aromatics, acridones, styryls, base styryls, coumarins, and xanthones are preferable, and xanthones are more preferable. Of the xanthones, diethylthioxanthone and isopropylthioxanthone are particularly preferred

  In the radiation-sensitive composition, the [D] sensitizer may be used alone or in combination of two or more.

  In the radiation sensitive composition, the content of [D] sensitizer is preferably 0.1 part by mass to 8 parts by mass with respect to 100 parts by mass of the polymer [A], and 1 part by mass to 4 parts by mass. Is more preferable. [D] By making content of a sensitizer into the above-mentioned range, the sensitivity of a radiation sensitive composition can be optimized.

<[E] quencher>
The radiation-sensitive composition of the embodiment of the present invention can contain an [E] quencher in addition to the above-described [A] polymer, [C] acid generator, and [D] sensitizer.

  The [E] quencher functions as an acid diffusion inhibitor that prevents the diffusion of acid from the [C] acid generator. [E] As the quencher, a photodegradable base that generates a weak acid by exposure to radiation can be used. The photodegradable base generates an acid in the exposed area, while the non-exposed area exhibits a high acid scavenging function by an anion to supplement the acid from the [C] acid generator, and from the exposed area to the unexposed area. Deactivates the diffusing acid. That is, since the acid is deactivated only in the unexposed area, the contrast of the protecting group elimination reaction is improved, and as a result, the resolution can be further improved. As an example of the photodegradable base, there is an onium salt compound that is decomposed by exposure and loses acid diffusion controllability.

  In the radiation-sensitive composition, the [E] quencher may be used alone or in combination of two or more.

  In the radiation-sensitive composition, the content of [E] quencher is preferably 0.001 to 5 parts by mass, and 0.005 to 3 parts by mass with respect to 100 parts by mass of [A] polymer. Part is more preferred. [D] By making content of a sensitizer into the above-mentioned range, the reactivity of a radiation sensitive composition can be optimized.

<[F] polymerizable compound>
The radiation sensitive composition can cure the radiation sensitive composition by containing the [F] polymerizable compound.

  [F] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. However, [A] is a compound other than a polymer.

  As such a [F] polymerizable compound, monofunctional, bifunctional, or trifunctional or higher (meth) from the viewpoint of good polymerizability and improved strength of the film obtained from the radiation-sensitive composition. Acrylic acid esters are preferred.

  The monofunctional compound refers to a compound having one (meth) acryloyl group, and the bifunctional or trifunctional or higher functional compound is a compound having two or three (meth) acryloyl groups, respectively. I mean.

  Examples of the monofunctional (meth) acrylic acid ester described above include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxy Propyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ω-carboxypolycaprolactone monoacrylate. As a commercial item, for example, Aronix (registered trademark) M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd.); KAYARAD (registered trademark) TC-110S, TC- 120S (above, Nippon Kayaku Co., Ltd.); Biscote 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the bifunctional (meth) acrylic acid ester described above include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetra Examples include ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate. Examples of commercially available products include Aronix (registered trademark) M-210, M-240, M-6200 (above, Toagosei Co., Ltd.); KAYARAD (registered trademark) HDDA, HX-220, R-604 ( As mentioned above, Nippon Kayaku Co., Ltd.); Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.); Light acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.) can be mentioned.

  Examples of the above-described trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, diester. Pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2- Acryloyloxyethylene ) Phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, tris (acryloxyethyl) isocyanurate, linear alkylene group and alicyclic ring A compound having a formula structure and having two or more isocyanate groups and one or more hydroxyl groups in the molecule and having three, four or five (meth) acryloyloxy groups The polyfunctional urethane acrylate type compound obtained by making it react with is mentioned. Examples of commercially available products include Aronix (registered trademark) M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, and M-8060. TO-1450 (above, Toagosei Co., Ltd.); KAYARAD (registered trademark) TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12 (above, Nippon Kayaku Co., Ltd.); Biscoat 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.); commercial products containing polyfunctional urethane acrylate compounds include New Frontier ( Registered trademark) R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD (registered trademark) DPHA-40H (Nippon Kayaku Co., Ltd.), and the like.

  Among these [F] polymerizable compounds, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, 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, polyfunctional urethane Commercial products containing acrylate compounds are preferred. Among them, a tri- or higher functional (meth) acrylic acid ester is preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferable.

  In the radiation-sensitive composition, the [F] polymerizable compound may be used alone or in combination of two or more.

  In the radiation-sensitive composition, the amount of the [F] polymerizable compound used is preferably 1 part by mass to 300 parts by mass and more preferably 3 parts by mass to 200 parts by mass with respect to 100 parts by mass of the polymer [A]. 5 mass parts-100 mass parts are more preferable. [F] By making the usage-amount of a polymeric compound into the above-mentioned range, the height of the coating film obtained from a radiation sensitive resin composition can be raised, and heat resistance can be made more favorable.

<[G] Radiation sensitive polymerization initiator>
[G] The radiation-sensitive polymerization initiator is a compound that accelerates the polymerization of the [F] polymerizable compound when irradiated with radiation. Therefore, when a radiation sensitive composition contains a [F] polymeric compound, it is preferable to use a [G] radiation sensitive polymerization initiator.

  [G] Examples of radiation sensitive polymerization initiators include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds and the like.

  Specific examples of the O-acyloxime compound described above include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1 -[9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-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. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime). These O-acyloxime compounds can be used alone or in admixture of two or more.

  Among these, preferable O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -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. -Carbazol-3-yl] -1- (O-acetyloxime).

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

  Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl). Examples include -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

  Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane- Examples thereof include 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl phenyl ketone.

  The above acetophenone compounds can be used alone or in admixture of two or more.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is particularly preferred.

  Specific examples of the above-mentioned 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, Mention may be made of 2'-biimidazole. These biimidazole compounds can be used alone or in admixture of two or more.

  Among these biimidazole compounds, 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 is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is particularly preferred.

  In the radiation-sensitive composition, when a biimidazole compound is used as the [G] radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group can be added to sensitize it. . Hereinafter, an aliphatic or aromatic compound having a dialkylamino group is referred to as an amino sensitizer.

  Examples of such amino sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferred. These amino sensitizers can be used alone or in admixture of two or more.

  Furthermore, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen radical donor. A biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to neutral imidazole, and a component having a sulfur radical having a high polymerization initiating ability is generated. For this reason, when a biimidazole compound, an amino sensitizer, and a thiol compound are added to the radiation-sensitive composition, a film having high hardness can be formed even at a low radiation dose.

Specific examples of such thiol compounds include aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;
Bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified.

  These thiol compounds can be used alone or in admixture of two or more.

  Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  When a biimidazole compound and an amino sensitizer are used in combination, the use amount of the amino sensitizer is preferably 0.1 parts by mass to 50 parts by mass with respect to 100 parts by mass of the biimidazole compound. More preferably, it is 1 mass part-20 mass parts. The reactivity at the time of exposure can be improved by making the usage-amount of an amino sensitizer into the above-mentioned range.

  Moreover, when using together a biimidazole compound, an amino type sensitizer, and a thiol compound, as the usage-amount of a thiol compound, Preferably it is 0.1 mass part-50 mass parts with respect to 100 mass parts of biimidazole compounds. More preferably, it is 1 mass part-20 mass parts. By making the usage-amount of a thiol compound in the above-mentioned range, the reactivity at the time of exposure can be improved more.

  When the radiation sensitive composition contains a [G] radiation sensitive polymerization initiator, it preferably contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound, and further a biimidazole compound. It may contain.

  [G] A radiation-sensitive polymerization initiator may be used alone or in combination of two or more.

  [G] The amount of the radiation-sensitive polymerization initiator used is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the [A] polymer. It is. [G] By making the usage-amount of a radiation-sensitive polymerization initiator into the above-mentioned range, the radiation-sensitive composition can cure the coating film with high radiation sensitivity even at a low exposure amount.

<Other optional components>
The radiation-sensitive composition of the embodiment of the present invention can further contain other optional components as long as the effects of the present invention are not impaired.

Examples of other optional components include a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver.
Other optional components may be used alone or in combination of two or more.

  Next, the metal wire forming composition used in the method for producing a substrate having a metal wire according to an embodiment of the present invention and used for forming a fair metal wire will be described.

[Metal wire forming composition]
The metal wire forming composition described above is not particularly limited. The metal wire forming composition may be any material that can form a metal wire, and is preferably a liquid ink or paste having fluidity.

  That is, the metal line forming composition is preferably a metal line forming ink and a metal line forming paste. Specifically, an ink or paste in which metal particles are dispersed, an ink or paste containing a metal salt and a reducing agent, under a reducing atmosphere. An ink or paste in which metal oxide particles that can be metallized by heating with is dispersed is preferable.

  These inks or pastes can be formed into a layer of the ink or paste by the above-described various coating methods, and thus a layer of the metal wire forming composition can be formed. And the layer of the metal wire forming composition can be heated to form a metal wire as described above.

As such a metal line forming ink and metal line forming paste, the viscosity (temperature: 20 ° C., shear rate: 10 sec ⁻¹ ) is preferably 0.001 Pa · s to 100 Pa · s, more preferably 0.001 Pa · s. A material in the range of s to 1 Pa · s is desirable.

  In addition, in the process (iii) of the manufacturing method of the base material which has a metal wire of embodiment of this invention mentioned above, when forming the layer of a metal wire formation composition by methods, such as offset printing and screen printing, it is high viscosity. The material of the region is suitable, and the viscosity of the metal wire forming composition at this time is preferably 1 Pa · s to 50 Pa · s. Particularly in the case of offset printing, the viscosity is preferably 10 Pa · s to 50 Pa · s.

<Metal salt>
When the metal wire forming composition contains a metal salt and a reducing agent, metal ions contained in the metal salt are reduced by the reducing agent to form a simple metal, and as a result, a metal wire is formed.

  The metal salt is preferably a silver salt or a copper salt.

  For example, when the metal salt is a silver salt, silver ions contained in the silver salt are reduced by a reducing agent to form silver alone, and a metal wire made of silver is formed. When the metal salt is a copper salt, copper ions contained in the copper salt are reduced by a reducing agent to form copper alone, thereby forming a metal wire made of copper.

  The said metal salt may be used individually by 1 type, and 2 or more types may be mixed and used for it.

The silver salt is not particularly limited as long as it is a silver salt.
For example, silver nitrate, silver acetate, silver oxide, silver acetylacetone, silver benzoate, silver bromate, silver bromide, silver carbonate, silver chloride, silver citrate, silver fluoride, silver iodate, silver iodide, silver lactate, Mention may be made of silver nitrite, silver perchlorate, silver phosphate, silver sulfate, silver sulfide and silver trifluoroacetate.

  The copper salt is not particularly limited as long as it is a compound containing copper ions. For example, a copper salt composed of copper ions and at least one of an inorganic anion species and an organic anion species is used. Can be mentioned. Among these, from the viewpoint of solubility, it is preferable to use one or more selected from the group consisting of a copper carboxylate, a copper hydroxide, and a complex salt of copper and an acetylacetone derivative.

  Examples of the copper carboxylate described above include copper salts with dicarboxylic acids such as copper malonate, copper succinate and copper maleate, copper salts with aromatic carboxylic acids such as copper benzoate and copper salicylate, and copper acetate. , Copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper 2-ethylbutyrate, copper valerate, copper isovalerate, copper pivalate, copper hexanoate, copper heptanoate, It has a monocarboxy group such as copper octanoate, copper 2-ethylhexanoate, copper nonanoate, copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper tartrate, copper malate, copper citrate, etc. A copper salt with an organic acid is mentioned as a suitable compound. Note that copper formate may be anhydrous or hydrated. Examples of the hydrate of copper formate include tetrahydrate.

  Examples of the complex salt of copper and an acetylacetone derivative described above include acetylacetonato copper, 1,1,1-trimethylacetylacetonato copper, 1,1,1,5,5,5-hexamethylacetylacetonate. Copper, 1,1,1-trifluoroacetylacetonatocopper, and 1,1,1,5,5,5-hexafluoroacetylacetonatocopper are suitable compounds.

  Among these, considering the solubility and dispersibility in the reducing agent or solvent, and the electrical resistance characteristics of the formed wiring, copper acetate, copper propionate, copper isobutyrate, copper valerate, copper isovalerate, copper formate Copper carboxylates such as copper formate tetrahydrate and copper glyoxylate are preferred.

  As the metal salt, it is preferable to use a silver salt capable of forming a silver-white metal wire from the viewpoint of suppressing coloring of the formed metal wire. As the metal salt, it is preferable to use a copper salt from the viewpoint of suppressing migration of metal atoms. Of the copper salts, copper formate is particularly preferred because of its excellent reducibility. Copper formate may be anhydrous or copper formate tetrahydrate.

  As content of the metal salt in a metal wire formation composition, the range of 0.01 mass%-50 mass% is preferable with respect to the whole quantity of a metal wire formation composition, and the range of 0.1 mass%-30 mass% is preferable. More preferred. By setting the content of the metal salt in the above range, a wiring having stable and excellent conductivity can be formed. From the viewpoint of obtaining a low resistance wiring, the content of the metal salt is preferably 0.01% by mass or more. From the viewpoint of obtaining a chemically stable metal wire forming composition, the metal salt content is preferably 50% by mass or less.

<Reducing agent>
The metal line forming composition described above preferably contains a reducing agent together with the metal salt described above for the purpose of reducing the metal ions contained in the metal salt to form a simple metal. The reducing agent is not particularly limited as long as it has reducibility to the metal ion contained in the metal salt used.

  Examples of the reducing agent include monomolecular compounds having one or more functional groups selected from the group consisting of thiol groups, nitrile groups, amino groups, hydroxy groups, and hydroxycarbonyl groups, nitrogen atoms, oxygen atoms And a polymer having in its molecular structure one or more heteroatoms selected from the group consisting of sulfur atoms.

  Examples of the monomolecular compound include alkanethiols, amines, hydrazines, monoalcohols, diols, hydroxyamines, α-hydroxyketones and carboxylic acids.

  Examples of the polymer include polyvinyl pyrrolidone, polyethyleneimine, polyaniline, polypyrrole, polythiophene, polyacrylamide, polyacrylic acid, carboxymethylcellulose, polyvinyl alcohol, and polyethylene oxide.

  Among these, considering the solubility of the metal salt and the like, at least one selected from the group consisting of alkanethiols and amines is preferable.

  Examples of the alkanethiols include ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, n- Examples include heptane thiol, n-octane thiol, and 2-ethylhexane thiol.

  Examples of the amines include amine compounds such as 3- (2-ethylhexyloxy) propylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t -Butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, 2-ethylhexylpropylamine, 3-ethoxypropylamine, n-nonylamine, n-decylamine Monoamine compounds such as n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, benzylamine, aminoacetaldehyde diethyl acetal, Range amine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, 1,4-butanediamine, N, N′-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N, N′-dimethyl-1 , 5-pentanediamine, 1,6-hexanediamine, N, N′-dimethyl-1,6-hexanediamine, diamine compounds such as isophoronediamine, diethylenetriamine, N, N, N ′, N ″ N ″ − Pentamethyldiethylenetriamine, N- (aminoethyl) piperazine, N- (aminopropyl) piperazine, etc. Triamine compounds.

  Examples of the hydrazines described above include 1,1-di-n-butylhydrazine, 1,1-di-t-butylhydrazine, 1,1-di-n-pentyldrazine, 1,1-di-n. -Hexylhydrazine, 1,1-dicyclohexylhydrazine, 1,1-di-n-heptylhydrazine, 1,1-di-n-octylhydrazine, 1,1-di- (2-ethylhexyl) hydrazine, 1,1- Diphenylhydrazine, 1,1-dibenzylhydrazine, 1,2-di-n-butylhydrazine, 1,2-di-t-butylhydrazine, 1,2-di-n-pentyldrazine, 1,2-di -N-hexylhydrazine, 1,2-dicyclohexylhydrazine, 1,2-di-n-heptylhydrazine, 1,2-di-n-octylhydrazine, 1,2-di- (2-ethylhexyl) ) Hydrazine, 1,2-diphenyl hydrazine and 1,2-benzyl hydrazine.

  Examples of the monoalcohols described above include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, and cyclohexanol. , Benzyl alcohol, and terpineol.

  Examples of the diols described above include ethylene glycol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2,3-butanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 3,4-hexanediol, 3,4-heptanediol, 3,4-octanediol, 3,4-nonanediol, 3,4-decanediol, 4 , 5-octanediol, 4,5-nonanediol, 4,5-decanediol, 5,6-decanediol, 3-N, N-dimethylamino-1,2-propanediol, 3-N, N-diethylamino -1,2-propanediol, 3-N, N-di-n-propylamino-1,2-propanediol, 3-N, N-di- -Propylamino-1,2-propanediol, 3-N, N-di-n-butylamino-1,2-propanediol, 3-N, N-di-i-butylamino-1,2-propanediol And 3-N, N-di-t-butylamino-1,2-propanediol.

  Examples of the hydroxyamines described above include N, N-diethylhydroxylamine, N, N-di-n-propylhydroxylamine, N, N-di-n-butylhydroxylamine, N, N-di-n- Mention may be made of pentylhydroxylamine and N, N-di-n-hexylhydroxylamine.

  Examples of the α-hydroxy ketones described above include hydroxyacetone, 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 1-hydroxy-2-pentanone, 3-hydroxy-2-pentanone, and 2-hydroxy. -3-pentanone, 3-hydroxy-2-hexanone, 2-hydroxy-3-hexanone, 4-hydroxy-3-hexanone, 4-hydroxy-3-heptanone, 3-hydroxy-4-heptanone and 5-hydroxy-4 -Octanone.

  The carboxylic acids described above are not particularly limited as long as they have a reducing property with respect to metal salts. For example, formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid, and citric acid can be used. Can be mentioned.

  The above reducing agents can be used by appropriately selecting or combining one or two or more of those capable of reducing them according to the kind of the metal salt. For example, when copper formate is used as the metal salt, the reducing agent is preferably an amine compound, more preferably 2-ethylhexylpropylamine or 3-ethoxypropylamine.

  As content of the reducing agent in the metal wire formation composition mentioned above, the range of 1 mass%-99 mass% is preferable with respect to the whole quantity of a metal wire formation composition, and the range of 10 mass%-90 mass% is more. preferable. By setting the content of the reducing agent in the range of 1% by mass to 99% by mass, a high-definition metal wire patterned with high accuracy can be formed. Furthermore, the metal wire excellent in adhesiveness with the layer used as a foundation | substrate can be formed by setting it as the range of 10 mass%-90 mass%.

<Metal fine particles>
The metal line forming composition described above can contain metal fine particles for the purpose of improving the reduction precipitation rate of the metal salt or adjusting the viscosity of the metal line forming composition.

  The metal fine particles are not particularly limited, but from the viewpoint of the conductivity and stability of the particles, for example, one or more selected from the group consisting of gold, silver, copper, platinum and palladium It is preferable that the particles contain the above metal species. These metal species may be simple substances or alloys with other metals. When these metal species are simple substances, preferable metal fine particles include at least one kind or a combination of two or more kinds selected from the group consisting of gold fine particles, silver fine particles, copper fine particles, platinum fine particles and palladium fine particles.

  Among the metal fine particles, there are metal fine particles containing one or more metal species selected from the group consisting of silver, copper and palladium from the viewpoint of cost, availability, and catalytic ability when forming wiring. preferable. Metal fine particles other than these may be used. For example, when a copper salt is used as the metal salt, the metal fine particles are oxidized by copper ions, or the catalytic ability is reduced to reduce the copper salt to metal copper. Since the deposition rate may be reduced, it is more preferable to use the metal fine particles described above.

  The average particle size of the metal fine particles is preferably in the range of 0.01 μm to 5 μm. From the viewpoint of preventing the metal surface activity from increasing and causing an oxidation reaction, and from the viewpoint of preventing aggregation of the metal fine particles, the particle diameter of the metal fine particles is preferably 0.01 μm or more as described above. From the viewpoint of forming a high-definition metal wire, the average particle size of the metal fine particles is preferably 5 μm or less as described above.

  The method for measuring the average particle size is as follows.

  Select any three locations from the field of view observed using a microscope such as a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), or a field emission scanning electron microscope (FE-SEM). Then, shoot at the most suitable magnification for particle size measurement. From each of the obtained photographs, 100 particles were arbitrarily selected, and the long axis of the particles was selected from transmission electron microscope (TEM), field emission transmission electron microscope (FE-TEM), field emission scanning electron microscope (FE). -SEM) or the like, the particle size is calculated by dividing the measurement magnification, and these values can be obtained by arithmetic averaging. Further, the standard deviation can be obtained from the particle diameter and number of individual metal fine particles during the above observation.

  The metal fine particles may be commercially available or may be synthesized by a known method, and are not particularly limited. As a known synthesis method, for example, a gas phase method (dry method) such as a sputtering method or an in-gas deposition method, or a liquid phase in which a metal compound solution is reduced in the presence of a surface protective agent to precipitate metal fine particles. Method (wet method).

  The metal purity in the metal fine particles is not particularly limited, but is preferably 95% or more, and more preferably 99% or more, because the low purity may adversely affect the conductivity of the resulting wiring.

  As content of the metal fine particle in a metal wire formation composition, the range of 0 mass%-60 mass% is preferable with respect to the whole quantity of a metal wire formation composition, 1 mass%-40 mass% are more preferable, 1 mass A range of% to 20% by mass is particularly preferable.

<Solvent>
The metal wire forming composition described above preferably contains a solvent from the viewpoint of adjusting the viscosity of the metal wire forming composition to improve the productivity of the metal wire and obtaining a uniform shaped metal wire. .

  Examples of the solvent include an organic solvent that can dissolve or disperse each component in the metal wire forming composition and does not participate in the reduction reaction of the metal salt. Specifically, one type selected from the group consisting of ethers, esters, aliphatic hydrocarbons and aromatic hydrocarbons or a mixture of two or more types compatible with each other can be used.

  Examples of ethers, aliphatic hydrocarbons, and aromatic hydrocarbons include compounds exemplified as the [B] solvent of the radiation-sensitive composition described above.

  Examples of the esters include methyl formate, ethyl formate, butyl formate, γ-butyrolactone, and other compounds exemplified as the [B] solvent of the radiation-sensitive composition described above.

  Of these organic solvents, ethers are preferable, particularly hexyl methyl ether, diethylene glycol dimethyl ether, and the like from the viewpoint of easy adjustment of the viscosity of the metal wire-forming composition.

  The content of the solvent contained in the metal wire forming composition is preferably in the range of 0% by mass to 95% by mass with respect to the total amount of the metal wire forming composition, and in the range of 1% by mass to 70% by mass. More preferably, it is particularly preferably in the range of 10% by mass to 50% by mass.

  A metal wire formation composition can be manufactured by mixing each above-mentioned ingredient. In this case, the mixing method is not particularly limited, and examples thereof include stirring with a stirring blade, stirring with a stirrer and a stirrer, stirring with a shaker, and stirring with ultrasonic waves (homogenizer). As stirring conditions, for example, in the case of stirring with stirring blades, the rotation speed of the stirring blades is usually in the range of 1 rpm to 4000 rpm, preferably in the range of 100 rpm to 2000 rpm.

(Polarizing element)
The polarizing element of embodiment of this invention is a wire grid type polarizing element manufactured using the manufacturing method of the base material which has a metal wire of embodiment of this invention. The polarizing element of the embodiment of the present invention is characterized in that the period of the metal grating made of the metal wire is 10 nm to 200 nm.

The polarizing element of embodiment of this invention can be manufactured according to the manufacturing method of the base material which has a metal wire of embodiment of this invention demonstrated using FIGS. That is, the polarizing element of the embodiment of the present invention is manufactured by the manufacturing method including the following steps (i) to (iv), which is the same as the above-described manufacturing method of the substrate having the metal wire of the embodiment of the present invention. be able to.
(I) The process of forming the coating film of the film forming composition containing the polymer which has an acid dissociable group, and an acid generator on a base material (ii) The process of irradiating a predetermined part of the said coating film with radiation (iii) ) A step of providing a layer of a metal line forming composition having a line width of 0.1 μm or more and 20 μm or less, ie, a line width of 0.1 μm to 20 μm, on the coating film that has been irradiated with radiation (iv) The metal line forming composition Heating the layer

  And the process of said (ii) can include the process of heating the coating film after the said radiation irradiation.

  Therefore, the polarizing element according to the embodiment of the present invention has the same structure as the substrate having a metal wire shown in FIG. 5, for example. More specifically, the polarizing element according to the embodiment of the present invention can be configured using, for example, a substrate having a metal wire shown in FIG. Therefore, when the configuration of the polarizing element according to the embodiment of the present invention is described with reference to the drawings, the same reference numerals are given to the same components as those of the substrate having a metal wire in FIG. Is omitted.

  FIG. 6 is a plan view schematically showing the configuration of the polarizing element of the embodiment of the present invention.

  FIG. 7 is a diagram schematically showing a cross-sectional structure of the polarizing element according to the embodiment of the present invention.

  A polarizing element 100 according to an embodiment of the present invention shown in FIGS. 6 and 7 is configured by providing a metal grid made of metal wires 101 on a substrate 1 as an example of a base material. As described above, the metal grid is formed on the substrate 1 according to the method for manufacturing the base material having the metal wire according to the embodiment of the present invention. The metal lattice has a structure in which a plurality of extremely thin metal wires 101 are arranged at a substantially constant period so as to be substantially parallel to each other. Each of the metal wires 101 corresponds to the pattern 6 formed from the metal wire forming material layer of FIG. 5 described above, and is used as a metal wire.

  And the metal wire 101 uses the metal wire forming material mentioned above, and as shown in FIG.6 and FIG.7, on the board | substrate 1 which has the liquid-repellent convex part 12 and the lyophilic concave part 13 from it, It is formed along the recess 13. In addition, the convex part 12 on the board | substrate 1 is formed from a radiation sensitive composition as mentioned above, can have a light transmittance, and can form a light transmissive area | region on the board | substrate 1. FIG. In the example shown in FIG. 7, the layer 103 is disposed at the bottom of the recess 13 and below the metal wire 101 as in FIGS. 3 to 5. The layer 103 of the concave portion 13 is the same as that formed by heating the radiation emitting portion 3 of FIG. 2 described above by the heating step of FIG. 3, and serves as a base layer that can impart lyophilicity to the concave portion 13.

  In the polarizing element 100 of the embodiment of the present invention, the line width of the metal wire 101 is preferably 0.1 μm to 20 μm, and the period of the metal grating made of the metal wire 101 is greater than 0.1 μm and less than 200 μm. Preferably there is.

  In the polarizing element 100, the interval between the metal lines 101, that is, the period of the metal grating needs to be considerably smaller than the wavelength of the light to be polarized. Thereby, it can be used as a polarizing element such as a polarizing plate. The polarizing plate is not limited to a plate-like body, and includes other forms such as a sheet-like body and a film-like body.

  In the polarizing element 101 having such a configuration, the light component (A) substantially parallel to the longitudinal direction of the metal wire 101 is reflected by the metal wire 101 functioning as a metal. On the other hand, the light component (B) substantially orthogonal to the longitudinal direction of the metal wire 101 is transmitted. That is, the polarizing element 101 functions as a transparent body with respect to the light component (B) even if the metal wire 101 exists. For this reason, the polarizing element 101 exhibits a polarizing function by reflecting a part of the light to be polarized by the metal wire 101 and transmitting the remaining light.

  The polarizing element 100 according to the embodiment of the present invention can constitute a reflective polarizing element, and is superior in terms of light utilization efficiency as compared with a conventionally known absorbing polarizing element such as a polarizing plate.

[Electrode substrate]
An electrode substrate according to an embodiment of the present invention is manufactured using the method for manufacturing a base material having a metal wire according to an embodiment of the present invention, and has an electrode having a metal electrode configured by arranging extremely thin metal wires in a grid pattern. It is a substrate. The electrode substrate according to the embodiment of the present invention is characterized in that the metal line constituting the electrode has a line width of 0.1 μm to 20 μm.

As described above, the electrode substrate according to the embodiment of the present invention can be manufactured according to the method for manufacturing a base material having a metal wire according to the embodiment of the present invention described with reference to FIGS. That is, the polarizing element of the embodiment of the present invention can be manufactured by the manufacturing method including the following steps (i) to (iv), which is the same as the manufacturing method of the substrate having the metal wire of the embodiment of the present invention. it can.
(I) The process of forming the coating film of the film forming composition containing the polymer which has an acid dissociable group, and an acid generator on a base material (ii) The process of irradiating a predetermined part of the said coating film with radiation (iii) ) A step of providing a layer of a metal line forming composition having a line width of 0.1 μm or more and 20 μm or less, that is, a line width of 0.1 μm to 20 μm, on the coating film that has been irradiated with radiation (iv) The metal line forming composition Heating the layer

  And the process of said (ii) can include the process of heating the coating film after the said radiation irradiation.

  Therefore, the electrode substrate according to the embodiment of the present invention includes, for example, components common to the substrate having the metal wire shown in FIG. 5 and has a similar structure. Therefore, when the configuration of the electrode substrate of the embodiment of the present invention is described with reference to the drawings, the same reference numerals are given to the same components as those of the substrate having metal wires in FIG. Is omitted.

  FIG. 8 is a plan view schematically showing the configuration of the electrode substrate according to the embodiment of the present invention.

  FIG. 9 is a diagram schematically showing a cross-sectional structure of the electrode substrate according to the embodiment of the present invention.

  The electrode substrate 200 according to the embodiment of the present invention shown in FIGS. 8 and 9 is configured by arranging metal wires 201 in a grid pattern on a light-transmitting substrate 1 as an example of a base material. As described above, the grid-like metal wire 201 is formed on the substrate 1 according to the method for manufacturing a base material having a metal wire according to the embodiment of the present invention. That is, each of the metal lines 201 corresponds to the pattern 6 formed from the above-described layer of the metal line forming material in FIG. 5 and is used as a metal line.

  And the metal wire 201 uses the metal wire forming material mentioned above, and as shown in FIG.8 and FIG.9, on the board | substrate 1 which has the liquid-repellent convex part 12 and the lyophilic concave part 13 from it, It is formed along the recess 13. At this time, the electrode substrate 200 according to the embodiment of the present invention has the metal wires 201 arranged in a grid pattern in the step (ii) of the manufacturing method of the base material having the metal wires according to the embodiment of the present invention used for the manufacture thereof. The grid pattern is drawn and exposed through a photomask having a grid pattern or by using a direct drawing type exposure apparatus so that the radiation irradiation section 3 having the same shape as that shown in FIG. As a result, in the example shown in FIG. 9, the recesses 13 are formed in a lattice shape so as to correspond to the lattice-like arrangement of the metal wires 201 shown in FIG. And the convex part 12 on the board | substrate 1 is formed from a radiation sensitive composition as mentioned above, can have a light transmittance, and can form a light transmissive area | region on the board | substrate 1. FIG.

  In the example shown in FIG. 9, the layer 203 is disposed at the bottom of the recess 13 and below the metal wire 101 as in FIGS. 3 to 5. The layer 203 of the concave portion 13 is the same as that formed by heating the radiation emitting portion 3 of FIG. 2 described above by the heating step of FIG. 3, and serves as an underlayer capable of imparting lyophilicity to the concave portion 13.

  In the electrode substrate 200 of the embodiment of the present invention, the line width of the metal wire 201 is preferably 0.1 μm to 20 μm. The arrangement period of the plurality of metal lines 201 that are substantially parallel to each other is equal to the line width of the metal lines 201 in both the plurality of metal lines 201 extending in the vertical direction and the plurality of metal lines 201 extending in the horizontal direction in FIG. Is preferably set to about 5 to 10 times. That is, when the metal line 201 has a line width of 100 nm (0.1 μm), the arrangement period of the plurality of metal lines 201 is preferably 500 nm (0.5 μm) to 1000 nm (1 μm). By setting the line width and arrangement period of the metal wires 201 in this way, the electrode substrate 200 according to the embodiment of the present invention can achieve a high visible light transmittance of about 60% to 80%.

  Therefore, the electrode substrate 200 according to the embodiment of the present invention can achieve a high aperture ratio by providing ultrafine metal wires with a line width of 0.1 μm to 20 μm in a grid pattern on the light transmissive substrate 1. The electrode substrate 200 includes a metal electrode having excellent conductivity and excellent light transmittance, and can be used for manufacturing a display element for a transmissive display element.

  As a result, the electrode substrate 200 according to the embodiment of the present invention can be substituted for the electrode substrate with ITO using ITO as an electrode, which is feared to be depleted of raw materials.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is limited to this Example and is not interpreted.

[GPC analysis]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer (A) and the polymer (PA) were determined by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8220). Was measured in terms of polystyrene under conditions of tetrahydrofuran (THF) solvent.
Measurement method: Gel permeation chromatography (GPC) method Standard material: Polystyrene conversion Device: Tosoh Co., Ltd., trade name: HLC-8220
Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected Solvent: tetrahydrofuran Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1mL / min

[Measurement of ¹ H-NMR]
¹ H-NMR was measured at 25 ° C. and CDCL ₃ with a nuclear magnetic resonance apparatus (AVANCE III AV400N manufactured by Bruker).

  In this example, a polymer (hereinafter referred to as [A] polymer) which was an example of the polymer having an [A] acid dissociable group according to the embodiment of the present invention described above was synthesized.

<[A] Synthesis of polymer>
[Synthesis Example 1]
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 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 were charged, the temperature of the solution was raised to 80 ° C. while gently stirring in a nitrogen atmosphere, and this temperature was maintained for 4 hours for polymerization. As a result, a solution containing the polymer (A-1) as a copolymer was obtained (solid content concentration = 34.6% by mass, Mw = 26000, Mw / Mn = 2.2). In addition, solid content concentration means the ratio of the copolymer mass which occupies for the total mass of a copolymer solution.

Next, to 10 parts by mass of the solution containing the obtained polymer (A-1), 13 parts by mass of diethylene glycol dimethyl ether, 3,3,4,4,5,5,6,6,7,7,8,8, After adding 4.8 parts by mass of 8-tridecafluoro-1-vinyloxyoctane and stirring sufficiently, 0.27 parts by mass of trifluoroacetic acid was added and reacted at 80 ° C. for 9 hours in a nitrogen atmosphere. Subsequently, the reaction solution was cooled to room temperature, and 0.3 parts by mass of pyridine was added to quench the reaction. The resulting reaction solution is purified by reprecipitation by adding dropwise to a large excess of methanol, and subsequently dissolved in 10 parts by mass of diethylene glycol dimethyl ether, followed by reprecipitation purification by adding dropwise to a large excess of hexane, After drying, 6.8 parts by mass of [A] polymer (P-1) was obtained as a white solid copolymer. The obtained [A] polymer (P-1) was analyzed using ¹ H-NMR to confirm that acetalization had progressed (chemical shift: 4.80 ppm, acetal group C—H). .

<Preparation of radiation-sensitive composition>
[Example 1]
100 parts by mass of [A] polymer (P-1) obtained in Synthesis Example 1 above, 2 parts by mass of N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester as [C] acid generator, and [D] increase 1 part by mass of 2-isopropylthioxanthone as a sensitizer and 2-phenylbenzimidazole as an [E] quencher are mixed, and 0.1 part by mass of Polyflow No75 (manufactured by Kyoeisha Chemical Co., Ltd.) is added as a surfactant. Then, after adding diethylene glycol dimethyl ether as a [B] solvent so that the solid content concentration was 20% by mass, a radiation sensitive composition was prepared by filtering with a Millipore filter having a pore size of 0.5 μm.

<Metal wire forming composition>
As a metal wire (silver wire) forming composition for forming a metal wire made of silver, NPS-JL manufactured by Harima Kasei Co., Ltd., which is a metal wire (silver wire) forming ink, was used.

<Membrane evaluation>
[Example 2]
Film formation was performed using the radiation-sensitive composition prepared in Example 1, and the following evaluation was performed.

[Contact angle]
The radiation-sensitive composition prepared in Example 1 was applied onto an alkali-free glass substrate with a spinner, and then prebaked on a 90 ° C. hot plate for 2 minutes to form a 0.5 μm thick coating film. Subsequently, the obtained coating film was irradiated with radiation through a quartz mask (contact) using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kaken Co., Ltd.) and an exposure amount of 250 mJ / cm ² . Then, by baking for 5 minutes at 110 ° C. using a hot plate, the exposed part (concave part) becomes a lyophilic part, and the part other than the exposed part (convex part) becomes a lyophobic part. A film patterned by the above (hereinafter, sometimes referred to as a “hydrophobic patterning film”) was formed. In the formed lyophobic patterning film, using a contact angle meter (CA-X manufactured by Kyowa Interface Science Co., Ltd.), the coating film surface of the exposed part corresponding to the lyophilic part, and the coating film of the unexposed part corresponding to the lyophobic part The contact angle of water and tetradecane on each surface was measured to confirm the repellency.

  As a result of the evaluation, the contact angle of water on the exposed surface was 73 degrees, and the contact angle of water on the unexposed surface was 108 degrees. The contact angle of tetradecane on the exposed surface was 5 degrees, and the contact angle of tetradecane on the unexposed surface was 64 degrees.

[Concave patterning confirmation]
Using the radiation-sensitive composition prepared in Example 1, regarding the film obtained by the same method as the above [Contact Angle], the film thickness of the exposed part (concave part) and the unexposed part (convex part) is changed to a contact type film. The thickness was measured with a thickness gauge (manufactured by Keyence: Alpha Step IQ). And the difference of the film thickness of an unexposed part and the film thickness of an exposed part was computed, and concave shape formation property was confirmed by calculating the film thickness reduction rate (%) from a following formula.

  As a result of the evaluation, the difference between the film thickness of the unexposed area and the film thickness of the exposed area was 0.13 μm, and the film thickness reduction rate (%) was 26%.

<Manufacture of a base material having a metal wire>
[Example 3]
Using a clean track ACT-8 manufactured by Tokyo Electron Co., Ltd., the radiation-sensitive composition prepared in Example 1 was coated on a non-alkali glass substrate as a base material with a spinner, and then 2 on a 90 ° C. hot plate. A 0.5 μm thick coating film was formed by pre-baking for a minute.

Next, the coating film on the obtained substrate was irradiated with an electron beam using a simple electron beam drawing apparatus (manufactured by Hitachi, model HL800D, output: 50 KeV, current density: 5.0 amperes / cm ² ). Then, exposure was performed. The exposure with the electron beam was performed such that a plurality of line-shaped electron beam irradiation portions extending in one direction were formed on the coating film, and they were spaced apart from each other and arranged at a constant period. As a result, each of the plurality of line-shaped electron beam irradiation units is disposed between the adjacent line-shaped electron beam irradiation units with the line-shaped electron beam non-irradiation units in the same manner. . The line-shaped electron beam irradiated portion and the line-shaped electron beam non-irradiated portion are arranged in stripes on the coating film. At this time, the line width of the electron beam irradiation part of the coating film was 200 nm, and the arrangement period was 400 nm.

  After exposure with an electron beam, heating was performed at 110 ° C. for 5 minutes in the same clean track ACT-8. By this heating after exposure, a concave portion was formed in the electron beam irradiated portion to become a lyophilic portion, and a non-electron beam irradiated portion formed a convex portion to become a liquid repellent portion. Hereinafter, the film patterned by the lyophilic part and the lyophobic part may be referred to as a lyophilic patterning film.

  Next, the metal wire (silver wire) forming composition described above was applied by a spinner on the substrate on which the above-described hydrophilic / repellent patterning film was formed. As a result, in the liquid repellent part of the lyophobic patterning film, the metal line forming composition was blown off, and a layer of the metal line forming composition was formed only in the lyophilic part. The layer of the metal line forming composition was formed along the above-mentioned concave portion constituting the lyophilic part, and had a line shape, and the line width was 200 nm.

  Next, the substrate on which the layer of the above-described line-shaped metal wire forming composition was formed was heat-treated at 200 ° C. for 10 minutes using a hot plate and a firing atmosphere as a reducing atmosphere using hydrogen gas. Then, a plurality of extremely thin silver wires were formed on the substrate to produce a substrate having a silver wire that is a metal wire.

  In the manufactured substrate having a silver wire, the silver wire had a shape and an arrangement corresponding to the shape and arrangement of the electron beam irradiation section described above. That is, each of the plurality of silver wires had a line width of 200 nm and an arrangement period of 400 nm. The obtained substrate having silver wires was able to constitute a reflective polarizing plate using the plurality of silver wires as a metal lattice.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.

  For example, in the above-described method for producing a substrate having a metal wire according to the embodiment of the present invention, the above steps (i) to (iv) are repeated twice or more, and different metal wires are formed on one surface of the substrate. It is also possible to provide a plurality of layers. In that case, the metal wires can be arranged on the base material with a smaller period in plan view, and a base material on which a finer metal lattice is formed can be easily manufactured.

  Moreover, in the manufacturing method of the base material which has a metal wire of embodiment of this invention mentioned above, the process of said (i)-(iv) is implemented and one surface (surface) of a light-transmissive base material is carried out. After forming a metal line with a predetermined line width and a predetermined period, the above-mentioned steps (i) to (iv) are performed on the other surface (back surface) of the substrate, and a predetermined line is formed on the back surface of the substrate. It is also possible to form a metal wire with a predetermined period in width. In plan view, the metal wires can be arranged on the base material with a smaller period, and a base material on which a higher-definition metal lattice is formed can be easily manufactured.

  The present invention can be used as a technique for forming highly accurate wiring on various substrates. The present invention can also be used as a technique for forming high-definition metal wires on various substrates.

DESCRIPTION OF SYMBOLS 1 Substrate 2, 2a Coating film 3 Radiation irradiation part 3-2 Radiation non-irradiation part 4 Metal wire formation material 5,103,203 Layer layer 6 Pattern 12 Convex part 13 Concave part 100 Polarizing element 101,201 Metal line 200 Electrode board

Claims (9)

The manufacturing method of the base material which has a metal wire characterized by having the process of following (i)-(iv).
(I) The process of forming the coating film of the film forming composition containing the polymer which has an acid dissociable group, and an acid generator on a base material (ii) The process of irradiating a predetermined part of the said coating film with radiation (iii) ) A step of providing a layer of a metal line forming composition having a line width of 0.1 μm to 20 μm on the coating film irradiated with the radiation. (Iv) A step of heating the layer of the metal line forming composition.   The method for producing a substrate having a metal wire according to claim 1, wherein the step (ii) includes a step of heating the coating film after irradiation with radiation.   The said acid dissociable group contains a fluorine atom, The manufacturing method of the base material which has a metal wire of Claim 1 or 2 characterized by the above-mentioned.   4. The metal wire according to claim 1, wherein the acid dissociable group is a group containing at least one structural unit selected from the group of an acetal bond and a hemiacetal ester bond. The manufacturing method of the base material which has. The group containing at least one structural unit selected from the group of the acetal bond and the hemiacetal ester bond is at least one selected from the group of structural units represented by the following formula (1-1) and the following formula (1-2). The manufacturing method of the base material which has a metal wire of Claim 4 characterized by the above-mentioned.

(In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rf independently represents an organic group having a fluorine atom. Indicates a binding site.)   The said film forming composition contains the polymeric compound which has an ethylenically unsaturated bond, The manufacturing method of the base material which has a metal wire of any one of Claims 1-5 characterized by the above-mentioned. The said film formation composition has at least 1 chosen from the group of the structural unit shown by following formula (2)-following formula (5), The any one of Claims 1-6 characterized by the above-mentioned. The manufacturing method of the base material which has a metal wire.

(In formulas (2) to (5), R ³ independently represents a hydrogen atom or a methyl group. R ⁴ independently represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. An alkenylene group, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 12 carbon atoms, or one or more hydrogens of these groups A group in which an atom is substituted with a fluorine atom, R ⁵ independently represents a hydrocarbon group in which one or more hydrogen atoms have been substituted with a fluorine atom, m represents 0 or 1, and n represents independently. 0-12 are shown.)   It is manufactured using the manufacturing method of the base material which has a metal wire of any one of Claims 1-7, The period of the metal lattice which consists of the said metal wire is larger than 0.1 micrometer and is 200 micrometers or less, It is characterized by the above-mentioned. A polarizing element.   An electrode substrate manufactured using the method for manufacturing a base material having a metal wire according to any one of claims 1 to 7.

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