JP6528384B2 - Method of manufacturing base material having lyophilic part and liquid repellent part, composition, method of forming conductive film, electronic circuit and electronic device - Google Patents

Description

  The present invention relates to a method for producing a substrate having a lyophilic portion and a liquid repellent portion, a composition, a method for forming a conductive film, an electronic circuit and an electronic device.

  In addition to downsizing and thinning, electronic devices such as liquid crystal displays, mobile information devices such as mobile phones and tablets, digital cameras, organic EL displays, organic EL lighting and sensors are required to have higher performance. Printed electronics technology that directly prints wiring has attracted attention as a method of manufacturing these electronic devices more inexpensively. Production of electronic parts by printing using this technology can usually skip multi-step processes including exposure and development and vacuum processes such as vapor deposition, and significant simplification of the processes is expected. .

  Printing methods such as ink jet printing, screen printing, gravure printing, gravure offset printing and the like can be used as a simple and low-cost process because wiring of a desired pattern can be directly formed on a substrate. However, when forming a wiring of a desired pattern, as a film forming material used for printing flows, these spreading and bleeding occur, and there is a limit to form a fine pattern excellent in linearity.

  In addition, a technology for patterning a film-forming material by printing and forming a metal wiring by heat baking or light baking has been actively studied (see, for example, Patent Document 1), but spreading or bleeding of material during printing In addition to the above problems, there is a problem in the adhesion of the obtained wiring to the substrate.

  Then, the above-mentioned subject is solved and high-definition printing is made possible, and the technique of providing the layer (underlayer) used as the ground of wiring is examined for high-definition film formation. The undercoating treatment for providing the undercoating layer is often performed for the purpose of suppressing the spread of the film-forming material coated on the substrate, bleeding and the like, and improving the printability.

  For example, techniques for grafting epoxy groups to a substrate are known (see, for example, Patent Documents 2 and 3). Moreover, the technique which apply | coats a photocatalyst on a board | substrate is known (for example, refer patent document 4 and patent document 5). Furthermore, there is known a technique for applying an acrylic copolymer on a substrate (see, for example, Patent Documents 6 and 7).

JP, 2011-241309, A Japanese Patent Application Publication No. 2003-114525 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 in which the conventional base layer is provided, the suppression of the wetting and spreading of the film forming material is not sufficient, and it has been difficult to form a high definition wiring. For example, in the conventional base treatment, the characteristics of the surface of the underlayer to which the film-forming material is applied are uniform. Therefore, when the film-forming material is printed in a predetermined pattern, it has not been possible to sufficiently suppress the material from spreading from the state immediately after printing.

  The present invention has been made based on the above findings. That is, an object of the present invention is to provide a method for producing a substrate having a base film which forms a high-definition pattern by suppressing wetting and spreading of film-forming ink, and a composition used for forming the base film. is there. The object of the present invention is to provide a substrate having a lyophilic area and a liquid repellent area used for forming a high-definition pattern by suppressing the spread and wetting of a film-forming ink, and a manufacturing method for manufacturing the same. It is to do.

  Another object of the present invention is to provide a method of forming a conductive film using the above-described method of manufacturing a substrate having a lyophilic portion and a liquid repellent portion, and an electronic circuit having the conductive film and the electronic circuit thereof. Providing an electronic device having

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

  Under such circumstances, the present inventors have intensively studied to solve the above problems, and as a result, it is found that the above problems can be solved by a method including a specific step and not including a development step. Completed the invention.

  The structural example of this invention is as follows.

[1] A lyophilic part and a liquid repellent part characterized by producing a substrate having a lyophilic part and a liquid repellent part including the following steps (i) and (ii) but not including the developing step. The manufacturing method of the base material which has.
(I) applying a composition containing a polymer having a silicon atom-containing group and an acid generator to form a coating film (ii) irradiating a predetermined portion of the coating film

  [2] The method for producing a substrate having a lyophilic part and a liquid repellent part according to [1], further comprising (iii) a step of heating the coating film after the radiation irradiation.

  [3] The method for producing a substrate having a lyophilic part and a liquid repellent part according to [1] or [2], wherein the group containing a silicon atom is an acid dissociable group.

  [4] The lyophilic liquid according to any one of [1] to [3], wherein the contact angle difference between the irradiated part and the non-irradiated part in the step (ii) with respect to tetradecane is 30 ° or more. The manufacturing method of the base material which has a part and a liquid repellant part.

  [5] The coated film obtained in the step (iii), characterized in that the film thickness of the lyophilic area is 10% or more lower than the initial film thickness before the formation of the lyophilic area [1] ] The manufacturing method of the base material which has a lyophilic part in any one of-[4], and a liquid repelling part.

  [6] The group containing a silicon atom is selected from the group of groups represented by the following formula (1-1), the following formula (1-2), the following formula (1-3) and the following formula (1-4) The method for producing a substrate having a lyophilic part and a liquid repellent part according to any one of [1] to [5], which is at least one of the following.

(In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rs independently represents a monovalent organic group having a silicon atom Indicates
In formulas (1-3) and (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom , An alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, a group in which part or all of hydrogen atoms of these groups are substituted with a substituent, or a monovalent organic group having a silicon atom Indicates a group.
In Formula (1-1), Formula (1-2), Formula (1-3) and (1-4), * represents a binding site. )

[7] The group containing a silicon atom is at least one selected from the group of groups represented by the following formula (1-3) and the following formula (1-4), and the following formula (1-3) and the following In formula (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or 1 to 20 carbon atoms. The alkyl group, the alicyclic hydrocarbon group, the aryl group, the group in which part or all of the hydrogen atoms of these groups are substituted with a substituent, the group represented by the following formula (1-5), or -SiR ^A ₃ is shown, and R ^A represents an alkyl group having 1 to 10 carbon atoms. Production of a substrate having a lyophilic area and a liquid repellent area according to any one of [1] to [6] Method.

(In Formula (1-5), R ^B is each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a group represented by Formula (1-5-2). L 1 is 0 to 20 Is an integer of
In formula (1-5-2), R ^C independently represents an alkyl group having 1 to 20 carbon atoms or a phenyl group. L2 is an integer of 0-5.
In Formula (1-3), Formula (1-4), Formula (1-5) and (1-5-2), * indicates a binding site. )

  [8] The base material having a lyophilic part and a liquid repellent part according to any one of [1] to [7], characterized in that the composition contains a polymerizable compound having an ethylenically unsaturated bond. Production method.

  [9] A method for producing a substrate comprising a polymer having a group containing a silicon atom and an acid generator and having a lyophilic part and a liquid repellent part according to any one of [1] to [8] The composition characterized by the above.

  [10] A composition for forming a conductive film on the lyophilic portion formed by the method for producing a substrate having a lyophilic portion and a liquid repelling portion according to any one of [1] to [8] A method of forming a conductive film, comprising forming a conductive film.

  [11] An electronic circuit comprising a conductive film formed by the method for forming a conductive film according to [10].

  [12] An electronic device comprising the electronic circuit according to [11].

  According to the present invention, a method for producing a substrate having a lyophilic area and a lyophobic area, which is used to form a high-definition pattern by suppressing the spread and wetting of a film-forming ink, a lyophilic area and a lyophobic area There are provided a composition used in the production of a substrate having the following: a method of forming a conductive film, an electronic circuit, and an electronic device.

It is sectional drawing which shows typically the coating film of the composition of embodiment of this invention formed on the board | substrate. It is sectional drawing which demonstrates typically exposure of the coating film of the composition of embodiment of this invention on a board | substrate. It is sectional drawing which illustrates typically heating of the coating film of the composition of embodiment of this invention with which one part was exposed. It is sectional drawing which demonstrates typically application | coating of the film formation material in the film formation method 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 figure which shows the quartz mask used in the Example, (a) is a top view, (b) is sectional drawing.

  Hereinafter, an embodiment of the present invention will be described. First, a method of manufacturing a substrate having a lyophilic part and a liquid repellent part according to the embodiment of the present invention will be described. Then, the composition of embodiment of this invention is demonstrated.

[Method of producing base material having lyophilic part and liquid repellent part]
The manufacturing method of the base material which has the lyophilic part and the liquid repelling part of the embodiment of the present invention is characterized by including the following steps (i) to (ii) and not including the developing step. And it is preferable that the manufacturing method of the base material which has a lyophilic part and a liquid repelling part of embodiment of this invention includes the process of following (iii).
(I) applying a composition containing a polymer having a silicon atom-containing group and an acid generator to a substrate to form a coating film,
(Ii) irradiating a predetermined portion of the coating with radiation;
(Iii) a step of heating the coating after the radiation irradiation

  The method for producing a substrate having a lyophilic part and a liquid repellent part according to an embodiment of the present invention is the above-mentioned steps (i) to (ii) (hereinafter also referred to as step (i) and step (ii)). Furthermore, by using the above-mentioned step (iii) (hereinafter also referred to as step (iii)), a concave pattern can be formed without using a development step required for conventional patterning, and the lyophilic part And a liquid repellent portion can be produced.

  And in the method for producing a substrate having a lyophilic part and a liquid repellent part according to the embodiment of the present invention, in the polymer having a group containing a silicon atom to be used, the group containing a silicon atom is an acid dissociable group Is preferred. That is, a composition containing a polymer having a silicon atom-containing group and an acid generator used in step (i) has a composition containing a polymer having an acid dissociable group containing a silicon atom and an acid generator. It is preferable that it is a thing. Since the composition of step (i) contains a polymer having an acid-dissociable group containing a silicon atom and an acid generator, after step (i), the above-mentioned step (ii) and further step (iii) By being applied, a concave pattern can be efficiently formed without using a developing step which is conventionally required for patterning. And it has a concave pattern and can manufacture a substrate which has a lyophilic part and a liquid repelling part.

  Hereinafter, as a composition containing a polymer having a group containing a silicon atom in step (i) and an acid generator, a composition containing a polymer having an acid dissociable group containing a silicon atom described above and an acid generator The steps in the method for producing a substrate having a lyophilic part and a liquid repellent part according to the embodiment of the present invention will be described by taking the case of using as an example.

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

  In step (i), the substrate 1 is coated with a composition containing a polymer having an acid-dissociable group containing a silicon atom and an acid generator, preferably by heating (prebaking) the coated surface. 1 is a step of forming a coating film 2 on 1. The composition of the embodiment of the present invention has radiation sensitivity, and can be applied to step (ii) described later after step (i) to form a recess on the substrate 1.

  That is, in the step (i), by using the composition of the present embodiment having radiation sensitivity, a recess can be formed on the substrate 1 without performing the developing step in the following step (iii) or the like.

  Hereinafter, the composition of the embodiment of the present invention is also referred to as "a radiation sensitive composition". The composition (the radiation sensitive composition) of the embodiment of the present invention will be specifically described later.

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

  Moreover, since it is preferable to use the substrate with wiring finally obtained by the method of manufacturing a wiring according to the present invention as the substrate 1 for the electronic circuit etc. as it is, a resin-made substrate conventionally used for the electronic circuit , Glass substrates and semiconductor substrates are preferable.

  Before applying the radiation sensitive composition to the substrate 1, if necessary, the substrate surface may be subjected to pretreatment such as cleaning, roughening, provision of a minute uneven surface, and the like.

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

  The thickness of the coating film 2 formed in step (i) may be appropriately adjusted according to the desired application, but is preferably 0.1 μm to 20 μm, and more preferably 0.2 μm to 10 μm.

  Although the conditions of prebaking change also with compositions etc. of the radiation sensitive composition to be used, Preferably it is about 1 minute-10 minutes at 60 degreeC-120 degreeC.

[Step (ii)]
A process (ii) exposes by irradiating a radiation to at least one part of the coating film 2 formed at the process (i).

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

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

  In step (ii), the acid-dissociable group present in the coating film 2 of FIG. 1 is eliminated and volatilized by the effect of the acid generator. As a result, the film thickness of the radiation irradiated part 3 becomes thinner than the film thickness of the radiation unexposed part 3-2, and a concave pattern is formed (in FIG. 2, this film thickness change is not clearly shown. ). At this time, if the acid dissociable group has a silicon atom, the coating film 2 obtained in the step (i) and the non-irradiated portion 3-2 thereof exhibit liquid repellency, but the irradiated portion 3 With the disappearance of the acid dissociable group, it becomes more lyophilic than the non-irradiated part 3-2.

  Therefore, in the step (i), in the case where the composition of the present embodiment to be used contains a polymer having an acid-dissociable group containing a silicon atom, the liquid repellency on the substrate 1 in the step (ii) A coating film is formed having the radiation non-irradiated portion 3-2 and the radiation irradiated portion 3 which is a concave pattern more lyophilic than the radiation non-irradiated portion 3-2.

  In the step (ii), a predetermined pattern is formed through a photomask having a predetermined pattern or using a direct writing exposure apparatus so that the radiation irradiation unit 3 having the same shape as the shape of the wiring to be formed is formed. Can be drawn and exposed.

  In the present invention, visible radiation, ultraviolet radiation, far ultraviolet radiation, charged particle radiation, X-rays and the like can be used as radiation used for exposure. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure dose in the step (ii) is preferably exposed to radiation so that the film thickness of the recess obtained after the following step (iii) falls within the following range. Specifically, the intensity of the radiation at the wavelength of 365 nm is as a value measured by meter (OAI model356, OAI Optical Associates Ltd. Inc.), is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , more preferably at ^{20mJ / cm 2 ~500mJ / cm 2} .

[Step (iii)]
FIG. 3 is a cross-sectional view schematically illustrating heating of a coating film of the composition of the embodiment of the present invention which is partially exposed.

  In the step (iii), by heating the coating film obtained in the step (ii), as shown in FIG. 3, the recess 13 corresponding to the portion which was the radiation-irradiated part of the step (ii) A coated film is formed having the convex portion 12 corresponding to the portion which has not been irradiated with the radiation of ii).

  In the step (iii), it is possible to further volatilize the component which is generated in the irradiation part of the step (ii) and from which the acid dissociable group has been eliminated by the effect of the acid generator. As a result, the concave recess in the radiation irradiated part is further deepened (the film thickness of the recess 13 becomes thinner), and the film thickness of the recess 13 is thinner than the film thickness of the protrusion 12 by 10% or more. Can be formed.

  In the step (i), when the composition of the embodiment to be used contains a polymer having an acid-dissociable group containing a silicon atom, a liquid-repellent convex portion on the substrate in the step (iii) A coating film having 12 and a recess 13 more lyophilic than the portion is formed. Then, when a film-forming material in liquid form is applied onto such a coating, the film thickness difference between the convex portion 12 and the concave portion 13 is large, so the material easily gathers on the concave portion 13 due to the unevenness of the coating surface. Not only the effect of the coating film surface shape but also the lyophilic and liquid repellent properties of the surface make the film-forming material more likely to be collected on the recess 13, and more specifically, high definition wiring having a desired shape. It becomes easy to form.

  Further, in the step (i), in the case where the composition of the present embodiment to be used contains a polymer having an acid-dissociable group containing a silicon atom, the group having a silicon atom is eliminated by irradiation with radiation. Become. Since this leaving group is relatively easily volatilized, it is possible to form a coating film having a large difference in film thickness between the convex portion 12 and the concave portion 13 more easily in the step (iii).

  As a method of heating the coated film in the step (iii), for example, a method of heating the coated substrate using a hot plate, a batch type oven or a conveyor type oven, a method of hot air drying using a dryer or the like, There is a method of vacuum baking.

  Although the conditions of the said heating change also with the composition of the radiation sensitive composition used at process (i), the thickness of the coating film obtained at process (ii), etc., Preferably it is 3 minutes at 60 degreeC-150 degreeC. It is about 30 minutes.

  In the step (iii), the film thickness of the recess 13 is preferably 10% or more, more preferably 11% or more, more preferably 12% to 70% thinner than the film thickness of the projection. It is desirable to form When the coating film obtained has such a shape, when the film-forming material is applied to the recess 13, the film-forming material is less likely to overflow from the recess 13 due to the level difference of the unevenness on the surface of the coating film. Since the film-forming material is unlikely to remain in portions other than the concave portion 13, a large amount of film-forming material can be applied, and high-definition wiring can be obtained even if a large amount of wiring material is used.

  Specifically, the film thickness of the concave portion 13 and the convex portion 12 can be measured by the method described in the examples to be described later.

  In addition, although the film thickness of the recessed part 13 obtained by process (iii) may be suitably adjusted 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, further preferably Is 50 ° or more. When the contact angle difference is in the above range, even in the case where a liquid film-forming material is applied also to the surface of the convex portion 12 in the step (iv) described later, the convex portion 12 which is a liquid repellent portion The film forming material is repelled to facilitate the movement of the film forming material to the concave portion 13 which is a lyophilic portion, whereby the wiring along the concave portion 13 can be formed.

Specifically, the contact angle difference can be measured by the method described in the examples described later.
The surface of the concave portion 13 and the surface of the convex portion 12 refer to the surface of the coating film formed on the substrate 1 on the side opposite to the side in contact with the substrate 1, as shown in FIG.

  The film thickness of the recess 13 is 10% or more thinner than the film thickness of the protrusion 12 and the contact angle difference between the surface of the recess 13 and the surface of the protrusion 12 against tetradecane is 30 ° If the above conditions are satisfied, it is possible to easily apply a large amount of film forming material only on the recess 13 for the same reason as described above.

[Method of forming a film on a recess]
In the embodiment of the present invention, the base material of the embodiment of the present invention in which the concave portion 13 and the convex portion 12 are formed on the substrate 1 obtained in the step (iii), ie, the lyophilic portion and the liquid repellent portion By using the base material, it is possible to include a method of forming a film on the concave portion 13 which is the lyophilic portion.

[Step (iv)]
FIG. 4 is a cross-sectional view schematically illustrating application of a film-forming material in the film-forming method of the embodiment of the present invention.

In the step (iv), as shown in FIG. 4, using the substrate 1 obtained by the method for producing a substrate having a lyophilic part and a liquid repellent part according to the embodiment of the present invention, a concave part as the lyophilic part The film forming material 4 is applied on 13.
The film forming material 4 will be specifically described later.

  It does not specifically limit as a method of application | coating of the film formation material mentioned above, For example, the coating method using a brush or a brush, the dipping method, the spray method, the roll coating method, the spin coating method (spin coating method), slit die An appropriate method such as a coating method, a bar coating method, a squeegee method, flexographic printing, offset printing, inkjet printing, a dispensing method can be adopted. Among these, dipping, spraying, spin coating, slit die coating, offset printing, inkjet printing, and dispensing are particularly preferable.

  In addition, offset printing is preferable from the viewpoint of forming a fine, thick, low resistance, and hard to break wire. The offset printing can be performed based on, for example, the descriptions of JP-A-2010-159350 and JP-A-2011-178006.

  As described above, according to the method of manufacturing a base having a lyophilic area and a liquid repelling area of the embodiment of the present invention, the liquid repellent convex portion 12 and the lyophilic concave portion 13 are formed on the substrate 1. Is formed. Therefore, the coating film 5 of the film-forming material 4 obtained in the step (iii) is a film-forming material in the convex portion 12 when using the liquid film-forming material 4 regardless of any of the above-mentioned coating methods. 4 is repelled and easily collected in the recess 13, so that the coating film of the film forming material 4 is formed along the recess 13.

[Step (v)]
In the step (v), the substrate with a film forming material obtained in the step (iv) is heated.

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

  The pattern 6 is formed by the step (v) shown in FIG.

  The temperature for heating in step (iv) is not particularly limited, but is preferably 190 ° C. or less. When a film having poor heat resistance such as polyethylene terephthalate is used as the substrate 1, the heat resistance temperature or less of the film, specifically 150 ° C. or less is preferable.

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

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

[Method of forming conductive pattern]
In the embodiment of the present invention, the substrate formed by the step (i), the step (ii) and the step (iii) of the method for producing a substrate having a lyophilic part and a liquid repellent part according to an embodiment of the present invention The conductive film of the present invention can be formed by the same method as the film forming method of the embodiment of the present invention described above by using the conductive film forming ink or the conductive film forming paste as the film forming material. That is, using the above-described base material having a lyophilic area and a liquid repellent area of the present invention, a method of applying a conductive film forming ink on the lyophilic area which is the concave pattern, and the lyophilic area above which is the concave pattern The conductive pattern of the present invention can be formed as the conductive film of the present invention by carrying out the method of forming the conductive film in the above.

  In addition, the conductive pattern of the present embodiment formed on the film of the radiation sensitive composition of the present embodiment is excellent in characteristics such as conductivity and adhesion, and is effective for formation of high definition wiring and electrodes. It becomes.

  And patterns, such as a conductive pattern of this embodiment, can be suitably used for formation of an electronic circuit of an embodiment of the present invention as a conductive film of an embodiment of the present invention. That is, the electronic circuit of the embodiment of the present invention is configured to have a pattern such as the conductive pattern of the embodiment of the present invention.

[Electronic circuit and electronic device]
The electronic circuit of the present invention has a wiring manufactured by the method of forming a conductive pattern, and preferably has a laminate of a wiring and a substrate manufactured by the method of forming a conductive pattern.

  Moreover, the electronic device of this invention has the said electronic circuit. Therefore, the electronic device is miniaturized, thinned, and sophisticated.

  Examples of the electronic device include liquid crystal displays, portable information devices such as mobile phones, digital cameras, organic displays, organic EL lighting, various sensors, and wearable devices.

〔Composition〕
The composition of the embodiment of the present invention (hereinafter sometimes simply referred to as a composition) contains, as components, a polymer having a group containing a silicon atom and an acid generator. The composition according to the embodiment of the present invention is used in the method for producing a substrate having the lyophilic part and the liquid repellent part according to the embodiment of the present invention described above, without using the developing step conventionally required for patterning. A concave pattern can be formed to produce a substrate having a lyophilic area and a liquid repellent area.

  And in the composition of the embodiment of the present invention, in the polymer having a group containing a silicon atom, it is preferable that the group containing a silicon atom is an acid dissociable group. That is, it is preferable that the composition of embodiment of this invention contains the polymer which has an acid dissociative group containing a silicon atom as a polymer which has a group containing a silicon atom. As a result, the composition according to the embodiment of the present invention includes the steps (i) and (ii) and the step (iii) in the method for producing a substrate having the lyophilic part and the liquid repellent part according to the embodiment of the present invention described above. And a concave pattern can be formed more efficiently without using the developing step conventionally required for patterning, and a substrate having a lyophilic area and a liquid repellent area can be produced.

  Hereinafter, as a composition according to the embodiment of the present invention, a composition containing a polymer having an acid-dissociable group containing a silicon atom will be described as an example and described in more detail. In the following description, a polymer having an acid-dissociable group containing a silicon atom may be simply referred to as [A] polymer.

  The composition of the present embodiment can contain a solvent in addition to the polymer [A]. Moreover, the composition of this embodiment can contain an acid generator. Furthermore, the composition of the present embodiment can include a polymerizable compound having an ethylenically unsaturated bond, and can also include a radiation sensitive polymerization initiator.

  The composition of the present embodiment exhibits a liquid state by containing a solvent (hereinafter, may be referred to as [B] solvent), forms a coating film by coating, and easily forms an underlayer. it can.

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

Furthermore, the composition of the present embodiment can contain a polymerizable compound having an ethylenically unsaturated bond (hereinafter, may be referred to as a [F] polymerizable compound). Furthermore, the composition of the present embodiment can contain a radiation sensitive polymerization initiator (hereinafter sometimes referred to as [G] radiation sensitive polymerization initiator).
And the composition of embodiment of this invention 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 composition of the embodiment of the present invention may be adjusted depending on the desired coating method, the thickness of the coating film to be formed, and the like. In the case of forming a coating film having a film thickness of 0.5 μm to 2 μm and using a spin coating method as the coating method, preferably 5 cP (0.003 Pa · s) to 20 cP (0.02 Pa · s) can be exemplified. In the case of using a slit die coating method as the coating method, preferably, 1 cP (0.001 Pa · s) to 20 cP (0.01 Pa · s) can be exemplified.

  Hereinafter, each component which can be used as a composition of this embodiment is demonstrated.

<[A] polymer>
The polymer ([A] polymer) having an acid dissociable group containing [A] silicon atom, which is a component of the composition of the present embodiment, has the following formula (1-1), the following formula (1-2), It has at least one group selected from the group of groups represented by the following formula (1-3) and the following formula (1-4).

(In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rs independently represents a monovalent organic group having a silicon atom Show.
In formulas (1-3) and (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom , An alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, a group in which part or all of hydrogen atoms of these groups are substituted with a substituent, or a monovalent organic group having a silicon atom Indicates a group.
In Formula (1-1), Formula (1-2), Formula (1-3) and (1-4), * represents a binding site. )

  Describing in more detail, in the above formula (1-1) and the above formula (1-2), Rs can be each independently a group represented by the following formula (1-1-1).

In the above formula ^{(1-1-1), R 11} represents a single bond or a divalent organic group having 1 to 12 carbon atoms. Each of R ¹² , R ¹³ and R ¹⁵ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms of these groups A group substituted by a substituent, or -SiR ^B ₃ is shown. R ^B represents an alkyl group having 1 to 10 carbon atoms. R ¹⁴ independently represents a single bond or an oxygen atom. n is an integer of 1 to 20. * Indicates a binding site.

As a C1-C12 bivalent organic group in R ¹¹ of said Formula (1-1-1), a bivalent hydrocarbon group, the hetero atom containing group between carbon-carbon of this hydrocarbon group is mentioned, for example And groups in which some or all of the hydrogen atoms of these groups are substituted with a substituent.

  As a C1-C12 bivalent hydrocarbon group, a bivalent chain hydrocarbon group, a bivalent alicyclic hydrocarbon group, a bivalent aromatic hydrocarbon group is mentioned, for example.

Examples of the divalent chain hydrocarbon group include
Alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group and the like;
Alkenediyl groups such as ethenediyl group, propene diyl group, butene diyl group;
Alkynediyl groups such as ethynediyl group, propynediyl group, butyndiyl group and the like can be mentioned.

Examples of the divalent alicyclic hydrocarbon group include
A monocyclic cycloalkanediyl group such as cyclopropanediyl group, cyclobutanediyl group, cyclopentandiyl group, cyclohexanediyl group and the like;
A monocyclic cycloalkene diyl group such as cyclopropene diyl group and cyclobutene diyl group;
Polycyclic cycloalkanediyl groups such as norbornanediyl group, adamantandiyl group, tricyclodecanediyl group, tetracyclododecanediyl group and the like;
Examples thereof include polycyclic cycloalkene diyl groups such as norbornene diyl group and tricyclodecene diyl group.

Examples of the divalent aromatic hydrocarbon group include
Arelendiyl groups such as benzenediyl group, toluenediyl group, xylenediyl group, naphthalenediyl group and the like;
Arenedyl (cyclo) alkanediyl groups such as benzenediylmethanediyl group and naphthalenediylcyclohexanediyl group can be mentioned.

  The said hetero atom containing group means group which has a bivalent or more hetero atom in a structure. The hetero atom-containing group may have one hetero atom, or may have two or more hetero atoms.

  The hetero atom-containing group is not particularly limited as long as it is a hetero atom having a divalent or higher valence, and examples thereof include oxygen atom, nitrogen atom, sulfur atom, silicon atom, and phosphorus. An atom, a boron atom, etc. are mentioned.

Examples of the hetero atom-containing group include
A group consisting of only hetero atoms such as -SO-, -SO _2- , -SO ₂ O- and -SO _3- ;
-CO-, -COO-, -COS-, -CONH-, -OCOO-, -OCOS-, -OCONH-, -SCONH-, -SCSNH-, -SCSS-, etc. combining a carbon atom and a hetero atom And the like.

  As said substituent, a fluorine atom etc. are mentioned, for example.

Examples of the alkyl group having 1 to 20 carbon atoms as R ¹² , R ¹³ and R ¹⁵ include linear alkyl groups such as methyl, ethyl, n-propyl and n-butyl; i-propyl group And branched alkyl groups such as i-butyl group, sec-butyl group and t-butyl group. As said alkyl group, a C1-C10 alkyl group is preferable.

The alicyclic hydrocarbon group for R ¹² , R ¹³ and R ¹⁵ is, for example, monocyclic alicyclic hydrocarbon group such as cyclopentyl group and cyclohexyl group; multiple groups such as adamantyl group, norbornyl group and tetracyclodecanyl group And alicyclic hydrocarbon groups of the ring and the like.

The aryl group in R ^{12, R 13} and ^{R 15,} a phenyl group, a tolyl group, dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, and the like. As said aryl group, a C6-C10 aryl group is preferable.

  As said substituent, halogen atoms, such as a fluorine atom, a hydroxyl group, a carboxy group, a nitro group, a cyano group, etc. are mentioned, for example.

  As a specific example of preferable Rs in the said Formula (1-1) and said Formula (1-2), group shown by each following formula can be mentioned. In each formula, * indicates a binding site.

Next, groups represented by the formula (1-3) and the formula (1-4) will be described.
As described above, in the above formulas (1-3) and (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, a group in which part or all of the hydrogen atoms of these groups are substituted with a substituent, or It shows a monovalent organic group having a silicon atom.

Examples of the divalent organic group having 1 to 12 carbon atoms in ^{R 3} in the above formula (1-3) and the formula (1-4), for example, a divalent hydrocarbon radical, the carbon of the hydrocarbon group - carbon There may be mentioned a group containing a hetero atom-containing group, a group obtained by substituting a part or all of hydrogen atoms of these groups with a substituent, and the like.

  As a C1-C12 bivalent hydrocarbon group, a bivalent chain hydrocarbon group, a bivalent alicyclic hydrocarbon group, a bivalent aromatic hydrocarbon group is mentioned, for example.

Examples of the divalent chain hydrocarbon group include
Alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group and the like;
Alkenediyl groups such as ethenediyl group, propene diyl group, butene diyl group;
Alkynediyl groups such as ethynediyl group, propynediyl group, butyndiyl group and the like can be mentioned.

Examples of the divalent alicyclic hydrocarbon group include
A monocyclic cycloalkanediyl group such as cyclopropanediyl group, cyclobutanediyl group, cyclopentandiyl group, cyclohexanediyl group and the like;
A monocyclic cycloalkene diyl group such as cyclopropene diyl group and cyclobutene diyl group;
Polycyclic cycloalkanediyl groups such as norbornanediyl group, adamantandiyl group, tricyclodecanediyl group, tetracyclododecanediyl group and the like;
Examples thereof include polycyclic cycloalkene diyl groups such as norbornene diyl group and tricyclodecene diyl group.

Examples of the divalent aromatic hydrocarbon group include
Arelendiyl groups such as benzenediyl group, toluenediyl group, xylenediyl group, naphthalenediyl group and the like;
Arenedyl (cyclo) alkanediyl groups such as benzenediylmethanediyl group and naphthalenediylcyclohexanediyl group can be mentioned.

  The said hetero atom containing group means group which has a bivalent or more hetero atom in a structure. The hetero atom-containing group may have one hetero atom, or may have two or more hetero atoms.

  The hetero atom-containing group is not particularly limited as long as it is a hetero atom having a divalent or higher valence, and examples thereof include oxygen atom, nitrogen atom, sulfur atom, silicon atom, and phosphorus. An atom, a boron atom, etc. are mentioned.

Examples of the hetero atom-containing group include
A group consisting of only hetero atoms such as -SO-, -SO _2- , -SO ₂ O- and -SO _3- ;
-CO-, -COO-, -COS-, -CONH-, -OCOO-, -OCOS-, -OCONH-, -SCONH-, -SCSNH-, -SCSS-, etc. combining a carbon atom and a hetero atom And the like.

  As said substituent, a fluorine atom etc. are mentioned, for example.

Examples of the alkyl group having 1 to 20 carbon atoms as R ⁴ , R ⁵ and R ⁶ include, for example,
Straight-chain alkyl groups such as methyl, ethyl, n-propyl and n-butyl;
Examples thereof include branched alkyl groups such as i-propyl group, i-butyl group, sec-butyl group and t-butyl group.
As said alkyl group, a C1-C10 alkyl group is preferable.

As an alicyclic hydrocarbon group in R ⁴ , R ⁵ and R ⁶ , for example,
Monocyclic alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl;
Examples thereof include polycyclic alicyclic hydrocarbon groups such as adamantyl group, norbornyl group and tetracyclodecanyl group.

As an aryl group in R ⁴ , R ⁵ and R ⁶ , a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group and the like can be mentioned. As said aryl group, a C6-C10 aryl group is preferable.

  As said substituent, halogen atoms, such as a fluorine atom, a hydroxyl group, a carboxy group, a nitro group, a cyano group, etc. are mentioned, for example.

^The monovalent organic group having a silicon atom in R 4, ^{R 5} and ^{R 6,} for example, a group or a -SiR ^A _3, represented by the following formula (1-5). At this time, R ^A represents an alkyl group having 1 to 10 carbon atoms, and includes, for example, linear alkyl groups such as methyl, ethyl, n-propyl and n-butyl; i-propyl, i And branched alkyl groups such as -butyl group, sec-butyl group and t-butyl group.

(In Formula (1-5), R ^B is each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a group represented by Formula (1-5-2). L 1 is 0 to 20 Is an integer of
In formula (1-5-2), R ^C independently represents an alkyl group having 1 to 20 carbon atoms or a phenyl group. L2 is an integer of 0-5.
In formulas (1-5) and (1-5-2), * indicates a binding site. )

As a C1-C20 alkyl group in R ^B in the above formula (1-5), for example,
Straight-chain alkyl groups such as methyl, ethyl, n-propyl and n-butyl;
Examples thereof include branched alkyl groups such as i-propyl group, i-butyl group, sec-butyl group and t-butyl group.
As said alkyl group, a C1-C10 alkyl group is preferable.

As a C1-C20 alkyl group in R < ^C > in the said Formula (1-5-2), for example,
Straight-chain alkyl groups such as methyl, ethyl, n-propyl and n-butyl;
Examples thereof include branched alkyl groups such as i-propyl group, i-butyl group, sec-butyl group and t-butyl group.
As said alkyl group, a C1-C10 alkyl group is preferable.

  Although the groups represented by the following Formula (1-6) are included in the groups represented by the above Formula (1-3) and the above Formula (1-4), the groups represented by the following Formula (1-6) Preferred specific examples include the groups of the respective formulas shown thereafter. In each formula, * indicates a binding site.

  In the composition of the present embodiment, when the polymer [A] has a group represented by the above formula (1-1), the polymer represented by the following formula (1A) is represented by the hydroxyl group of the compound having a hydroxyl group which is its precursor. It is preferable that it is a polymer which the protective group derived from the vinyl ether compound (Hereafter, it may call a "compound (1A).") Introduce | transduced and comprised. When the polymer [A] has a group represented by the above formula (1-2), a protective group derived from the compound (1A) is present at the carboxyl group of the polymer having a carboxyl group which is its precursor. It is preferable that it is the polymer introduce | transduced and comprised.

In the formula ^{(1A), R 11, R} 12, R 13, R 14, R 15 and n, ^R 11 of formula (1-1-1) in the ^{aforementioned, R 12, R 13, R} 14, R ¹⁵ and n are respectively synonymous.

When the polymer [A] is a group represented by the above formula (1-3) and R ³ is a single bond, the polymer is a hydroxyl group of a compound having a hydroxyl group, which is a precursor similar to the above. It may be a polymer formed by introducing a protective group derived from a silyl compound represented by the following formula (1B) (hereinafter sometimes referred to as “compound (1B)”). Furthermore, when the polymer [A] is a group represented by the above formula (1-4) and has a group in which R ³ is a single bond, the polymer of the compound having a carboxyl group which is a precursor similar to the above It may be a polymer constituted by introducing a protective group derived from the compound (1B) into a carboxyl group.

In the above formula (1B), X is a halogen atom, preferably a chlorine atom. ^Further, R 4, ^{R 5} and ^{R 6,} and ^R 4, ^{R 5} and ^{R 6} in the above formula (1-6) is the same meaning.

  The compound to be the precursor of the above-mentioned [A] polymer, particularly the compound having a hydroxyl group as the precursor, has the property that the elimination of the protective group by heat is difficult to occur, while the elimination of the protective group by radiation is Can be suitably used to obtain the polymer [A] because of its property of being able to control Furthermore, the [A] polymer is preferable because the combination with the [C] acid generator to be described later can control the removal of the protecting group with higher precision by irradiation with radiation.

  The composition of the embodiment of the present invention contains the polymer [A] having the above structure, and is used for the method of producing a substrate having the lyophilic portion and the liquid repellent portion of the embodiment of the present invention described above . And the coating film formed at the process (i) mentioned above has the said Formula (1-1) which the [A] polymer has immediately after formation, the said Formula (1-2), the said Formula (1-3) And a characteristic derived from the group represented by the above formula (1-4). Specifically, when the composition of the embodiment of the present invention is used, first, in the above-mentioned step (i), a liquid repellent coating film derived from a silicon atom is formed. Next, when the coating film is irradiated with radiation in the above-mentioned step (ii), in the exposed portion, the above formula (1-1), the above formula (1-2), the above formula (1-3) and the above formula The group represented by any one of (1-4) is decomposed, and a state in which a protective group for a hydroxyl group or a carboxyl group is released is formed. As a result, in the coating film using the composition of the embodiment of the present invention, in the part where the protective group such as a hydroxyl group is released by the exposure, the hydroxyl group is left, and the liquid repellant caused by the protective group Sex is lost.

  Next, the method for obtaining the polymer [A] will be described in more detail.

  [A] There are two methods of obtaining a polymer, a method of using a polymer as a compound to be a precursor and a method of using a monomer as a compound to be a precursor.

  In the method of using a polymer as a compound to be a precursor, the polymer to be a precursor contains a hydroxyl group or a carboxyl group in the molecule, and the above compound (1A) or compound (1B) is contained in the hydroxyl group of the polymer to be a precursor. [A] polymer can be obtained by reacting (A).

  Further, in the method of using a monomer as a compound to be a precursor, the monomer to be a precursor contains a hydroxyl group or a carboxyl group in the molecule, and the above compound (1A) or compound is selected from the hydroxyl group or carboxyl group of a monomer to be a precursor. After reacting (1B), the resulting monomer can be polymerized to obtain the polymer [A].

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

(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 a precursor The compound (1A) or the compound (1B) described above is reacted with the hydroxyl group or carboxyl group of the polymer to obtain a polymer [A].

  As the above-mentioned monomer having a hydroxyl group, (meth) acrylic acid ester is preferable, and 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-hydroxy ethyl phthalic acid, dipropylene glycol methacrylate, dipropylene glycol acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl Acrylate, cyclohexane dimethanol monoacrylate, cyclohexane dimethanol monomethacrylate, ethyl α- (hydroxy) (Tyl) 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 The following can be listed: Plaxel FM1, Plaxcel FM1D, Plaxcel FM2D, Plaxel FM3X, Plaxel FM3X, Plaxel FM4, Plaxel FM5, Plaxel FA1D, Plaxel FA1DDM, Plaxel FA2D, Plaxel FA5, Plaxel FA10L, manufactured by Daicel Co., Ltd. it can.

  As the above-mentioned monomer having a carboxyl group, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyl oxyethyl phthalic acid, 2-methacryloyl oxyethyl phthalic acid, 2- Acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyltetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalate Acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropyl hexahydrophthalate Acid, and 2-methacryloyloxy propyl hexahydrophthalic acid.

  [A] A polymer having a hydroxyl group or a carboxyl group, which is a precursor of a polymer, can be obtained using only the monomer having a hydroxyl group or a carboxyl group as described above, and further, a 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 monomers having a hydroxyl group or a carboxyl group, (meth) acrylic acid linear 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 monomers other than these.

  More specifically, as the above-mentioned (meth) acrylic acid linear alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methacrylic 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 And 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate and the like.

Moreover, as the above-mentioned (meth) acrylic acid cyclic alkyl ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, methacryl Isobornyl acid, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, isobornyl acrylate and the like can be mentioned.

  Moreover, as the above-mentioned (meth) acrylic acid aryl ester, for example, phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate can be mentioned.

  Moreover, as said unsaturated aromatic compound, styrene, alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene is mentioned, for example.

  Moreover, as said conjugated diene, a 1, 3- butadiene, an isoprene, a 2, 3- dimethyl 1, 3- butadiene is mentioned, for example.

  Moreover, as the above-mentioned unsaturated compound containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one It can be mentioned.

  Moreover, as said maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, N- tolyl maleimide, N- naphthyl maleimide, N- ethyl maleimide, N- hexyl maleimide, N- benzyl maleimide is mentioned, for example.

As other monomers, for example, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (acryloyloxymethyl) ) 3-Ethyl oxetane, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl And acrylates.
The polymer obtained using the monomer which has polymeric groups, such as an epoxy group, an oxetanyl group, and (meth) acryloyl group, is especially preferable from being excellent in heat resistance and solvent resistance.

  [A] As a solvent used for a polymerization reaction for synthesizing a polymer having a hydroxyl group or a carboxyl group, which is a precursor of a polymer, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether And diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketones and esters.

[A] In the polymerization reaction for obtaining a polymer having a hydroxyl group or a carboxyl group, which is a precursor of a polymer, a molecular weight modifier can be used to adjust the molecular weight. As a molecular weight modifier, for example,
Halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

  As a polystyrene conversion weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the polymer which has a hydroxyl group or a carboxyl group, 1000-30000 are preferable and 5000-20000 are more preferable. By making Mw of the polymer which has a hydroxyl group or a carboxyl group into the above-mentioned range, the sensitivity with respect to the radiation of the composition of this embodiment containing a polymer [A] can be raised.

  Next, the above compound (1A) is reacted with the hydroxyl group or carboxyl group of the polymer having a hydroxyl group or carboxyl group to obtain the polymer [A], as shown by the following formula: It can be carried out by adding a vinyl ether group.

  Further, the method for obtaining the polymer [A] by reacting the above compound (1B) with the hydroxyl group or carboxyl group of the polymer having a hydroxyl group or carboxyl group is, for example, X is chlorine as shown by the following formula It can carry out by making it react with the hydroxyl group or carboxyl group of the polymer which has a hydroxyl group or a carboxyl group using a certain above-mentioned compound (1B).

  And the well-known method can be referred to the method of obtaining a [A] polymer.

  [A] Taking the case where the compound (1A) is used to obtain a polymer, for example, the method described in JP-A-2005-187609 can be referred to.

  Specifically, an acetal bond is formed by the hydroxyl group of the polymer having a hydroxyl group and the vinyl ether group of the above-mentioned compound (1A) to form an adduct. Alternatively, a hexacetal ester bond is formed by the carboxyl group of the monomer having a carboxyl group and the vinyl ether group of the above-mentioned compound (1A) to form an adduct.

As a more specific synthesis method, the following method can be mentioned as an example.
That is, after a polymer having a hydroxyl group or a carboxyl group is dissolved in an appropriate organic solvent, an equimolar or excess amount of the compound (1A) is added to the hydroxyl group or carboxyl group of the polymer, and the obtained reaction The mixture is cooled to a temperature of about 0 ° C. to room temperature (25 ° C.), and then an acid (for example, an oxalic acid solution) dissolved in the same solvent as the above organic solvent is added dropwise as a catalyst. Stir for 1 hour to 24 hours to react. After completion of the reaction, the target organic polymer [A] is obtained by removing the organic solvent.

(2) Method of Using Monomer as Compound to be Precursor In this method, the above compound (1A) or compound (1B) is reacted with the hydroxyl group or carboxyl group of the monomer having a hydroxyl group or carboxyl group to obtain an adduct. By polymerizing them, [A] polymer is obtained.

  The method of obtaining such [A] polymer can be referred to a known method.

  For example, when the polymer [A] is obtained by using the compound (1A), as described in JP-A-2005-187609, it is preferable to use a hydroxyl group-containing monomer and a vinyl ether compound. An acetal bond is formed by the vinyl ether group to form an adduct. Alternatively, a hexacetal ester bond is formed by the carboxyl group of the monomer having a carboxyl group and the vinyl ether group of the above-mentioned compound (1A) to form an adduct. Then, 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 described above.

  When the polymer [A] is obtained using the above-mentioned compound (1B), a monomer to which a silyl compound is added is formed, for example, according to the following reaction formula. Then, 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 described above.

  In the composition of the embodiment of the present invention, one of the polymers [A] may be used alone, or two or more thereof may be mixed and used.

<[B] solvent>
[B] The solvent is not particularly limited, but in addition to the [A] polymer, a solvent capable of uniformly dissolving or dispersing each component such as the [C] acid generator and the [F] polymerizable compound described later preferable.

  Preferred [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 hydrocarbon And aromatic hydrocarbons, ketones and esters.

As the above-mentioned alcohol solvents, long chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol, 1,8-octanediol and the like;
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;
Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and the like can be mentioned.
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 improvement of coating property.

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

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

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

  Examples of the above-mentioned 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.

  As the above-mentioned propylene glycol monoalkyl ether propionates, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate It 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.

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

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

  Examples of the above-mentioned 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, ethyl hydroxyacetate, 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 ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like can be mentioned.

  One of the above-mentioned [B] solvents may be used alone, or two or more thereof may be mixed and used.

  [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 components excluding the solvent [B] of the composition of the present embodiment It is. [B] By setting the amount of solvent used within the above range, the coating property of the composition to the glass substrate etc. is improved, and the occurrence of coating unevenness (line unevenness, pin mark unevenness, haze unevenness etc.) is further suppressed Thus, it is possible to obtain a coating film having improved film thickness uniformity.

<[C] acid generator>
[C] An acid generator is a compound which generates an acid at least upon irradiation with radiation. When the composition of the embodiment of the present invention 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, carboxylic acid ester compounds and the like.

  In the composition of the present embodiment, the [C] acid generator may be used alone or in combination of two or more.

[Oxime sulfonate compound]
As the above-mentioned oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (2) is preferable.

In the above formula ^{(2), R 21} is an alkyl group having 1 to 12 carbon atoms, fluoroalkyl group having 1 to 12 carbon atoms, alicyclic hydrocarbon group having 4 to 12 carbon atoms, aryl having 6 to 20 carbon atoms And a group or a group in which part or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups and aryl groups are substituted with a substituent.

The alkyl group represented by the above R ^21, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted by a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl-2 And alicyclic groups containing a bridged cyclic alicyclic group such as -oxonorbornyl group. A trifluoromethyl group, a pentafluoroethyl group, a heptyl fluoropropyl group etc. are mentioned as a C1-C12 fluoroalkyl group.

The alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R ²¹ described above may be substituted by a substituent, and as the substituent, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, A halogen atom is mentioned.

Examples of the aryl group having 6 to 20 carbon atoms represented by the above R ^21, a phenyl group, a naphthyl group, a tolyl group, xylyl group are preferable. The above-mentioned 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.

  As a compound containing the oxime sulfonate group represented by said Formula (2), the oxime sulfonate represented by following formula (2-1), following formula (2-2), and following formula (2-3), for example Compounds are mentioned.

In said Formula (2-1), said Formula (2-2), and said Formula (2-3), R < ²¹ > is synonymous with Formula (2) mentioned above. In said Formula (2-1) and said Formula (2-2), R < ²⁵ > is a C1-C12 alkyl group and a C1-C12 fluoroalkyl group.
In formula (2-3), Y is an alkyl group, an alkoxy group or a halogen atom. m is an integer of 0 to 3; However, when Y is plural, plural Y may be the same or different.

  As an alkyl group represented by Y of said Formula (2-3), a C1-C4 linear or branched alkyl group is preferable. As an alkoxy group represented by above-mentioned X, a C1-C4 linear or branched alkoxy group is preferable. As a halogen atom represented by above-mentioned X, a chlorine atom and a fluorine atom are preferable. As m, 0 or 1 is preferable. In the above formula (2-3), a compound in which m is 1, Y is a methyl group, and the substitution position of Y is an ortho position is particularly preferable.

  As an oxime sulfonate compound represented by said (2-3), the compound etc. which are represented by following formula (2-3-1)-(2-3-5) are mentioned, for example.

  The compounds represented by the formulas (2-3-1) to (2-3-5) are each (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-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, which is commercially available it can.

[Onium salt]
As preferred onium salts as acid generators, for example, diphenyliodonium salts, triphenylsulfonium salts, alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, benzothiazonium salts, tetrahydrothio Mention may be made of phenium salts.

  As the diphenyliodonium salt mentioned above, for example, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate , Diphenyliodoniumbutyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexanoate Fluoroarsenate, bis (4-t-butylphenyl) iodonium tri Fluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid It can be mentioned.

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

  As the above-mentioned alkyl sulfonium salt, for example, 4-acetoxyphenyldimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl sulfonium hexafluoroantimonate, dimethyl -4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate.

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

  Examples of the above-mentioned dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate. Methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4- Methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate is mentioned.

  Examples of the substituted benzylsulfonium salt described above include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4- Hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl And 3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the above-mentioned benzothiazonium salts include, for example, 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p -Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate.

  As the tetrahydrothiophenium salt mentioned above, for example, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophen Trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 1,1,2,2-tetrafluoro-2- (norbornane-2-yl) ethane sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxy) Carbonyloxybicyclo [2.2.1] heptan-2-yl) 1,1,2,2-tetrafluoroethane sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] Heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate is mentioned.

[Sulfonimide compound]
As a sulfonimide compound preferable 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) diphenyl maleimide, N- (camphor Fluoronyloxy) 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-trifluoromethylphenyl), 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-triful Methylphenyl sulfonyloxy) naphthyl dicarboximide, N- (4-fluorophenyl sulfonyloxy) naphthyl dicarboximide, N- (pentafluoroethyl sulfonyloxy) naphthyl dicarboximide, N- (heptafluoropropyl sulfonyloxy) naphthyl Dicarboximide, N- (nonafluorobutylsulfonyloxy) naphthyldicarboximide, N- (ethylsulfonyloxy) naphthyldicarboximide, N- (propylsulfonyloxy) naphthyldicarboximide, N- (butylsulfonyloxy) naphthyl Dicarboximide, N- (pentylsulfonyloxy) naphthyl dicarboximide, N- (hexylsulfonyloxy) naphthyl dicarboximide, N- (heptyl sulfone Nyloxy) naphthyl dicarboximide, N- (octylsulfonyloxy) naphthyl dicarboximide, N- (nonylsulfonyloxy) naphthyl dicarboximide and the like can be mentioned.

[Halogen-containing compound]
As a halogen-containing compound preferable as an acid generator [C], a haloalkyl group containing hydrocarbon compound and a haloalkyl group containing heterocyclic compound are mentioned, for example.

[Diazomethane compound]
Preferred examples of the diazomethane compound as the acid generator include 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, phenylsulfonyl (benzoyl) diazomethane and the like.

[Sulphone Compound]
As a sulfone compound preferable as an acid generator [C], the (beta) -keto sulfone compound, the (beta) -sulfonyl sulfone compound, and the diaryl disulfone compound are mentioned, for example.

[Sulfonic acid ester compound]
Examples of sulfonic acid ester compounds preferable as the acid generator include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and iminosulfonates.

[Carboxyl ester compound]
As a carboxylic acid ester compound preferable as an acid generator [C], carboxylic acid o-nitro benzyl ester is mentioned, for example.

  As the acid generator [C], an oxime sulfonate compound, an onium salt, and a sulfonic acid ester compound are preferable, and an oxime sulfonate compound is more preferable. As the above-mentioned oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the above formulas (2-3-1) to (2-3-5) is preferable, and it is represented by the above formula (2-3-5) Compounds are more preferred.

  Moreover, as the above-mentioned onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4-hydroxyphenylmethylsulfonium Hexafluorophosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferred. The above-mentioned sulfonic acid ester compound is preferably a haloalkyl sulfonic acid ester, more preferably N-hydroxynaphthalimide-trifluoromethane sulfonic acid ester. [C] By using the above-mentioned compound as the acid generator, the composition of the present embodiment can improve the sensitivity and can further improve the solubility.

  In the composition of the present embodiment, the content of the [C] acid generator is preferably 0.1 parts by mass to 10 parts by mass, and 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the [A] polymer. Part is more preferred. [C] The sensitivity of the radiation sensitive composition can be optimized by setting the content of the acid generator in the above-mentioned range, so that high resolution concave patterns can be obtained through the above-described steps (i) to (iii). Can be formed.

<[D] Sensitizer>
The radiation sensitive composition of the embodiment of the present invention can contain a [D] sensitizer.

  The composition of the embodiment of the present invention can further improve the radiation sensitivity of the composition by further containing a [D] sensitizer. [D] The sensitizer is preferably a compound that absorbs an actinic ray or radiation to be in an electronically excited state. The [D] sensitizer in the electron excited state comes in contact with the [C] acid generator to cause electron transfer, energy transfer, heat generation, etc., thereby causing the [C] acid generator to undergo a chemical change. It decomposes to form an acid.

  [D] As the sensitizer, compounds belonging to the following compounds and having an absorption wavelength in the range of 350 nm to 450 nm can be mentioned.

[D] As the sensitizer, compounds belonging to the following compounds and having an absorption wavelength in the range of 350 nm to 450 nm can be mentioned.

[D] As a sensitizer, for example,
Polynuclear aromatics such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene;
Xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, rose bengal;
Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone;
Cyanines such as thiacarbocyanines, oxacarbocyanines, etc.
Merocyanines such as merocyanine and carbomerocyanine;
Rhodacyanins;
Oxonols;
Thiazines such as thionine, methylene blue, toluidine blue;
Acridines such as acridine orange, chloroflavin, acriflavine;
Acridones such as acridone, 10-butyl-2-chloroacridone, etc.
Anthraquinones such as anthraquinone;
Squariums such as Squarium;
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] quinolizine- 11-non-coumarins etc. are mentioned.

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

  In the composition of the present embodiment, one kind of [D] sensitizer may be used alone, or two or more kinds thereof may be mixed and used.

  In the composition of the present embodiment, the content of the [D] sensitizer is preferably 0.1 parts by mass to 8 parts by mass, and 1 part by mass to 4 parts by mass with respect to 100 parts by mass of the [A] polymer. Part is more preferred. [D] By setting the content of the sensitizer in the above-mentioned range, the composition of the present embodiment can optimize the sensitivity as a radiation sensitive composition, so that the above steps (i) to (iii) By passing through, a high resolution concave pattern can be formed to manufacture a substrate having a lyophilic area and a liquid repellent area.

<[E] Quencher>
The composition of the embodiment of the present invention may contain an [E] quencher in addition to the aforementioned [A] polymer, [C] acid generator, and [D] sensitizer.

  The [E] quencher functions as an acid diffusion inhibitor that prevents the diffusion of the acid from the [C] acid generator. As the [E] quencher, a photodisintegrable base which is sensitized by exposure to generate a weak acid can be used. The photodisintegrable base generates an acid in the exposed area while the high acid trapping function by the anion is exhibited in the unexposed area to capture the acid from the [C] acid generator, and the unexposed area is exposed from the exposed area. Inactivate the diffusing acid. That is, since the acid is inactivated only in the unexposed area, the contrast of the elimination reaction of the protective group is improved, and as a result, the resolution can be further improved. One example of the photodisintegrable base is an onium salt compound which is decomposed by exposure to lose acid diffusion controllability.

  In the composition of the present embodiment, one kind of [E] quencher may be used alone, or two or more kinds may be mixed and used.

  In the composition of the present embodiment, the content of the [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 the [A] polymer. The parts by mass are more preferred. [D] Since the reactivity of the composition of the present embodiment can be optimized by setting the content of the sensitizer in the above-mentioned range, high resolution concaves can be obtained through the steps (i) to (iii). A pattern can be formed to produce a substrate having a lyophilic area and a liquid repellent area.

<[F] polymerizable compound>
The composition of the embodiment of the present invention can cure the composition by containing the [F] polymerizable compound.

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

  Such a [F] polymerizable compound has good polymerizability, and from the viewpoint of improving the strength of the film obtained from the composition of the present embodiment, a monofunctional, bifunctional or trifunctional or higher functional (meta ) Acrylic esters are preferred.

  A monofunctional compound is a compound having one (meth) acryloyl group, and a compound having two or three or more functional groups is a compound having two or more (meth) acryloyl groups, respectively. Say

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxy) Propyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxypolycaprolactone monoacrylate may be mentioned. Examples of commercially available products include ALONIX (registered trademark) M-101, M-111, M-114, and M-5300 (above, Toagosei Co., Ltd .; KAYARAD (registered trademark) TC-110S, and TC- 120S (above, Nippon Kayaku Co., Ltd.); Viscote 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.).

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

  Examples of the above-mentioned trifunctional or higher functional (meth) acrylic acid esters include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dierythritol Pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2- (2- Acryloyl oxyeth ) Phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, tris (acryloxyethyl) isocyanurate, linear alkylene group and alicyclic group A compound having the formula structure and having two or more isocyanate groups, and one or more hydroxyl groups in the molecule, and a compound having three, four or five (meth) acryloyloxy groups And polyfunctional urethane acrylate compounds obtained by reaction with Examples of commercially available products include ALONIX (registered trademark) M-309, M-315, M-400, M-405, M-450, M-7100, M-8030, and M-80060. , The same TO-1450 (above, Toagosei Co., Ltd.); KAYARAD (registered trademark) TMPTA, the same DPHA, the same DPCA-20, the same DPCA-30, the same DPCA-60, the same DPCA-120, the same DPEA-12 (above, Nippon Kayaku Co., Ltd .; Viscote 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industry Co., Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, 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 The commercial item etc. which contain an acrylate type compound are preferable. Among them, trifunctional or higher functional (meth) acrylic acid esters are preferable, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is particularly preferable.

  In the composition of the present embodiment, one kind of the [F] polymerizable compound may be used alone, or two or more kinds thereof may be mixed and used.

  In the composition of the present embodiment, the amount of the [F] polymerizable compound used is preferably 1 to 300 parts by mass, more preferably 3 to 200 parts by mass with respect to 100 parts by mass of the [A] polymer. Preferably, 5 parts by mass to 100 parts by mass is more preferable. [F] By setting the use amount of the polymerizable compound in the range described above, the height of the coating film obtained from the composition of the present embodiment can be increased, and the heat resistance can be further improved.

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

  [G] As a radiation sensitive polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound etc. can be mentioned.

  Specific examples of the above-mentioned O-acyloxime compounds 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] -octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethan-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. -Carbazol-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. And -carbazol-3-yl] -1- (O-acetyloxime). These O-acyl oxime compounds can be used alone or in combination of two or more.

  Among these, preferred 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. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] } -9. H. And -carbazol-3-yl] -1- (O-acetyloxime) can be mentioned.

  As an acetophenone compound mentioned above, an alpha-amino ketone compound and an alpha-hydroxy ketone compound can be mentioned, for example.

  As a specific example of the above-mentioned α-amino ketone compound, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) Mention may be made of -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

Specific examples of the above-mentioned α-hydroxy ketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane- Mention may be made of 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone.
The above acetophenone compounds can be used alone or in combination of two or more.

  Among these acetophenone compounds, α-amino ketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Particularly preferred is methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

  Specific examples of the above-mentioned biimidazole compounds 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 combination of two or more.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,2, 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 5'-Tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is particularly preferred.

  When a biimidazole compound is used as a [G] radiation-sensitive polymerization initiator in the composition of the present embodiment, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino”, in order to sensitize the same. System sensitizer) can be added.

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

  Furthermore, when using a biimidazole compound and an amino sensitizer in combination, a thiol compound can be added as a hydrogen radical donor. The biimidazole compound is sensitized by an amino sensitizer to be cleaved to generate an imidazole radical, but a high polymerization initiation ability may not be expressed as it is. However, when a thiol compound is added to a system in which a biimidazole compound and an amino sensitizer coexist, hydrogen radicals are donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to a neutral imidazole, and a component having a sulfur radical with high polymerization initiation ability is generated. Therefore, when a biimidazole compound, an amino sensitizer and a thiol compound are added to the composition of the present embodiment, a film with high hardness can be formed even with a low radiation dose.

Specific examples of such thiol compounds include aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole and 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate and the like;
Examples thereof include aliphatic thiol compounds having two or more functional groups such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate).

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

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

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

  When a biimidazole compound, an amino sensitizer and a thiol compound are used in combination, the amount of the thiol compound used is preferably 0.1 parts by mass to 50 parts by mass with respect to 100 parts by mass of the biimidazole compound. And more preferably 1 part by mass to 20 parts by mass. The reactivity at the time of exposure can be further improved by setting the amount of the thiol compound to be in the above-mentioned range.

  When the composition of the present embodiment 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 more preferably a biimidazole. It may contain a compound.

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

  In the composition of the present embodiment, the used amount of the [G] radiation-sensitive polymerization initiator is preferably 0.05 parts by mass to 30 parts by mass, more preferably 0 parts by mass with respect to 100 parts by mass of the [A] polymer. .1 part by mass to 15 parts by mass. [G] By setting the use amount of the radiation sensitive polymerization initiator within the above range, the composition of the present embodiment can cure the coating film with high radiation sensitivity even with a low exposure amount.

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

  As other optional components, surfactants, storage stabilizers, adhesion assistants, heat resistance improvers and the like can be mentioned.

  In the composition of the present embodiment, the other optional components may be used alone or in combination of two or more.

  Next, a film-forming material suitably used to form a high-definition pattern using the substrate obtained by the method for producing a substrate having a lyophilic part and a liquid repellent part according to an embodiment of the present invention Will be explained.

[Film-forming material]
The film-forming material is not particularly limited. For example, any material that can form a wiring may be used, and a fluid ink or paste having flowability is preferable.

  Examples of the film forming material include conductive film forming ink, conductive film forming paste, resin solution ink capable of forming a film, resin solution paste, coloring ink containing pigment and dye, coloring paste, organic semiconductor solution and oxidation A substance semiconductor dispersion, an organic EL light emitting solution or quantum dot, a nanocarbon conductive film forming ink, a carbon nanotube, a nanocarbon functional ink such as graphene or carbon black, a conductive film forming paste, etc. may be mentioned.

  Among these, conductive film-forming inks and conductive film-forming pastes are preferable. Specifically, ink or paste in which metal particles are dispersed, ink or paste containing metal salt and reducing agent, metallized by heating under a reducing atmosphere Ink or paste in which metal oxide particles capable of being dispersed are dispersed, dispersion or solution of conductive polymer, ink or paste in which nanocarbon such as carbon nanotube or graphene is dispersed, are preferable, especially from the viewpoint of conductivity and coatability From the above, an ink or paste in which metal particles are dispersed, an ink or paste containing a metal salt and a reducing agent are preferable.

  These inks or pastes can form a coating film by various printing methods and coating methods, and the coating film is heated to form a conductive conductive film (wiring).

As such ink or paste, 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 to 1 Pa · s Materials in the range are desirable.

  When applying a film-forming material by a method such as offset printing or screen printing in the step (iv) described above, a material with a high viscosity region is suitable, and the viscosity of the material at this time is 1 Pa · s to 50 Pa · s is preferred. Especially in the case of offset printing, the viscosity is preferably 10 Pa · s to 50 Pa · s.

(Metal salt)
In the metal salt, metal ions contained in the metal salt are reduced by the reducing agent to form a metal simple substance. And in the wiring formed, it plays the role which expresses conductivity. For example, when the metal salt is a copper salt, the copper ion contained in the copper salt is reduced by the reducing agent to form copper alone, whereby a conductive wiring is formed.

  As the metal salt, copper salts and silver salts are preferable.

  The metal salts may be used alone or in combination of two or more.

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

  Examples of the above-mentioned copper carboxylate 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, 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, Copper octanoate, copper 2-ethylhexanoate, copper nonanoate, copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper tartrate, copper malate, copper malate, etc. having a monocarboxy group Copper salts with organic acids are mentioned as suitable compounds. Copper formate may be an anhydrous form or may be hydrated. Hydrates of copper formate include tetrahydrates.

  Moreover, as a complex salt of copper and an acetylacetone derivative described above, for example, acetylacetonato copper, 1,1,1-trimethylacetylacetonato copper, 1,1,1,5,5,5-hexamethylacetylacetonato Copper, 1,1,1-trifluoroacetylacetonato copper, and 1,1,1,5,5,5-hexafluoroacetylacetonato copper are mentioned as suitable compounds.

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

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, silver benzoate, silver bromate, silver bromide, silver carbonate, silver chloride, silver citrate, silver fluoride, silver iodide, silver iodide, silver lactate, Silver nitrite, silver perchlorate, silver phosphate, silver sulfate, silver sulfide, and silver trifluoroacetate can be mentioned.

  The metal salt is preferably a copper salt from the viewpoint of suppressing migration of metal atoms in the formed wiring. Among copper salts, copper formate which is particularly excellent in reducibility is preferable. The copper formate may be an anhydride or copper formate tetrahydrate.

  The content of the metal salt in the film-forming material is preferably in the range of 0.01% by mass to 50% by mass, and more preferably in the range of 0.1% by mass to 30% by mass, with respect to the total amount of the film-forming material. 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. Further, from the viewpoint of obtaining a chemically stable film-forming material, the content of the metal salt is preferably 50% by mass or less.

(Reductant)
The film-forming material preferably contains a reducing agent together with the above-mentioned metal salt in order to reduce the metal ion contained in the metal salt into a single 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 two or more functional groups selected from the group consisting of thiol group, nitrile group, amino group, hydroxy group and hydroxycarbonyl group, nitrogen atom, oxygen atom And polymers having one or more hetero atoms selected from the group consisting of and sulfur atoms in the molecular structure.

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

  Examples of the polymer include polyvinyl pyrrolidone, polyethylene imine, polyaniline, polypyrrole, polythiophene, polyacrylamide, polyacrylic acid, carboxymethyl cellulose, polyvinyl alcohol and polyethylene oxide.

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

  Examples of the above-mentioned alkanethiols include ethanethiol, n-propanethiol, i-propanethiol, n-butanethiol, i-butanethiol, t-butanethiol, n-pentanethiol, n-hexanethiol, n- Heptanethiol, n-octanethiol, 2-ethylhexanethiol can be mentioned.

  Moreover, as said amines, an amine compound can be mentioned, For example, 3- (2-ethylhexyl oxy) 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 diethylacetal, etc. Diazineamine, 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 Diamine compounds such as 5-pentanediamine, 1,6-hexanediamine, N, N'-dimethyl-1,6-hexanediamine, isophoronediamine, diethylenetriamine, N, N, N ', N''N' '- Pentamethyldiethylenetriamine, N- (aminoethyl) piperazine, N- (aminopropyl) piperazine, etc. Triamine compounds.

  As the above-mentioned hydrazines, for example, 1,1-di-n-butylhydrazine, 1,1-di-t-butylhydrazine, 1,1-di-n-pentyldazine, 1,1-di-n -Hexyl hydrazine, 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-tert-butylhydrazine, 1,2-Di-n-Pentylazine, 1,2-Dihydro -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.

  As monoalcohols mentioned above, for example, methanol, ethanol, n-propialcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, cyclohexanol , Benzyl alcohol and terpineol.

  Examples of the above-mentioned diols 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 above-mentioned hydroxyamines include N, N-diethylhydroxylamine, N, N-di-n-propylhydroxylamine, N, N-di-n-butylhydroxylamine, N, N-di-n-butyl ester And pentylhydroxylamine and N, N-di-n-hexylhydroxylamine.

  Examples of the above-mentioned α-hydroxy ketones include hydroxyacetone, 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 1-hydroxy-2-pentanone, 3-hydroxy-2-pentanone, 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 -Include octanone.

  The above-mentioned carboxylic acids are not particularly limited as long as they have reducibility to metal salts, and for example, formic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, oxalic acid, tartaric acid, malic acid and citric acid It can be mentioned.

  As the above reducing agents, one or two or more types capable of reducing this can be appropriately selected or used in combination according to the type of the above-mentioned 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 and 3-ethoxypropylamine.

  The content of the reducing agent in the film-forming material is preferably in the range of 1% by mass to 99% by mass, and more preferably in the range of 10% by mass to 90% by mass, with respect to the total amount of the film-forming material. By setting the content of the reducing agent in the range of 1% by mass to 99% by mass, a wiring having excellent conductivity can be formed. Furthermore, by setting the content in the range of 10% by mass to 90% by mass, a wiring having a low resistance value and excellent adhesion to the electrode can be formed.

(Metal particles)
The film-forming material can contain metal particles for the purpose of improving the reduction deposition rate of the metal salt or adjusting the viscosity of the film-forming material.

  The metal particles are not particularly limited, but from the viewpoint of 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 it is a particle containing the metal species of These metal species may be single or alloys with other metals. When these metal species are simple substances, preferable metal fine particles include at least one or a combination of two or more 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, metal fine particles containing one or two 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 a wiring preferable. Although 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. It is more preferable to use the above-mentioned metal fine particles because the deposition rate may decrease.

  The average particle diameter of the metal fine particles is preferably in the range of 0.05 μm to 5 μm. The particle diameter of the metal fine particles is preferably 0.05 μm or more from the viewpoint of preventing the occurrence of oxidation reaction due to the increase of the activity of the metal surface and the prevention of aggregation of the metal fine particles. Further, from the viewpoint of preventing the sedimentation of the metal fine particles when storing the film forming material for a long time, the average particle diameter of the metal fine particles is preferably 5 μm or less.

  The measuring method of the said average particle diameter is as follows.

  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), three points can be arbitrarily selected And take pictures at the most appropriate magnification for particle size measurement. From each of the obtained photographs, 100 particles are arbitrarily selected, and the major axes of the particles are transmitted electron microscope (TEM), field emission type transmission electron microscope (FE-TEM), field emission scanning electron microscope (FE) The particle diameter can be calculated by dividing the measurement magnification by measurement using SEM or the like, and calculating the average of these values. Further, the standard deviation can be determined by the particle diameter and the number of individual metal fine particles at the time of the above-mentioned observation.

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

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

  The content of the metal fine particles in the film forming material is preferably in the range of 0% by mass to 60% by mass, more preferably 1% by mass to 40% by mass, and more preferably 1% by mass to 20%. The range of% by weight is particularly preferred.

(solvent)
The film-forming material preferably contains a solvent from the viewpoint of adjusting the viscosity of the material to improve the productivity of the wiring and from the viewpoint of obtaining a low resistance and uniform wiring.

  As the solvent, an organic solvent which can dissolve or disperse each component in the film-forming material and does not participate in the reduction reaction of the metal salt can be mentioned. Specifically, one or a mixture of two or more compatible ones selected from the group consisting of ethers, esters, aliphatic hydrocarbons and aromatic hydrocarbons can be mentioned.

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

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

  Among these organic solvents, from the viewpoint of easiness of adjustment of viscosity in particular, ethers are preferable, and hexyl methyl ether, diethylene glycol dimethyl ether and the like are particularly preferable.

  The content of the solvent contained in the film-forming material is preferably in the range of 0% by mass to 95% by mass, and more preferably in the range of 1% by mass to 70% by mass, with respect to the total amount of the film-forming material. The range of 10% by mass to 50% by mass is particularly preferable.

  The film-forming material can be produced by mixing the components described above. 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 an ultrasonic wave (homogenizer). As the stirring conditions, for example, in the case of stirring with a stirring blade, the rotational speed of the stirring blade is usually in the range of 1 rpm to 4000 rpm, preferably in the range of 100 rpm to 2000 rpm.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not construed as being limited to these examples.

[GPC analysis]
In this example, the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer were determined using gel permeation chromatography (GPC, manufactured by Tosoh Corp., trade name: HLC-8220). It measured by polystyrene conversion on the conditions of a tetrahydrofuran (THF) solvent.
Measurement method: gel permeation chromatography (GPC) method Standard substance: polystyrene conversion: apparatus: Tosoh Co., Ltd. trade name: HLC-8220
Column: Tosoh Corporation guard column _{H XL -H, TSK gel G7000H XL} , TSK gel GMH XL 2 present, TSK gel G2000H those obtained by sequentially connecting the _XL-solvent: tetrahydrofuran Sample concentration: 0.7 wt%
· Injection volume: 70 μL
・ Flow rate: 1 mL / min

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

  In the present example, the following polymers were synthesized as an example of the above-mentioned [A] polymer.

<[A] Synthesis of Polymer>
Synthesis Example 1
In a flask equipped with a condenser and a stirrer, 25 parts by mass of 2-hydroxyethyl methacrylate, 30 parts by mass of trimethylsilyl chloride, and 1.0 parts by mass of imidazole are charged and reacted by maintaining at 40 ° C. for 7 hours under a nitrogen atmosphere. The The obtained reaction solution was washed with water, separated, the solvent was removed by a rotary evaporator, and the unreacted component was removed by distillation under reduced pressure to obtain a compound (M-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 were charged. Subsequently, 70 parts by mass of the compound (M-1) obtained above and 30 parts by mass of benzyl methacrylate were charged, and after substituting with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was By holding for a while and polymerizing, a solution containing a copolymer [A] polymer (P-1) was obtained (Mw = 18000, Mw / Mn = 2.3).

Synthesis Example 2
In a flask equipped with a condenser and a stirrer, 25 parts by mass of methacrylic acid, 37 parts by mass of trimethylsilyl chloride, and 1.0 parts by mass of imidazole were charged, and reacted by maintaining at 30 ° C. for 4 hours under a nitrogen atmosphere. The obtained reaction solution was washed with water, separated, the solvent was removed by a rotary evaporator, and the unreacted component was removed by distillation under reduced pressure to obtain a compound (M-2).

  In a flask equipped with a condenser and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol 200 parts by mass of dimethyl ether were charged. Subsequently, 60 parts by mass of the compound (M-2) obtained above, 20 parts by mass of benzyl methacrylate, and 20 parts by mass of 3- (methacryloyloxymethyl) -3-ethyl oxetane are charged, and after nitrogen substitution, they are gently stirred. While raising the temperature of the solution to 80 ° C. and maintaining this temperature for 4 hours for polymerization, a solution containing the copolymer [A] polymer (P-2) was obtained (Mw = 20000, Mw / Mn = 2.1).

Synthesis Example 3
In a flask equipped with a condenser and a stirrer, 25 parts by mass of 2-hydroxyethyl methacrylate, 55 parts by mass of methyl diphenylsilyl vinyl ether, 2.0 parts by mass of trifluoroacetic acid (TFA) and 200 parts by mass of tetrahydrofuran (THF) are charged. The reaction was carried out by maintaining the temperature at 60 ° C. for 9 hours under a nitrogen atmosphere. After cooling, 2.1 parts by mass of pyridine was added to the reaction liquid to neutralize. The obtained reaction solution was washed with water, separated, the solvent was removed by a rotary evaporator, and the unreacted components were removed by distillation under reduced pressure to obtain an acetalized product (M-3).

  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 were charged. Subsequently, 60 parts by mass of the compound (M-3) obtained above and 40 parts by mass of benzyl methacrylate were charged, and after substituting with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. By holding for a while and polymerizing, a solution containing a copolymer [A] polymer (P-3) was obtained (Mw = 15000, Mw / Mn = 2.3).

Synthesis Example 4
In a flask equipped with a condenser and a stirrer, 25 parts by mass of methacrylic acid, 65 parts by mass of 3- (methyldiethylsilyl) propyl vinyl ether, 2.0 parts by mass of trifluoroacetic acid (TFA) and 200 parts by mass of tetrahydrofuran (THF) are charged. The reaction was carried out by maintaining the temperature at 60 ° C. for 9 hours under a nitrogen atmosphere. After cooling, 2.1 parts by mass of pyridine was added to the reaction liquid to neutralize. The obtained reaction solution was washed with water, separated, the solvent was removed by a rotary evaporator, and the unreacted components were removed by distillation under reduced pressure to obtain an acetalized product (M-4).

  In a flask equipped with a condenser and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol 200 parts by mass of dimethyl ether were charged. Subsequently, 60 parts by mass of the compound (M-4) obtained above, 20 parts by mass of benzyl methacrylate, and 20 parts by mass of glycidyl methacrylate are charged, and after substituting with nitrogen, the temperature of the solution is adjusted to 80.degree. The solution was raised and polymerized by maintaining this temperature for 4 hours to obtain a solution containing the copolymer [A] polymer (P-4) (Mw = 20000, Mw / Mn = 2.3 ).

[Comparative 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 were charged. Subsequently, 60 parts by mass of 1-butoxyethyl methacrylate and 20 parts by mass of 40 parts by mass of benzyl methacrylate are charged, and after substituting with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring, and this temperature is maintained for 4 hours Then, polymerization was carried out to obtain a solution containing the copolymer (p-1) (Mw = 15,000, Mw / Mn = 2.3).

[Comparison Example 2]
In a flask equipped with a condenser and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 2 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol 200 parts by mass of dimethyl ether were charged. Subsequently, 60 parts by mass of t-butyl methacrylate and 40 parts by mass of benzyl methacrylate are charged, and after substituting with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring, and this temperature is maintained for 4 hours to polymerize Thus, a solution containing the copolymer (p-2) was obtained (Mw = 14000, Mw / Mn = 2.3).

<Preparation of radiation sensitive composition>
Each component used for preparation of the radiation sensitive composition by the Example and the comparative example is shown below.

<[C] acid generator>
C-1: N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester C-2: 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile ("CGI-725" from BASF)

<[D] Sensitizer>
D-1: 2-isopropylthioxanthone

<[E] Quencher>
E-1: 2-phenylbenzimidazole E-2: 4- (dimethylamino) pyridine

<[F] polymerizable compound>
F-1: Dipentaerythritol hexaacrylate F-2: 1, 9-nonanediol diacrylate

<[G] Radiation-sensitive polymerization initiator>
G-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE (registered trademark) 907, manufactured by BASF)
G-2: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (IRGACURE (registered trademark) 379, manufactured by BASF AG)
G-3: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (IRGACURE (registered trademark) OXE02, manufactured by BASF AG) )

<Example>
[Examples 1 to 8 and Comparative Examples 1 to 4]
Each component of the type and content shown in Table 1 is mixed, 0.1 parts by mass of Polyflow No. 75 (manufactured by Kyoeisha Chemical Co., Ltd.) is added as a surfactant, and each has a solid content concentration of 20% by mass. [B] After adding diethylene glycol dimethyl ether as a solvent, each radiation sensitive composition was prepared by filtering with a millipore filter with a hole diameter of 0.5 micrometer. In addition, "-" in Table 1 represents that the corresponding component was not used.

<Film evaluation>
Film formation was performed using each of the radiation sensitive compositions prepared in Examples and Comparative Examples described above, and the following evaluation was performed.

[Contact angle]
The radiation-sensitive compositions prepared in Examples or Comparative Examples are respectively coated on a non-alkali glass substrate with a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a 0.5 μm thick coating film. did. Subsequently, radiation exposure was performed using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kagaku Co., Ltd.) through a quartz mask (contact) to the obtained coating film and setting the exposure dose to 250 mJ / cm ² . After that, using an hot plate and baking at 110 ° C. for 5 minutes, the exposed area (recessed area) becomes a lyophilic area, and the area other than the exposed area (convex area) becomes a lyophobic area. A film patterned by the following method (hereinafter, may be referred to as a "friendly lyophilic patterning film") was formed. In the formed lyophilic-patterned film, using a contact angle meter (CA-X manufactured by Kyowa Interface Science Co., Ltd.), the coated film surface of the exposed area corresponding to the lyophilic area, and the coated film of the unexposed area corresponding to the liquid repellent area The contact angles of water, decane and tetradecane at each of the surfaces were measured to confirm the lyophobic performance. In Table 2, the contact angle of water on the surface of the exposed portion is referred to as "lyophilic portion water", and the contact angle of water on the surface of the unexposed portion is referred to as "liquid repelling portion water". The same applies to the contact angles of decane and tetradecane.

[Ink application assist performance evaluation on lyophobic pattern]
FIG. 6 is a view showing a quartz mask used in the examples, (a) is a plan view, and (b) is a cross-sectional view.

  A lyophilic patterning film is formed by the same method as the above [contact angle] except that a quartz mask (L / S = 50 μm / 450 μm) as shown in FIG. 6 is used as a quartz mask, and a lyophilic portion is obtained. In the vicinity, 60 pl of tetradecane was dropped with a microcapillary using an automatic minimum contact angle meter (MCA-2 manufactured by Kyowa Interface Co., Ltd.), and after 5 seconds, the dropped portion was observed from the dropping direction (from above) with a microscope.

  As a result, if tetradecane could be patterned along the hydrophilicity pattern, it was evaluated as "o", and if tetradecane was present in a place other than the hydrophilicity pattern, it was evaluated as "x".

  Here, the state after 5 seconds of dropping tetradecane was observed in a short time of about 5 seconds, when the droplets can not be patterned, the droplets are dried and the position is different from the desired position. There is a possibility that liquid residue may occur, and wiring of a desired shape may not be formed.

  When patterning can not be performed in a short time, ink residue due to drying may occur.

[Exposure sensitivity evaluation of lyophilic patterning film formation]
As a quartz mask, a quartz mask (L / S = 50μm / 450μm ) of FIG. 6, the exposure amount ^{50mJ / cm 2, 100mJ / cm} 2, 150mJ / cm 2, 200mJ / cm 2, 250mJ / cm 2 and 300mJ A lyophilic patterning film was formed by the same method as the above [contact angle] except changing to / cm ² , and the film thickness reduction rate was calculated by the same method as the above [concave patterning property verification].

  The film thickness reduction rate increases as the exposure amount increases. However, the exposure sensitivity was evaluated using the exposure amount when the film thickness reduction rate reached 10% or more as the sensitivity.

[Resolution evaluation of lyophilic patterning film formation]
An affinity patterning film is formed in the same manner as the above [contact angle] except that a quartz mask (L / S = 10 μm / 90 μm) is used as a quartz mask, and an automatic minimum contact angle meter (MCA manufactured by Kyowa Interface Co., Ltd.) Using a microcapillary, a small amount (<10 pl) of tetradecane is dropped in the vicinity of the recess using (2) and observed from the dropping direction (from the top) with an electron microscope (Hitachi's scanning electron microscope SU3500). When the patterning was possible along the repellent pattern, the resolution was good ((), and when the lyophilic pattern was disturbed due to tetradecane existing in a place other than the hydrophilic repellent pattern, etc., it was evaluated as poor resolution (×).

  From the results shown collectively in Table 2, the lyophilic patterning film formed using the radiation-sensitive composition prepared in the example was formed using the radiation-sensitive composition prepared in the comparative example. It was found that the film had better lyophilic property, patterning property and ink application assist performance as compared with the film of the comparative example.

  That is, it was found that the radiation-sensitive composition prepared in the example can impart better lyophobic property and patterning property to the film to be formed as compared with the radiation-sensitive composition prepared in the comparative example. The And it turned out that the radiation sensitive composition prepared in the example can be suitably used for the manufacturing method of the base material which has a lyophilic part and a liquid repelling part of the present invention.

  The composition of the present invention can form a film by coating, and can impart lyophilic patterning to a film to be formed utilizing radiation irradiation. The film formed using the composition of the present invention is repellent when applied to various inks such as conductive film-forming ink using inkjet, screen printing, gravure printing, gravure offset printing, spin coating, etc. Patterning can be assisted. And the film | membrane formed using the composition of this invention can form a fine and elaborate pattern, and the obtained pattern is excellent also in adhesiveness. A film formed using the composition of the present invention can be suitably used as a base film in printed electronics.

  In the case of using a base film formed from the composition of the present invention, fine and fine wiring can be easily formed by a printing method using various conductive film forming inks. And the conductive pattern of metal wiring etc. obtained is excellent also in adhesion nature and conductivity, and becomes suitable for formation of an electronic circuit. Therefore, the present invention can be used as a high precision wiring technology. In addition, the concave pattern obtained by the present invention can be used in microchannels for biosensor applications. Furthermore, the present invention provides a wiring substrate mounted by an electronic device such as a semiconductor chip, a liquid crystal display, a portable information device such as a mobile phone, a digital camera, an organic display, an organic EL illumination, an electronic such as various sensors and wearable devices. It is effective for downsizing, thinning and functional enhancement in equipment.

Reference Signs List 1 substrate 2, 2a, 5 coating 3 radiation irradiated section 3-2 non-irradiated section 4 film forming material 6 pattern 12 convex section 13 concave section

Claims (10)

Following (i), (ii) and a substrate having a lyophilic part and the liquid repellent portion step only contains, characterized by producing a substrate having a lyophilic part and the liquid-repellent part of the (iii) Manufacturing method.
(I) obtained by polymerizing a monomer having a group containing a silicon atom which has at least one selected from acetal bond and hemiacetal ester bond and is at least one selected from the group of groups shown by the following formulas Applying a composition containing the selected polymer and an acid generator to form a coating film
(In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and Rs independently represents a monovalent organic group having a silicon atom Show.
In formulas (1-3) and (1-4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom , An alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, a group in which part or all of hydrogen atoms of these groups are substituted with a substituent, or a monovalent organic group having a silicon atom Indicates a group.
In Formula (1-1), Formula (1-2), Formula (1-3) and (1-4), * represents a binding site. )
(Ii) a step of irradiating a predetermined portion of the coating with radiation (iii) a step of heating the coating after the radiation of heating to volatilize the separated components The method for producing a substrate having a lyophilic part and a liquid repellent part according to claim 1, wherein the group containing a silicon atom is an acid dissociable group.   The group having a lyophilic part and a liquid repellent part according to claim 1 or 2, wherein the contact angle difference between the irradiated part and the unirradiated part in the step (ii) with respect to tetradecane is 30 ° or more. Material manufacturing method.   The lyophilic part according to any one of claims 1 to 3, wherein the lyophilic part is 10% or more thinner than the initial film thickness before the formation of the lyophilic part. The manufacturing method of the base material which has a liquid part. The group containing a silicon atom is at least one selected from the group of groups represented by the following formula (1-3) and the following formula (1-4), and the following formula (1-3) and the following formula (1) -4), R ³ represents a single bond or a divalent organic group having 1 to 12 carbon atoms, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms Or an alicyclic hydrocarbon group, an aryl group, a group in which part or all of the hydrogen atoms of these groups are substituted with a substituent, represented by the following formulas (1-5) and (1-5-2) group, or -SiR ^a ₃ indicates, ^{R a} is a lyophilic portion and the lyophobic part as claimed in any one of claims 1 to 4, characterized in that an alkyl group having 1 to 10 carbon atoms The manufacturing method of the base material which it has.
(In Formula (1-5), R ^B is each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a group represented by Formula (1-5-2). L 1 is 0 to 20 Is an integer of
In formula (1-5-2), R ^C independently represents an alkyl group having 1 to 20 carbon atoms or a phenyl group. L2 is an integer of 0-5.
In Formula (1-3), Formula (1-4), Formula (1-5) and (1-5-2), * indicates a binding site. ) The said composition contains the polymeric compound which has an ethylenically unsaturated bond, The manufacturing method of the base material which has the lyophilic part and the liquid repelling part of any one of the Claims 1-5 characterized by the above-mentioned. A polymer comprising a group having a silicon atom and an acid generator, which is used in the method for producing a substrate having a lyophilic part and a liquid repellent part according to any one of claims 1 to 6. Composition. A conductive film is formed on the lyophilic portion formed by the method for producing a substrate having a lyophilic portion and a liquid repellent portion according to any one of claims 1 to 6 using a composition for forming a conductive film. And forming a conductive film. An electronic circuit comprising a conductive film formed by using the method for forming a conductive film according to claim 8 . An electronic device comprising the electronic circuit according to claim 9 .