JP7630122B2 - A method for producing a photophilic/repellent pattern forming agent, a substrate having a photophilic/repellent pattern forming agent on its surface, and an article having a photophilic/repellent pattern on at least a part of its surface - Google Patents

Description

The present disclosure relates to a repellent pattern forming agent, a substrate having a repellent pattern forming agent on its surface, and a method for manufacturing an article having a repellent pattern on at least a portion of its surface.

A method for producing a pattern formation body has been proposed, which is characterized in that a photocatalyst-containing layer side substrate having at least a photocatalyst-containing layer and a substrate for a pattern formation body having a property change layer whose properties change due to the action of at least the photocatalyst in the photocatalyst-containing layer are arranged so that the photocatalyst-containing layer and the property change layer are in contact with each other, and then exposed to light to change the properties of the property change layer in the exposed portion, and then the photocatalyst-containing layer side substrate is removed to obtain a pattern formation body having a pattern with changed properties on the property change layer (Patent Document 1).

JP 2000-249821 A

The objective of this disclosure is to provide a new method for forming lyophilic/lyophobic patterns using a liquid-repellent polymer that becomes lyophilic due to photocatalytic activity.

（式中、
Ｘは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ^１Ｘ^２基（但し、Ｘ^１及びＸ^２は、同一又は異なって、水素原子、フッ素原子又は塩素原子である。）、シアノ基、炭素数１～２１の直鎖状若しくは分岐状のフルオロアルキル基、置換若しくは非置換のベンジル基、置換若しくは非置換のフェニル基、又は炭素数１～２０の直鎖状または分岐状アルキル基であり、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１～１０の炭化水素基、－ＣＨ_２ＣＨ_２Ｎ（Ｒ^１）ＳＯ_２－基（但し、Ｒ^１は炭素数１～４のアルキル基であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）、－ＣＨ_２ＣＨ（ＯＹ^１）ＣＨ_２－基（但し、Ｙ^１は水素原子またはアセチル基であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）、又は－（ＣＨ_２）_ｎＳＯ_２－基（ｎは１～１０であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）であり、
Ｒｆは炭素数１～２０の直鎖状若しくは分岐状のフルオロアルキル基、又は分子量４００～５,０００のフルオロポリエーテル基である。）；

（式中、Ｗ^１はフッ素原子、又は炭素数１～３のパーフルオロアルキル基若しくはパーフルオロアルコキシ基であり、Ｗ^２及びＷ^３はそれぞれ独立に、フッ素原子、又は酸素原子を含んでよい炭素数１～６のパーフルオロアルキル基であり、Ｗ^２とＷ^３とによって環状構造を形成してもよい。）；及び

（式中、Ｗ^４及びＷ^５はそれぞれ独立に、フッ素原子、又は酸素原子を含んでよい炭素数１～８のパーフルオロアルキル基である。Ｗ^４とＷ^５とによって環状構造を形成してもよい。）。
項２．
さらに非フッ素系溶剤を含む、項１に記載の親撥パターン形成剤。
項３．
前記光触媒が、酸化チタン（ＴｉＯ_２）である、項１又は２に記載の親撥パターン形成剤。
項４．
前記重合体が、４５質量％以上のフッ素元素を含有する重合体である項１～３のいずれか１項に記載の親撥パターン形成剤。
項５．
前記重合体が、４５質量％未満のフッ素元素を含有する含フッ素重合体であり、溶剤中のフッ素系溶剤の含有量が３０質量％未満である項１～３のいずれか１項に記載の親撥パターン形成剤。
項６．
項１～５のいずれか１項に記載の親撥パターン形成剤を表面に有する基材。
項７．
項６に記載の基材を有する有機及び／又は無機のパターン状導電体。
項８．
項７に記載のパターン状導電体を有する物品。
項９．
有機トランジスタ、有機ＥＬディスプレイ、有機ＥＬ照明、及び有機太陽電池から選択される少なくとも一種の物品である項８に記載の物品。
項１０．
親撥パターンを少なくとも一部の表面に有する物品の製造方法であって、
項１～５のいずれか一項に記載の親撥パターン形成剤が適用された前記表面において、パターン状に電磁波を照射することにより親撥パターンを形成する工程
を含む、製造方法。
項１１．
光触媒と、一般式（１）で表される化合物に基づく構成単位を有する重合体とを含有する組成物：

（式中、
Ｘは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ^１Ｘ^２基（但し、Ｘ^１及びＸ^２は、同一又は異なって、水素原子、フッ素原子又は塩素原子である。）、シアノ基、炭素数１～２１の直鎖状若しくは分岐状のフルオロアルキル基、置換若しくは非置換のベンジル基、置換若しくは非置換のフェニル基、又は炭素数１～２０の直鎖状または分岐状アルキル基であり、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１～１０の炭化水素基、－ＣＨ_２ＣＨ_２Ｎ（Ｒ^１）ＳＯ_２－基（但し、Ｒ^１は炭素数１～４のアルキル基であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）、－ＣＨ_２ＣＨ（ＯＹ^１）ＣＨ_２－基（但し、Ｙ^１は水素原子またはアセチル基であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）、又は－（ＣＨ_２）_ｎＳＯ_２－基（ｎは１～１０であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）であり、
Ｒｆは炭素数１～２０の直鎖状若しくは分岐状のフルオロアルキル基、又は分子量４００～５,０００のフルオロポリエーテル基である。）。 Item 1.
A photophilic/repellent pattern forming agent containing a photocatalyst,
The following general formula (1), or the following general formula (2-1) and/or (2-2):
A phobic/philic pattern forming agent containing a polymer having a repeating unit derived from a fluorine-containing compound represented by the formula:

(Wherein,
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are the same or different and are a hydrogen atom, a fluorine atom, or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms;
Y is a direct bond, a _{hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a -CH2CH2N (} ^R1 ) _SO2- group (wherein ^R1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf and the left end is bonded to O), a _-CH2CH ( ^OY1 ) _CH2- group (wherein ^Y1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the _{left end is bonded to O), or a -(CH2)nSO2- group (} wherein n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000;

(In the formula, W ¹ is a fluorine atom, or a perfluoroalkyl group or perfluoroalkoxy group having 1 to 3 carbon atoms, W ² and W ³ are each independently a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms which may contain an oxygen atom, and W ² and W ³ may together form a cyclic structure); and

(In the formula, ^W4 and ^W5 are each independently a perfluoroalkyl group having 1 to 8 carbon atoms which may contain a fluorine atom or an oxygen atom. ^W4 and ^W5 may combine together to form a cyclic structure).
Item 2.
Item 2. The repellent pattern forming agent according to Item 1, further comprising a non-fluorinated solvent.
Item 3.
Item 3. The photophilic/repellent pattern forming agent according to Item 1 or 2, wherein the photocatalyst is titanium oxide (TiO ₂ ).
Item 4.
4. The photophilic/repellent pattern forming agent according to any one of items 1 to 3, wherein the polymer contains 45% by mass or more of elemental fluorine.
Item 5.
4. The photosensitive pattern forming agent according to any one of items 1 to 3, wherein the polymer is a fluorine-containing polymer containing less than 45% by mass of elemental fluorine, and the content of a fluorine-containing solvent in the solvent is less than 30% by mass.
Item 6.
Item 6. A substrate having the repellent pattern forming agent according to any one of items 1 to 5 on its surface.
Item 7.
Item 7. An organic and/or inorganic patterned conductor having the substrate according to item 6.
Item 8.
Item 8. An article having the patterned conductor according to item 7.
Item 9.
Item 9. The article according to item 8, which is at least one article selected from the group consisting of an organic transistor, an organic EL display, an organic EL lighting device, and an organic solar cell.
Item 10.
A method for producing an article having a repellent pattern on at least a portion of a surface thereof, comprising the steps of:
Item 6. A method for producing a photoresist pattern comprising the step of irradiating an electromagnetic wave in a pattern on the surface to which the photoresist pattern forming agent according to any one of Items 1 to 5 has been applied, thereby forming a photoresist pattern.
Item 11.
A composition containing a photocatalyst and a polymer having a structural unit based on a compound represented by general formula (1):

(Wherein,
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are the same or different and are a hydrogen atom, a fluorine atom, or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms;
Y is a direct bond, a _{hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a -CH2CH2N (} ^R1 ) _SO2- group (wherein ^R1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf and the left end is bonded to O), a _-CH2CH ( ^OY1 ) _CH2- group (wherein ^Y1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the _{left end is bonded to O), or a -(CH2)nSO2- group (} wherein n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000.

This provides a new method for forming lyophilic/repellent patterns using a liquid-repellent polymer that becomes lyophilic due to photocatalytic activity.

1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle for Examples 1 to 3 and Comparative Example 1. 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle in Example 4 and Comparative Example 2. 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle for Examples 5 to 7 and Comparative Example 3. 1 is a graph showing the relationship between UV exposure time (accumulated light amount) and water contact angle in Examples 9 to 10 and Comparative Example 5.

（式中、
Ｘは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ^１Ｘ^２基（但し、Ｘ^１及びＸ^２は、同一又は異なって、水素原子、フッ素原子又は塩素原子である。）、シアノ基、炭素数１～２１の直鎖状若しくは分岐状のフルオロアルキル基、置換若しくは非置換のベンジル基、置換若しくは非置換のフェニル基、又は炭素数１～２０の直鎖状または分岐状アルキル基であり、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１～１０の炭化水素基、－ＣＨ_２ＣＨ_２Ｎ（Ｒ^１）ＳＯ_２－基（但し、Ｒ^１は炭素数１～４のアルキル基であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）、－ＣＨ_２ＣＨ（ＯＹ^１）ＣＨ_２－基（但し、Ｙ^１は水素原子またはアセチル基であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）、又は－（ＣＨ_２）_ｎＳＯ_２－基（ｎは１～１０であり、式の右端がＲｆに、左端がＯにそれぞれ結合している。）であり、
Ｒｆは炭素数１～２０の直鎖状若しくは分岐状のフルオロアルキル基、又は分子量４００～５,０００のフルオロポリエーテル基である。）；

（式中、Ｗ^１はフッ素原子、又は炭素数１～３のパーフルオロアルキル基若しくはパーフルオロアルコキシ基であり、Ｗ^２及びＷ^３はそれぞれ独立に、フッ素原子、又は酸素原子を含んでよい炭素数１～６のパーフルオロアルキル基であり、Ｗ^２とＷ^３とによって環状構造を形成してもよい。）；及び

（式中、Ｗ^４及びＷ^５はそれぞれ独立に、フッ素原子、又は酸素原子を含んでよい炭素数１～８のパーフルオロアルキル基である。Ｗ^４とＷ^５とによって環状構造を形成してもよい。）。 In the present disclosure, "(meth)acrylic acid" is used as a general term for "acrylic acid" and "methacrylic acid."
1. Photophilic pattern forming agent
A photophilic/repellent pattern forming agent containing a photocatalyst,
The following general formula (1), or the following general formula (2-1) and/or (2-2):
The present invention relates to a photophilic/phobic pattern forming agent that contains a polymer having a repeating unit derived from a fluorine-containing compound represented by the formula:

(Wherein,
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are the same or different and are a hydrogen atom, a fluorine atom, or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms;
Y is a direct bond, a _{hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a -CH2CH2N (} ^R1 ) _SO2- group (wherein ^R1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf and the left end is bonded to O), a _-CH2CH ( ^OY1 ) _CH2- group (wherein ^Y1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the _{left end is bonded to O), or a -(CH2)nSO2- group (} wherein n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000;

(In the formula, W ¹ is a fluorine atom, or a perfluoroalkyl group or perfluoroalkoxy group having 1 to 3 carbon atoms, W ² and W ³ are each independently a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms which may contain an oxygen atom, and W ² and W ³ may together form a cyclic structure); and

(In the formula, ^W4 and ^W5 are each independently a perfluoroalkyl group having 1 to 8 carbon atoms which may contain a fluorine atom or an oxygen atom. ^W4 and ^W5 may combine together to form a cyclic structure).

In conventional methods such as those described in Patent Document 1, it is necessary to prepare a photocatalyst-containing layer side substrate having a photocatalyst-containing layer for each shape of the affinity-repellent pattern, specifically, a photomask having a photocatalyst-containing layer, which makes the affinity-repellent pattern formation process complicated. By using the affinity-repellent pattern forming agent of the present disclosure, it is possible to easily form lyophilic regions in a predetermined pattern shape on the treated surface, and further, by applying a functional ink to this treated surface by a printing method, it is possible to achieve a state in which the ink is applied selectively to only the lyophilic regions.

In the disclosed repellent pattern forming agent, it is also possible to selectively chemically bond functional materials to the functional groups in the repellent polymer that are generated as the polymer changes to lyophilicity.

1.1 Fluorine-containing polymer (1)
The fluorine-containing polymer (1) is a polymer containing repeating units derived from the fluorine-containing compound represented by the above general formula (1).

When the fluoropolymer (1) is exposed to electromagnetic waves, it changes from liquid repellency to liquid affinity. This change occurs when the fluoroalkyl groups of the fluoropolymer (1) change to hydrophilic groups such as carboxylic acid or hydroxyl groups.

In the above general formula (1), the fluoroalkyl group represented by Rf is an alkyl group in which at least one hydrogen atom is replaced with a fluorine atom, and also includes a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.

Although not particularly limited, the fluorine-containing compound represented by the above general formula (1) is preferably a linear or branched fluoroalkyl group having 2 to 6 carbon atoms, and particularly preferably a linear or branched perfluoroalkyl group having 4 to 6 carbon atoms, in terms of the low environmental impact caused by the long-chain fluoroalkyl group-containing compound.

When Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, in terms of improving liquid repellency, it is preferable that the substituent at the α-position represented by X in the above general formula (1) is a methyl group, an alkyl group other than a hydrogen atom, or a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and of these, fluorine atoms and chlorine atoms are preferred.

Specific examples of fluorine-containing compounds represented by the above general formula (1) are as follows:

[Chemical formula 10]
Rf-SO ₂ (CH ₂ ) ₃ -OCO-CH=CH ₂
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(－F)－C(=O)－O－(CH ₂ ) ₂ －SO ₂ －Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(－Cl)－C(=O)－O－(CH ₂ ) ₂ －SO ₂ －Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₃ −S−Rf
CH ₂ =C(－Cl)－C(=O)－O－(CH ₂ ) ₃ －SO ₂ －Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ −Rf
CH ₂ =C(H)－C(=O)－O－(CH ₂ ) ₂ -Rf

The fluorine-containing polymer (1) may be a polymer containing repeating units derived from one of the fluorine-containing compounds represented by the general formula (1) described above, or may be a polymer containing repeating units derived from two or more of the fluorine-containing compounds represented by the general formula (1) described above.

In the fluorine-containing polymer (1), the proportion of repeating units derived from the fluorine-containing compound represented by general formula (1) in all repeating units is preferably 50 mol % to 100 mol %, and more preferably 60 mol % to 90 mol %.

The fluorine-containing polymer (1) may further contain a repeating unit derived from a compound different from the fluorine-containing compound represented by the above general formula (1). The compound that is the base of such a repeating unit is not limited.

Examples of such compounds include (meth)acrylic acid esters represented by the following general formula (2).
CH ₂ =C(R ¹ )COOR ² (2)
(In the formula, ^R1 is H or _CH3 , and ^R2 is a group having a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more.)

In the general formula (2), specific examples of saturated alkyl groups having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more include groups having a bridged hydrocarbon ring, such as isobornyl, bornyl, fencel (all of the above are C ₁₀ H ₁₇ , carbon atoms/hydrogen atoms=0.58), adamantyl (C ₁₀ H ₁₅ , carbon atoms/hydrogen atoms=0.66), and norbornyl (C ₇ H ₁₂ , carbon atoms/hydrogen atoms=0.58). These bridged hydrocarbon rings may be directly bonded to the COO group, or may be bonded to the COO group via a linear or branched alkylene group having 1 to 5 carbon atoms. At least one or more hydrogen atoms of these bridged hydrocarbon rings may be substituted with a hydroxyl group or an alkyl group (number of carbon atoms, for example, 1 to 5).

In the general formula (2), R ² preferably has 1 to 20 carbon atoms.

Specific examples of the (meth)acrylic acid ester represented by the general formula (2) include (meth)acrylates having an isobornyl group, (meth)acrylates having a norbornyl group, and (meth)acrylates having an adamantyl group. Among these, examples of the (meth)acrylates having an isobornyl group include isobornyl methacrylate and isobornyl acrylate, and examples of the (meth)acrylates having a norbornyl group include 3-methyl-norbornylmethyl (meth)acrylate, norbornylmethyl (meth)acrylate, norbornyl (meth)acrylate, and 1,3,3-trimethyl-norbornyl (meth)acrylate. Examples of (meth)acrylates having an adamantyl group include 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, and 1-adamantyl-α-trifluoromethyl (meth)acrylate. Among these, isobornyl methacrylate is preferred.

Examples of compounds that are the basis of repeating units different from the repeating units derived from the fluorine-containing compound represented by the above general formula (1) contained in the fluorine-containing polymer (1) include, in addition to the (meth)acrylic acid ester represented by the above general formula (2), methyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, and the like.

The fluorine-containing polymer (1) is preferably a copolymer of a fluorine-containing compound represented by general formula (1) and a (meth)acrylic acid ester represented by general formula (2). In this case, the preferred mass ratio of the fluorine-containing compound represented by general formula (1) to the (meth)acrylic acid ester represented by general formula (2) is 50:50 or more and less than 100:0.

From the viewpoint of achieving excellent liquid repellency in regions where the repellent pattern forming agent of the present disclosure is not applied, or in regions where the agent is applied but not irradiated with electromagnetic waves, the mass ratio of the fluorine-containing compound represented by general formula (1) to the (meth)acrylic acid ester represented by general formula (2) is preferably 95:5 to 75:25, and more preferably 90:10 to 80:20. These regions have excellent liquid repellency, and the regions that change to lyophilic have excellent lyophilicity after the change, which can create a large difference in wettability inside and outside the boundary of the pattern.

On the other hand, from the viewpoint of being able to use a solvent with excellent dispersibility of the photocatalyst, the mass ratio of the fluorine-containing compound represented by general formula (1) to the (meth)acrylic acid ester represented by general formula (2) is preferably 75:35 to 40:60, and more preferably 70:30 to 50:50.

（式中、Ｒ^３、Ｒ^４及びＲ^５は、同一又は異なって、炭素数１～４のアルコキシ基であり、Ｒ^６は、ラジカル重合性不飽和結合を含む基である。）で表されるアルコキシシリル基含有ラジカル重合性モノマー等が挙げられる。アルコキシ基としては、メトキシ基、及びメトキシ基などが好ましく、Ｒ^３、Ｒ^４及びＲ^５が全てメトキシ基又はエトキシ基であることが特に好ましい。Ｒ^６に含まれるラジカル重合性不飽和結合としては、例えば、ビニル基、及び（メタ）アクリロイル基等が挙げられる。Ｒ^６は、好ましくは炭素数が２～１２であり、より好ましくは２～１０である。Ｒ^６は、ラジカル重合性不飽和結合が、直接ケイ素原子に結合していてもよいし、炭素数１～１２の直鎖状若しくは分枝鎖状であり、炭化水素環で中断されていてもよいアルキレン基又はカルボニル基を介して、ケイ素原子に結合していてもよい。 The compound which is a base of the repeating unit different from the repeating unit derived from the fluorine-containing compound represented by the above general formula (1) contained in the fluorine-containing polymer (1) is a compound represented by the following general formula (3):

(wherein R ³ , R ⁴ and R ⁵ are the same or different and are alkoxy groups having 1 to 4 carbon atoms, and R ⁶ is a group containing a radically polymerizable unsaturated bond). Examples of the alkoxy group include a methoxy group and a methoxy group, and it is particularly preferable that R ³ , R ⁴ and R ⁵ are all methoxy groups or ethoxy groups. Examples of the radically polymerizable unsaturated bond contained in R ⁶ include a vinyl group and a (meth)acryloyl group. R ⁶ preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms. In R ⁶ , the radically polymerizable unsaturated bond may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linear or branched alkylene group or a carbonyl group having 1 to 12 carbon atoms and optionally interrupted by a hydrocarbon ring.

Specific examples of the alkoxysilyl group-containing radically polymerizable monomer represented by the general formula (3) include monomers represented by the following general formula:

In the above formulas, R ³ , R ⁴ and R ⁵ are the same as above, R ⁶ is a hydrogen atom, a methyl group or a chlorine atom, and n is an integer of 1-10.

The above-mentioned alkoxysilyl group-containing radical polymerizable monomers can be used alone or in combination of two or more.

The fluorine-containing polymer (1) may be a copolymer of a fluorine-containing compound represented by general formula (1), a (meth)acrylic acid ester represented by general formula (2), and an alkoxysilyl group-containing radical polymerizable monomer represented by general formula (3). In this case, it is preferable that the proportion of the alkoxysilyl group-containing radical polymerizable monomer represented by general formula (3) in all repeating units is 0.5 mol % to 5 mol %.

The polymerization method is not particularly limited and can be appropriately selected. Radical polymerization is preferred as the polymerization method. The means for causing the radical polymerization reaction is not particularly limited and can be appropriately selected. Examples of the means for causing the radical polymerization reaction include polymerization by an organic or inorganic radical initiator, light, ionizing radiation, or heat. The mode of the polymerization reaction is not particularly limited and can be appropriately selected. Examples of the mode of the polymerization reaction include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
The weight average molecular weight (Mw) of the fluoropolymer (1) is preferably from 10,000 to 1,000,000.

The composition of the fluorine-containing polymer (1) can be confirmed by ¹ H-NMR, ¹⁹ F-NMR, FT-IR, LC/MS, GC/MS or the like.

From the viewpoint of achieving excellent liquid repellency in an area where the repellent pattern forming agent of the present disclosure is not applied, or an area where the agent is applied but not irradiated with electromagnetic waves, the fluorine-containing polymer (1) is preferably a polymer containing 45% or more by mass of fluorine elements. The upper limit is not particularly limited, but may be, for example, 99.9% by mass.

On the other hand, from the viewpoint of being able to use a solvent with excellent dispersibility of the photocatalyst, it is particularly preferable that the fluorine-containing polymer (1) is a polymer containing less than 45% by mass of fluorine element. The lower limit is not particularly limited, but may be, for example, 20% by mass.

1.2 Fluorine-containing polymer (2)
The fluorine-containing polymer (2) is a polymer containing repeating units derived from the fluorine-containing compound represented by the above general formula (2-1) and/or (2-2) (the fluorine-containing compounds represented by the above general formulas (2-1) and (2-2) may be referred to as "fluorine-containing compound (2-1)" and "fluorine-containing compound (2-2)", respectively).

The fluorine-containing polymer (2) changes from liquid repellent to liquid philic when exposed to electromagnetic waves. This change occurs when the fluoroalkyl groups of the fluorine-containing polymer (2) change to hydrophilic groups such as carboxylic acid or hydroxyl groups.

In the above general formula (2-1), the cyclic structure formed by ^W2 and ^W3 may be, for example, a six-membered ring containing two etheric oxygen atoms.
In the above general formula (2-2), the cyclic structure formed by W ⁴ and W ⁵ may be, for example, a 5-membered ring containing one etheric oxygen atom, or a 6-membered ring containing no etheric oxygen atom.

As the fluorine-containing compound (2-1), from the viewpoint of liquid repellency, a compound in which W ¹ is a fluorine atom and W ² and W ³ are both a perfluoromethyl group having one carbon atom is preferred.

As the fluorine-containing compound (2-2), from the viewpoint of liquid repellency, one in which either W ⁴ or W ⁵ is a fluorine atom and the other is a perfluoromethyl group having one carbon atom is preferred.

Specific examples of the fluorine-containing compound (2-1) include perfluoro(2,2-dimethyl-1,3-dioxole) (PDD) represented by the following formula (2-1A):

Specific examples of the fluorine-containing compound (2-1) further include compounds represented by the following formulas (2-1A) to (2-1C).

Specific examples of the fluorine-containing compound (2-2) include perfluoro(2-methylene-1,3-dioxolane) represented by the following formula (2-2A) and perfluoro(2-methylene-4-methyl-1,3-dioxolane) (MMD) represented by the following formula (2-2B).

The fluorine-containing polymer (2) preferably contains at least one of the repeating units derived from the fluorine-containing compound (2-1) and the fluorine-containing compound (2-2) in an amount of 10 mol % or more based on the total repeating units. When the fluorine-containing polymer (2) contains both repeating units derived from the fluorine-containing compound (2-1) and the fluorine-containing compound (2-2), it preferably contains a total of 10 mol % or more of both repeating units.

The fluorine-containing polymer (2) may contain one type or two or more types of repeating units derived from the fluorine-containing compound (2-1). The fluorine-containing polymer (2) may contain one type or two or more types of repeating units derived from the fluorine-containing compound (2-2).

The repeating units of the fluorine-containing polymer (2) may all be either repeating units derived from the fluorine-containing compound (2-1) or repeating units derived from the fluorine-containing compound (2-2), but may also contain repeating units that do not fall into either of the repeating units derived from the fluorine-containing compound (2-1) or the fluorine-containing compound (2-2) (hereinafter also referred to as other repeating units).

The fluorine-containing polymer (2) preferably contains the repeating units derived from the fluorine-containing compound (2-1) and the fluorine-containing compound (2-2) in a proportion of 10 mol % or more, and particularly preferably 50 mol % or more, based on the total repeating units. When the fluorine-containing polymer (2) contains other repeating units, the content of the other repeating units is preferably 90 mol % or less, and particularly preferably 50 mol % or less, based on the total repeating units.

The other repeating units are not particularly limited and can be selected from a wide range. For example, perfluoroalkylenes having 4 or 6 fluorine atoms (e.g., tetrafluoroethylene (TFE)) and perfluorovinyl ethers (e.g., perfluorobutenyl vinyl ether (BVE)) can be mentioned.

As the other repeating unit, from the viewpoint of improving liquid repellency, it is preferable to use a repeating unit (C) derived from tetrafluoroethylene (TFE) or a repeating unit derived from a compound (3) represented by the following formula (3-1) or formula (3-2).

In formula (3-1), X represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms. n is 0 or 1. In formula (3-2), Y represents a perfluoroalkyl group having 1 to 8 carbon atoms, or a perfluoroalkoxy group having 1 to 8 carbon atoms. When the fluorine-containing polymer (2) contains a repeating unit derived from the compound of formula (3-1) or formula (3-2), toughness can be imparted to the liquid-repellent layer obtained from the composition containing this fluorine-containing polymer (2).

The fluorine-containing polymer (2) can be obtained, for example, by homopolymerizing the fluorine-containing compound (2-1) or the fluorine-containing compound (2-2), or by copolymerizing the fluorine-containing compound (2-1) with the fluorine-containing compound (2-2). The polymer (B) can also be obtained by copolymerizing the fluorine-containing compound (2-1) and/or the fluorine-containing compound (2-2) with tetrafluoroethylene (TFE) or the compound (3).

The polymerization method is not particularly limited and can be selected as appropriate. Radical polymerization is preferred as the polymerization method. The means for inducing a radical polymerization reaction is not particularly limited and can be selected as appropriate. Examples of the means for inducing a radical polymerization reaction include polymerization using an organic or inorganic radical initiator, light, ionizing radiation, or heat. The polymerization reaction type is not particularly limited and can be selected as appropriate. Examples of the polymerization reaction type that can be used include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

The weight average molecular weight (Mw) of the fluoropolymer (2) is preferably 10,000 to 1,000,000.

The composition of the fluorine-containing polymer (2) can be confirmed by ¹ H-NMR, ¹⁹ F-NMR, FT-IR, LC/MS, GC/MS or the like.

1.3 Photocatalysis
The photocatalyst may be any photocatalyst that can change the fluoropolymers (1) and (2) from liquid repellent to liquid repellent by its photocatalytic activity, and such photocatalysts can be appropriately selected from a wide range.

Examples of photocatalysts include titanium oxide (TiO ₂ ), tungsten oxide, zinc oxide, nitrogen-doped titanium oxide tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ). One or more of these may be selected and used in combination.

As a photocatalyst, _TiO2 is preferred because it is extremely stable physically and chemically, has high photocatalytic activity, is non-hazardous and non-toxic, is environmentally friendly, and is made from inexpensive raw materials.

There are anatase and rutile types of _TiO2 , and the anatase type is preferred because of its high photocatalytic activity.

The smaller the primary particle size of the photocatalyst, the more effective the photocatalytic reaction, and the smaller the particle size of the photocatalyst is, the more preferable it is. The average primary particle size of the photocatalyst is preferably 50 nm or less, and particularly preferably 20 nm or less. The average primary particle size of the photocatalyst is usually 5 to 300 nm.

The repellent pattern forming agent of the present disclosure preferably contains 10 to 5000% by mass of the photocatalyst relative to the fluorine-containing polymer, more preferably 100 to 1000% by mass, and even more preferably 300 to 700% by mass.

1.4 Solvent
The repellent pattern forming agent of the present disclosure preferably comprises a solvent.

As the solvent, one that can dissolve the fluorine-containing polymers (1) and/or (2) and disperse the photocatalyst while suppressing aggregation is preferred. As appropriate, a fluorine-based solvent or a non-fluorine-based solvent can be used alone, or a mixture of both can be used as the solvent.

In either case where a fluorine-based solvent or a non-fluorine-based solvent is used alone, or where a mixture of these two is used as the solvent, the fluorine-based solvent may be used alone or in combination of two or more. In this case, the non-fluorine-based solvent may be used alone or in combination of two or more. In particular, from the viewpoint of dispersing the photocatalyst well, it is preferable that the photophilic pattern forming agent of the present disclosure contains a non-fluorine-based solvent.

The non-fluorine-based solvent is not particularly limited and can be selected from a wide range of solvents. Specific examples include isopropyl alcohol, ethanol, methanol, and butyl alcohol. As a non-fluorine-based solvent, isopropyl alcohol is preferred because of its excellent dispersibility in titanium oxide.

The fluorine-based solvent is not particularly limited and can be selected from a wide range of solvents. Specific examples include HFE7300, HFE7200, HFE7100 [all manufactured by 3M Japan Ltd.], AC-6000, AE-3000 [all manufactured by AGC Ltd.], hexafluoroacetone, hexafluoroisopropanol, m-xylene hexafluoride [all manufactured by Central Glass Co., Ltd.], etc. As the fluorine-based solvent, HFE7300, HFE7200, AC-6000 and m-xylene hexafluoride are preferred because of their high solubility in isopropyl alcohol.

In particular, when using polymers containing 45% or more by mass of fluorine element as the fluorine-containing polymers (1) and (2), it is preferable to use a mixture of a fluorine-based solvent and a non-fluorine-based solvent. In this case, the total content of the non-fluorine-based solvent in the entire solvent can be 3% by mass to 80% by mass. 20% by mass to 70% by mass is more preferable, and 40% by mass to 60% by mass is particularly preferable.

In particular, when a polymer containing less than 45% by mass of fluorine element is used as the fluorine-containing polymers (1) and (2), it is preferable that the total content of fluorine-based solvents in the entire solvent is less than 30% by mass. Furthermore, it is particularly preferable to use a non-fluorine-based solvent alone without containing a fluorine solvent.

The surface tension of the solvent is preferably 13 to 23 mN/m, and particularly preferably 16 to 23 mN/m. The surface tension of the solvent is a value measured by the Wilhelmy method.

1.5 Other ingredients
The repellent pattern forming agent of the present disclosure may further contain other components, such as a fluorescent agent and a pigment.

1.6 Method for producing repellent pattern forming agent
The method for producing the pattern forming agent of the present disclosure is not limited. The pattern forming agent of the present disclosure can be produced, for example, as follows.

First, the photocatalyst is dispersed in a solvent. Then, a polymer containing repeating units derived from a fluorine-containing compound is dispersed in the solvent in which the photocatalyst has been dispersed. By dispersing in this order, the dispersibility of the photocatalyst in the polymer is improved. This makes it possible to obtain a more uniform photophilic/repellent pattern forming agent compared to when the order is changed.

1.7 Applications
The lyophilic/repellent pattern forming agent of the present disclosure is used for forming a lyophilic/repellent pattern consisting of a region exhibiting lyophilicity to a functional ink and a region exhibiting lyophobicity to the same ink. More specifically, the lyophilic/repellent pattern forming agent of the present disclosure is used for (1) forming an organic and/or inorganic conductive pattern on a flexible substrate having excellent durability against bending and stretching, and (2) forming an organic and/or inorganic semiconductor or insulator pattern, etc.

The parent-repellent pattern forming agent of the present disclosure can be used to form a parent-repellent pattern by applying electromagnetic waves in a pattern to a treated surface to which it has been applied. The method of applying electromagnetic waves in a pattern is generally a method of applying electromagnetic waves to the entire surface of a substrate through a photomask on which a pattern has been drawn, but is not limited thereto. For example, a maskless exposure device capable of drawing ultraviolet LED light in a pattern using a digital micromirror device (DMD) may be used.

2. Substrate
The substrate of the present disclosure is a substrate having a repellent pattern forming agent on its surface.

The substrate of the present disclosure has a photophilic/repellent pattern forming agent on its surface, and thus a photophilic/repellent pattern can be formed on the surface by irradiating electromagnetic waves in a pattern. By irradiating a metal substrate with electromagnetic waves and printing a conductive ink, an organic and/or inorganic patterned conductor can be produced. For this reason, the substrate of the present disclosure can be used as an advantageous article having a photophilic/repellent pattern formed on its surface. Such articles are not particularly limited and can be selected from a wide range. Specific examples of such articles may be devices having patterns of organic and/or inorganic conductors, semiconductors, or insulators. Specific examples of such articles include organic electronic devices such as organic transistors, organic EL displays, organic EL lighting, and organic solar cells.

3. Method for manufacturing an article having a repellent pattern on at least a part of its surface
The manufacturing method of the present disclosure for an article having a parent-repellent pattern on at least a portion of its surface is a manufacturing method including a step of forming a parent-repellent pattern by irradiating electromagnetic waves in a pattern shape on the surface of an article to which the parent-repellent pattern forming agent has been applied.

The method of electromagnetic wave irradiation (irradiation is also called exposure) is not particularly limited, and a wide range of methods can be selected that can change the properties of the lyophilic/repellent pattern forming agent from liquid repellent to liquid affinity. Specific examples include ordinary ultraviolet light (200 to 400 nm), vacuum ultraviolet light (172 nm), electron beams, and soft X-ray synchrotron radiation.

The electromagnetic wave irradiation (exposure) time is preferably 5 s to 300 min, and more preferably 5 s to 200 min.

The integrated light quantity of the electromagnetic waves is preferably 5 mJ/cm ² to 300 J/cm ² , and more preferably 10 mJ/cm ² to 200 J/cm ^2. When the substrate is covered with a photomask, the high concentration of ozone generated by the photocatalyst between the substrate and the photomask promotes lyophilization. Even when performing maskless exposure, the same effect can be obtained by covering the substrate with quartz glass.

A substrate coated with the lyophilic/repellent pattern forming agent of the present disclosure is irradiated with electromagnetic waves in a predetermined pattern shape to obtain a lyophilic/repellent pattern substrate, and then a functional ink is applied by a printing method to the lyophilic/repellent pattern substrate, whereby the functional ink spreads selectively in the position only in the patterned lyophilic regions. This principle makes it possible to manufacture high-definition functional material patterns at low cost. In the lyophilic/repellent pattern forming agent of the present disclosure, functional groups, such as carboxylic acids, generated as a result of the change to lyophilicity can also be selectively chemically bonded to functional materials, such as silver. For example, carboxylic acids extending from a polymer main chain as disclosed in JP 2015-044373 A can be generated with normal ultraviolet light (wavelength 200 to 400 nm) without using high-energy electromagnetic waves such as vacuum ultraviolet light (wavelength 172 nm).

Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

The present disclosure will be explained in more detail below with reference to manufacturing examples and working examples.

Production Example 1 [Phot-and-phobic pattern-forming agent (fluorine element concentration in fluorine-containing polymer: 50% by mass, IPA content in solvent: 4.9% by mass)]
A four-neck flask was charged with 30.625 g of perfluorohexyl methacrylate ( _CH2 =C( _CH3 ) _{COOCH2CH2C6F13} , hereinafter sometimes abbreviated as "Rf(C6) methacrylate"), 4.375 g of isobornyl methacrylate (hereinafter sometimes abbreviated _as "iBMA" ₎ , and ₆₆ g of _{perfluorobutyl} ethyl ether ( _C6F13OCH3 , _hereinafter sometimes abbreviated as "HFE7300"), purged with nitrogen for 10 minutes, and heated to 70°C. 0.149 g of azobisisobutyronitrile (hereinafter sometimes abbreviated as "AIBN") was added thereto, and the mixture was reacted for 6 hours to obtain a copolymer with an Rf(C6) methacrylate/iBMA=100/14.3 (mass ratio).

After cooling to room temperature, the fluoropolymer was precipitated with methanol and dried under reduced pressure. The molecular weight of the fluoropolymer obtained by the above method was measured by GPC using a fluorine-based solvent [HCFC225/hexafluoroisopropanol = 90/10 (by weight)] as the eluent, and the weight average molecular weight was 115,500.

0.2 g of the above fluoropolymer was dissolved in 93.92 g of HFE7300, and 5.88 g of "TKD-701" [manufactured by Teika Corporation, 17% by mass IPA dispersion], a product in which photocatalytic titanium oxide has been dispersed in IPA in advance, was added and uniformly dispersed (component ratio: _TiO2 : 1.00 g, IPA: 4.88 g). The mixture was then irradiated with ultrasonic waves for 5 minutes in an ultrasonic cleaner to prepare a "philic-repellent pattern forming agent."

Production Example 2 [Phot-and-phobic pattern forming agent (fluorine element concentration in fluorine-containing polymer: 50% by mass, IPA content in solvent: 25% by mass)]
A photophile-repellent pattern forming agent was prepared in the same manner as in Preparation Example 1, except that the amount of HFE7300 blended in the photophile-repellent pattern forming agent was changed from 93.92 g to 74.1 g and 24.7 g of IPA was newly added.

Production Example 3 [Phot-and-phobic pattern forming agent (fluorine element concentration in fluorine-containing polymer: 50% by mass, IPA content in solvent: 50% by mass)]
A repellent pattern forming agent was prepared in the same manner as in Preparation Example 1, except that the amount of HFE7300 blended in the repellent pattern forming agent was changed from 93.92 g to 46.96 g and 46.96 g of IPA was newly added.

Reference Example [Surface tension of IPA/HFE7300 mixed solvent]
The surface tension of the IPA/HFE7300 mixed solvent was measured by Wilhelmy method, and the results are shown in Table 1. The surface tension of the solvent used in the phobic/philic pattern forming agent in the examples of the present disclosure is in the range of 14 to 23 mN/m.

Comparative Production Example 1 [Fluorine element concentration of fluoropolymer: 50% by mass, IPA content in solvent: 0% by mass, no titanium oxide]
Comparative Production Example 1 was prepared by the same method as in Production Example 1 except that the amount of HFE7300 blended in the repellent pattern forming agent was changed from 93.92 g to 99.8 g and TKD-701 was not added.

Example 1
A "parent-repellent pattern forming agent coated substrate" was prepared by spin-coating (2000 rpm, 25 seconds, no heat treatment) the parent-repellent pattern forming agent of Production Example 1 onto a silicon wafer (thickness 0.5 mm) cut to 23 mm square. Quartz glass was placed on top of this coated substrate, and the water contact angle (WCA (°)) was measured while irradiating UV light in increments of 50 J/cm ² cumulative light amount up to 150 J/cm ² using a UV exposure device Mask Aligner ES20d [manufactured by Minaga Electric Manufacturing Co., Ltd. and Nanotec Co., Ltd. Illuminance: 16.67 mW/cm ² , UV wavelength: i (365 nm), h (405 nm), g (436 nm) line mixture]. The water contact angle was measured 5 seconds after the droplet was deposited with a droplet volume of 2 μL.

Examples 2 and 3, Comparative Example 1
The pattern-forming agent of Example 1 was replaced with the pattern-forming agents of Production Examples 2 and 3, and Comparative Production Example 1, respectively, to give Examples 2, 3, and Comparative Example 1. Except for the above-mentioned substitutions, substrates coated with the pattern-forming agent were prepared in the same manner as in Example 1, and the water contact angles were measured while exposing to UV light.

The relationship between UV exposure time (accumulated light amount) and water contact angle for Examples 1 to 3 and Comparative Example 1 is shown in Table 2 and Figure 1.

Production Example 4 [Phot-and-phobic pattern-forming agent (fluorine element concentration in fluorine-containing polymer: 34% by mass, IPA content in solvent: 100% by mass)]
A four-neck flask was charged with 21 g of Rf(C6) methacrylate, 14 g of iBMA, and 66 g of IPA, and the flask was purged with nitrogen for 10 minutes and heated to 70° C. 0.149 g of AIBN was added thereto and reacted for 6 hours to obtain a copolymer with an Rf(C6) methacrylate/iBMA=3/2 (mass ratio).

The polymer was isolated in the same manner as in Production Example 1, and the molecular weight was measured by GPC, resulting in a weight average molecular weight of 138,000.

0.2 g of the above fluoropolymer was dissolved in 93.92 g of IPA, and then TKD-701, a product in which photocatalytic titanium oxide had been dispersed in IPA, was added and dispersed uniformly. The mixture was then irradiated with ultrasonic waves for 5 minutes in an ultrasonic cleaner to prepare a photophilic/repellent pattern forming agent.

Comparative Production Example 2 [Fluorine element concentration of fluoropolymer: 34% by mass, IPA content in solvent: 100% by mass, no titanium oxide]
Comparative Example 4 was prepared by the same method as in Example 4 except that the amount of IPA added to the repellent pattern forming agent was changed from 93.92 g to 99.8 g and TKD-701 was not added.

Example 4, Comparative Example 2
A substrate coated with an phil-repellent pattern-forming agent was prepared in the same manner as in Example 1, except that the phil-repellent pattern-forming agent of Example 1 was replaced with the phil-repellent pattern-forming agent of Production Example 4 or Comparative Production Example 2, and the water contact angle was measured while exposing the substrate to UV light.

The relationship between UV exposure time (accumulated light amount) and water contact angle for Example 4 and Comparative Example 2 is shown in Table 3 and Figure 2.

Examples 5 to 7 [Phase-forming agent in which the fluorine-containing polymer is replaced from Rf(C6) methacrylate/iBMA copolymer to Teflon (registered trademark) AF]
Substrates coated with the photophilic/repellent pattern-forming agent were prepared in the same manner as in Examples 1 to 4, except that the fluorine-containing polymer Rf(C6) methacrylate/iBMA copolymer blended in the photophilic/repellent pattern-forming agents of Production Examples 1 to 4 was replaced with Teflon AF1600 (manufactured by DuPont), and UV exposure and water contact angles were measured.

Comparative Example 3 [Phot-phobic pattern forming agent in which the fluorine-containing polymer was replaced from Rf(C6) methacrylate/iBMA copolymer to Teflon AF, IPA content in solvent: 0 mass %, no titanium oxide]
A substrate coated with an affinity-repellent pattern-forming agent was prepared in the same manner as in Example 5, except that the amount of IPA in Example 5 was changed from 93.92 g to 99.8 g and that TKD-701 was not added. A substrate coated with an affinity-repellent pattern-forming agent was prepared in the same manner as in Example 5, and the water contact angle was measured while exposing the substrate to UV light.

The relationship between UV exposure time (accumulated light amount) and water contact angle for Examples 5 to 7 and Comparative Example 3 is shown in Table 4 and Figure 3.

Example 8 and Comparative Example 4 [Printing of Ag nanometal ink on a substrate with a repellent pattern]
A substrate coated with the parent-repellent pattern forming agent prepared in Example 3 and Comparative Example 1 was exposed to UV light at an integrated light quantity of 50 J/ ^cm2 through a photomask on which lines and spaces with line widths of 50 μm to 500 μm and lengths of 2 cm were drawn, to prepare a parent-repellent pattern substrate. Next, Ag nanometal ink was printed under the following conditions.
・Production method of Ag nanometal ink:
Ag nanometal ink refers to a dispersion of silver nanowires (sometimes called silver particles) in ethanol at a concentration of 0.1 to 1% by mass, and is prepared by the method described in the inventor's paper Nano Research, February 2014, Volume 7, Issue 2, pp. 236-245. That is, it was chemically synthesized by reducing silver nitrate in an ethylene glycol (EG) solvent in which polyvinylpyrrolidone (PVP) and chloride ions are dissolved. First, a PVP solution was prepared by mixing 0.163 g of PVP (average molecular weight: 360 k) with 22 g of EG solvent. A silver nitrate solution [solvent: EG 3 g, solute: silver (I) 0.18 g] and an iron chloride solution 2.8 g [solvent: EG, solute: iron (III) chloride, concentration: 600 μmol/L] were added in that order to the PVP solution to prepare a mixed solution before reaction. The mixed solution was reacted at 110° C. for 12 hours with a stirring speed of 60 rpm, and then the reaction solution was centrifuged three times and replaced with an ethanol solvent to prepare Ag nanometal ink.
Equipment: 2-axis stage controller [Sigma Koki Co., Ltd.]
Coating conditions:
(S: minimum) 100pps = 0.4mm/s
(F: maximum) 100pps = 0.4mm/s
(R: acceleration/deceleration time) R=200ms
As a result, when the photophilic/repellent pattern forming agent-coated substrate prepared in Example 3 (IPA content in the pattern forming agent solvent: 50% by mass) was used, good quality metal wiring with a line width of 100 μm or more was produced. On the other hand, when the photophilic/repellent pattern forming agent-coated substrate prepared in Comparative Example 1 (IPA content in the pattern forming agent solvent: 0% by mass, no titanium oxide) was used, the Ag nanometal ink could not be applied in a pattern.

Examples 9 to 11 and Comparative Example 5 [Relationship between UV integrated light amount and water contact angle when the substrate is replaced from a silicon wafer to a film]
The parent-repellent pattern-forming agent of Production Example 3 (IPA content in the solvent: 50% by mass) was applied to flexible resin films (1) PET film (film thickness: 100 μm), (2) diX-SR [paraxylylene-based polymer manufactured by KISCO Corporation] evaporated PET film (film thickness: 100 μm), and (3) COP film (film thickness: 190 μm) instead of silicon wafers (Examples 1 to 3, Comparative Example 1), and was applied to UV irradiation and water contact angle measurement in a manner similar to that of Example 1. Examples 9, 10, and 11 were used. Comparative Example 5 was used to apply the parent-repellent pattern-forming agent of Comparative Production Example 1 (IPA content in the solvent: 0% by mass, no TiO ₂ ) to a PET film (film thickness: 100 μm) in a manner similar to that of Example 1, was applied to UV irradiation, and water contact angle measurement in a manner similar to that of Example 1. The resin film was attached to a silicon wafer (φ10 cm) with double-sided tape, and the portion protruding from the Si wafer was cut off, and then the parent-repellent pattern-forming agent was spin-coated.

The results of the water contact angle when irradiated with UV are shown in Table 5 and Figure 4. In all resin films, the water contact angle was hydrophilized to approximately 10° or less at an integrated light dose of 50 J/ ^cm2 , similar to the silicon wafer.

Example 12 and Comparative Example 6 [Printing of Ag nanometal ink onto a polymeric/repellent pattern-forming resin film]
The parent-repellent pattern-forming agent-coated substrates produced in Example 3 and Comparative Example 1 were exposed to UV light at an integrated light quantity of 50 J/ ^cm2 through a photomask on which lines and spaces with line widths of 50 μm to 500 μm and lengths of 2 cm were drawn, to produce parent-repellent pattern substrates. Next, Ag nanometal ink was printed under the same conditions as in Example 8 and Comparative Example 4.
As a result, when the photophilic/repellent pattern forming agent-coated substrate prepared in Example 3 (IPA content in the pattern forming agent solvent: 50% by mass) was used, good quality metal wiring with a line width of 100 μm or more was produced. On the other hand, when the photophilic/repellent pattern forming agent-coated substrate prepared in Comparative Example 1 (IPA content in the pattern forming agent solvent: 0% by mass, no titanium oxide) was used, the Ag nanometal ink could not be applied in a pattern.

Claims (10)

A lyophilic/repellent pattern-forming agent containing a photocatalyst, which is used to change from liquid repellency to liquid affinity by irradiating a pattern-wise electromagnetic wave, thereby forming a lyophilic/repellent pattern,
The following general formula (1), or the following general formula (2-1) and/or (2-2):
A photophilic/phobic pattern forming agent comprising a polymer containing a repeating unit derived from a fluorine-containing compound represented by the formula:
(Wherein,
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are the same or different and are a hydrogen atom, a fluorine atom, or a chlorine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms;
Y is a direct bond, a _{hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a -CH2CH2N (} ^R1 ) _SO2- group (wherein ^R1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf and the left end is bonded to O), a _-CH2CH ( ^OY1 ) _CH2- group (wherein ^Y1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to Rf and the _{left end is bonded to O), or a -(CH2)nSO2- group (} wherein n is 1 to 10, and the right end of the formula is bonded to Rf and the left end is bonded to O);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000;
(In the formula, W ¹ is a fluorine atom, or a perfluoroalkyl group or perfluoroalkoxy group having 1 to 3 carbon atoms, W ² and W ³ are each independently a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms which may contain an oxygen atom, and W ² and W ³ may together form a cyclic structure); and
(In the formula, ^W4 and ^W5 are each independently a perfluoroalkyl group having 1 to 8 carbon atoms which may contain a fluorine atom or an oxygen atom. ^W4 and ^W5 may combine together to form a cyclic structure). The agent for forming a repellent pattern according to claim 1, further comprising a non-fluorinated solvent. The photophilic/repellent pattern forming agent according to claim 1 or 2, wherein the photocatalyst is titanium oxide (TiO ₂ ). The agent for forming a repellent pattern according to any one of claims 1 to 3, wherein the polymer contains 45% by mass or more of fluorine element. The agent for forming a repellent pattern according to any one of claims 1 to 3, wherein the polymer is a fluorine-containing polymer containing less than 45% by mass of fluorine element, and the content of the fluorine-based solvent in the solvent is less than 30% by mass. A substrate having a photophilic/repellent pattern formed on its surface by the photophilic/repellent pattern forming agent according to any one of claims 1 to 5. An organic and/or inorganic patterned conductor having the substrate according to claim 6. An article having the patterned conductor according to claim 7. The article according to claim 8, which is at least one article selected from an organic transistor, an organic EL display, an organic EL lighting device, and an organic solar cell. A method for producing an article having a repellent pattern on at least a portion of a surface thereof, comprising the steps of:
A manufacturing method comprising the step of changing the liquid repellency of the surface to which the agent for forming a repellent pattern according to any one of claims 1 to 5 has been applied from liquid repellency to liquid affinity by irradiating the surface with electromagnetic waves in a pattern shape, thereby forming a repellent pattern.