JP6900951B2 - Hardened film forming composition - Google Patents

Description

The present invention relates to a cured film-forming composition containing a polymer having a fluoroalkyl group, and further relates to a cured film and an electronic device produced by using the composition.

In the manufacturing process of electronic devices, it has been proposed to apply a separate coating technique utilizing the difference in wettability of liquids to patterning of functional thin films in forming patterns of electrodes and functional thin films. In this method, a patterning layer consisting of a region that is easily wetted with a liquid and a region that is not easily wetted with a liquid is formed on the surface of the substrate, and then a liquid containing a functional thin film forming material is applied onto the patterning layer and subsequently dried. This is a method in which a functional thin film is formed only in a region that is easily wetted with a liquid, and wiring or the like in an electronic device is manufactured.

When printing the image forming liquid used for pattern formation of the electrodes by various printing methods such as inkjet and screen printing, in order to suppress the wet spread of the liquid in areas other than the target part, only the target part is used. It is necessary to make the surface hydrophilic and the surface of the region other than the site hydrophobic.
In recent years, a polyimide precursor containing a hydrophobic side chain or a polyimide obtained from the polyimide precursor has been adopted as a patterning layer for an electrode, a functional thin film, or the like, and the water contact angle has been adjusted by changing the hydrophobicity of the polyimide film. Utilizing the fact that it can be changed, a technique for separately coating a coating type functional material has been widely studied.

For example, the characteristics of a polyimide precursor having an aliphatic ring or a wettability changing layer obtained by using polyimide are specified (see, for example, Patent Document 1). In the literature, it is presumed that the cleavage of the aliphatic ring of polyimide is one of the factors that bring about the change in the hydrophobicity, and the larger the amount of side chains (that is, the number of side chains), the more the surface. It is also speculated that the energy (critical surface tension) becomes low and the liquid becomes sparse.
Further, in the examples of the same document, when a polyamic acid obtained by using an acid dianhydride having an aliphatic ring and a diamine having a hydrocarbon group in the side chain is used as a wettability changing layer, it becomes hydrophobic by ultraviolet irradiation. It is shown that the amount of change is large, and that an electrode layer made of PEDOT / PSS is formed on the wettability change layer to produce an electronic element.

International Publication No. 2006/137366 Pamphlet

Generally, the image forming liquid is designed to have a lower surface tension than water in order to enable film formation. Therefore, the image forming liquid is often an organic solvent system having a lower surface tension than water in consideration of ease of application.
However, in the hydrophobic side chain exemplified in the above document, the hydrophobicity (that is, water repellency) of the unexposed portion cannot be said to be sufficiently high even when the content of the side chain is sufficiently increased, for example. When the image forming liquid protrudes into the unexposed portion, the image forming liquid dries as it is, and there is a problem that the desired image cannot be obtained. Further, since the wettability change layer does not form a crosslinked structure, there is a problem that the wettability change layer is dissolved depending on the type of the solvent used in the image forming liquid.

The present invention has been made in view of such circumstances, and the formed underlayer film for image formation has high liquid repellency (sparse liquid property), and easy liquid repellency can be easily achieved with a small amount of ultraviolet exposure. It is an object of the present invention to provide a resin composition for forming a cured film, which can be changed to the above and has a high solvent resistance in the parent liquid portion.

As a result of diligent studies to achieve the above object, the present inventors have made a polymer containing a structural unit derived from a specific monomer having a desorbable fluorine-containing side chain, and made the liquid-repellent property by ultraviolet irradiation. We have found that it can be greatly changed, and have completed the present invention.

（式中、Ｒ^１は水素またはメチル基を表し、
Ｒ^２はそれが結合する酸素原子を伴って脱離可能なフッ素含有基を表す。）
［２］ Ｒ^２が、分岐および／または環化していてもよく、芳香族環、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＳ−、−ＮＨ−、又はこれらの組合せにより中断されていてもよい、フッ素で置換された炭化水素基を表す、［１］に記載の硬化膜形成用樹脂組成物。
［３］ Ｒ^２の炭素原子数が２以上である、［１］又は［２］に記載の硬化膜形成用樹脂組成物。
［４］ （Ａ）成分の重合体が、熱により（Ａ）成分の重合体同士の間、又は（Ａ）成分の重合体と（Ｂ）成分の重合体との間に共有結合を形成し得る基（基（ｘ））を有する第２モノマー由来の構造単位をさらに含有することを特徴とする、［１］乃至［３］のいずれか一項に記載の硬化膜形成用樹脂組成物。
［５］ （Ｂ）成分の重合体が、熱により（Ｂ）成分の重合体同士の間、又は（Ａ）成分の重合体と（Ｂ）成分の重合体との間に共有結合を形成し得る基（基（ｘ））を有するモノマー由来の構造単位を含有することを特徴とする、［１］乃至［４］のいずれか一項に記載の硬化膜形成用樹脂組成物。
［６］ 基（ｘ）がヒドロキシ基、カルボキシル基、アミド基、アルコキシシリル基、イソシアネート基、ブロック化イソシアネート基、及び下記式（２）で表される基からなる群から選ばれる少なくとも１つの基である［４］又は［５］に記載の硬化膜形成用樹脂組成物。

（式中、Ｒ^３はアルキル基、アルコキシ基、またはフェニル基を表す。）
［７］ （Ｄ）成分として基（ｘ）と熱反応し得る基を一分子あたり２つ以上有する化合物をさらに含有する、［４］乃至［６］のいずれか一項に記載の硬化膜形成用樹脂組成物。
［８］ （Ａ）成分の重合体中のフッ素含有率が、重合体の全重量に基づいて５重量％以上である、［１］乃至［７］のいずれか一項に記載の硬化膜形成用樹脂組成物。
［９］ （Ｂ）成分の重合体中のフッ素含有率が、重合体の全重量に基づいて５重量％未満である、［１］乃至［８］のいずれか一項に記載の硬化膜形成用樹脂組成物。
［１０］ ［１］乃至［９］のいずれか一項に記載の硬化膜形成用樹脂組成物を用いて得られ、紫外線露光部が未露光部より親液化することを特徴とする硬化膜。
［１１］ 紫外線露光部と未露光部のプロピレングリコールモノメチルエーテルアセテートに対する接触角の差が５°以上である、［１０］に記載の硬化膜。
［１２］ ［１０］又は［１１］の硬化膜からなる配線形成補助層。
［１３］ 硬化膜形成用樹脂組成物の製造のための、下記式（１）の構造を有する第１モノマー由来の構造単位を含む重合体の使用。

（式中、Ｒ^１は水素またはメチル基を表し、
Ｒ^２はそれが結合する酸素原子を伴って脱離可能なフッ素含有基を表す。）
［１４］ 硬化膜形成用樹脂組成物の製造のための、下記式（１）の構造を有する第１モノマー由来の構造単位、及び熱により（Ａ）成分の重合体同士の間、又は（Ａ）成分の重合体と（Ｂ）成分の重合体との間に共有結合を形成し得る基（基（ｘ））を有する第２モノマー由来の構造単位を含む共重合体の使用。

（式中、Ｒ^１は水素またはメチル基を表し、
Ｒ^２はそれが結合する酸素原子を伴って脱離可能なフッ素含有基を表す。）
［１５］ 紫外線露光部が未露光部より親液化する硬化膜の製造のための、［１］乃至［９］のいずれか一項に記載の硬化膜形成用樹脂組成物の使用。
［１６］ 紫外線露光部と未露光部のプロピレングリコールモノメチルエーテルアセテートに対する接触角の差が５°以上である、［１５］に記載の使用。The present invention includes the following.
[1] As a component (A), a polymer containing a structural unit derived from a first monomer having the structure of the following formula (1), and
As the component (B), a polymer other than the component (A) having a fluorine content lower than that of the component (A) based on the total weight of the polymer.
As a component (C), a photoacid generator and
A resin composition for forming a cured film, which comprises a solvent.

(In the formula, R ¹ represents a hydrogen or methyl group and represents
R ² represents a fluorine-containing group that can be eliminated with the oxygen atom to which it is attached. )
[2] R ² may be branched and / or cyclized and is interrupted by an aromatic ring, -O-, -S-, -CO-, -CS-, -NH-, or a combination thereof. The resin composition for forming a cured film according to [1], which may represent a hydrocarbon group substituted with fluorine.
[3] The resin composition for forming a cured film according to [1] or [2], wherein ^{R 2 has 2 or more carbon atoms.}
[4] The polymer of the component (A) forms a covalent bond between the polymers of the component (A) or between the polymer of the component (A) and the polymer of the component (B) by heat. The resin composition for forming a cured film according to any one of [1] to [3], which further contains a structural unit derived from a second monomer having a group (group (x)) to be obtained.
[5] The polymer of the component (B) forms a covalent bond between the polymers of the component (B) or between the polymer of the component (A) and the polymer of the component (B) by heat. The resin composition for forming a cured film according to any one of [1] to [4], which contains a structural unit derived from a monomer having a group (group (x)) to be obtained.
[6] At least one group selected from the group in which the group (x) consists of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the following formula (2). The resin composition for forming a cured film according to [4] or [5].

(In the formula, R ³ represents an alkyl group, an alkoxy group, or a phenyl group.)
[7] The cured film formation according to any one of [4] to [6], further containing a compound having two or more groups capable of thermally reacting with the group (x) as a component (D). Resin composition for use.
[8] The cured film formation according to any one of [1] to [7], wherein the fluorine content of the component (A) in the polymer is 5% by weight or more based on the total weight of the polymer. Resin composition for use.
[9] The cured film formation according to any one of [1] to [8], wherein the fluorine content of the component (B) in the polymer is less than 5% by weight based on the total weight of the polymer. Resin composition for use.
[10] A cured film obtained by using the resin composition for forming a cured film according to any one of [1] to [9], wherein the ultraviolet-exposed portion is liquefied from the unexposed portion.
[11] The cured film according to [10], wherein the difference in contact angle between the ultraviolet exposed portion and the unexposed portion with respect to propylene glycol monomethyl ether acetate is 5 ° or more.
[12] A wiring forming auxiliary layer made of the cured film of [10] or [11].
[13] Use of a polymer containing a structural unit derived from a first monomer having the structure of the following formula (1) for producing a resin composition for forming a cured film.

(In the formula, R ¹ represents a hydrogen or methyl group and represents
R ² represents a fluorine-containing group that can be eliminated with the oxygen atom to which it is attached. )
[14] A structural unit derived from a first monomer having the structure of the following formula (1) for producing a resin composition for forming a cured film, and between polymers of the component (A) by heat, or (A). ) Use of a copolymer containing a structural unit derived from a second monomer having a group (group (x)) capable of forming a covalent bond between the polymer of the component (B) and the polymer of the component (B).

(In the formula, R ¹ represents a hydrogen or methyl group and represents
R ² represents a fluorine-containing group that can be eliminated with the oxygen atom to which it is attached. )
[15] Use of the resin composition for forming a cured film according to any one of [1] to [9] for producing a cured film in which the ultraviolet-exposed portion is liquefied from the unexposed portion.
[16] The use according to [15], wherein the difference in contact angle between the ultraviolet exposed portion and the unexposed portion with respect to propylene glycol monomethyl ether acetate is 5 ° or more.

The resin composition for forming a cured film containing a polymer containing a structural unit derived from a specific monomer having a desorbable fluorine-containing side chain according to the present invention is mainly composed of a solvent having a low surface tension in the film formed from the polymer. A large contact angle change, that is, a change in pro-liquid property can be imparted to the image forming liquid used as the solvent by irradiation with ultraviolet rays. Therefore, it is possible to form an underlayer film capable of forming an image of a functional material such as an electrode by utilizing these characteristics.
Further, the cured film formed from the composition of the present invention is an effective material in terms of productivity because the image forming liquid can be applied not only by inkjet but also by various methods such as spin coating and dip method. It becomes.

The present invention provides a resin composition suitable for forming a cured film which is a lower layer film for image formation including a liquid-based region and a liquid-repellent region on the surface of a substrate.

The resin composition according to the present invention is applied onto a substrate to form an undried coating film. At this time, the rich fluorine polymer (component (A)) and the poor fluorine polymer (component (B)) contained in the resin composition according to the present invention are on the side where the film is in contact with the substrate. Form a two-layer or concentration gradient so that is present at a relatively high concentration.

Next, this undried coating film is dried by heating to obtain a cured film for patterning. At this time, cross-linking occurs between the rich fluorine polymers, between the poor fluorine polymers, or between the rich fluorine polymer and the poor fluorine polymer, and the cured film for patterning becomes insoluble in the image forming liquid. Further, the poor fluorine polymer is immobilized on the side where the film is in contact with the substrate, and the rich fluorine polymer is immobilized on the surface side of the surface layer of the film in a relatively high concentration state.

The cured film for patterning is irradiated with ultraviolet rays in a pattern. The irradiation amount in this case may be lower than the irradiation amount in the prior art. Then, the coating film is heat-treated. By performing the heat treatment in the presence of the acid generated from the photoacid generator contained in the resin composition according to the present invention, the region exposed to ultraviolet rays of the fluorinated polymer present on the surface at a relatively high concentration is formed. It releases fluorine-containing groups (eg, as alcohol molecules) to cause self-crosslinking. Therefore, the region exposed to ultraviolet rays loses liquid repellency and changes to liquidity. Thus, the cured film for patterning can be efficiently used as a lower layer film for image formation including a lipophilic region and a liquid-repellent region. The lyophilized region becomes able to selectively accept the image-forming solution.

（式中、Ｒ^１は水素またはメチル基を表し、
Ｒ^２はそれが結合する酸素原子を伴って脱離可能なフッ素含有基を表す。）The cured film-forming composition of the present invention has a polymer containing a structural unit derived from a monomer having the structure of the following formula (1) as a component (A) and a fluorine content based on a weight as a component (B). A resin composition for forming a cured film, which comprises a polymer containing less than the component A), a photoacid generator as the component (C), and a solvent.

(In the formula, R ¹ represents a hydrogen or methyl group and represents
R ² represents a fluorine-containing group that can be eliminated with the oxygen atom to which it is attached. )

Further, in addition to the component (A), the component (B), the component (C) and the solvent, a cross-linking agent can be contained as the component (D). Furthermore, other additives can be contained as long as the effects of the present invention are not impaired.

The present invention will be described with reference to the following items.
1. 1. (A) Ingredient 2. (B) Ingredient 3. (C) Ingredient 4. (D) Ingredient 5. Other additives 6. Solvent 7. Preparation of cured film forming composition 8. Method for manufacturing coating film and cured film 9. Use as an underlayer film for image formation: Method for manufacturing electrodes for image formation

1. 1. Component (A) The component (A) contained in the cured film-forming composition of the present invention is a polymer containing a structural unit derived from the first monomer having the structure of the above formula (1). The component (A) is a fluorine-rich polymer having a higher fluorine content than the component (B), and when the resin composition is applied onto a substrate, the component (A) is relatively high on the surface surface side of the coating layer. It is present in concentration. Preferably, the fluorine content of the component (A) in the polymer is 5% by weight or more based on the total weight of the polymer.
The component (A) contained in the cured film-forming composition of the present invention is a polymer containing at least a structural unit derived from a monomer having the structure of the above formula (1) (in the formula, R ¹ and R ² are As defined above.).

The polymer of the component (A) in the present invention has an unsaturated double bond such as an acrylic acid ester, a methacrylic acid ester, styrene, or a derivative thereof, in addition to the monomer having the structure of the above formula (1). A polymer obtained by copolymerizing with a monomer is also included.

Therefore, the component (A) in the present invention includes
(a) A homopolymer of a type of monomer having the structure of the above formula (1),
(b) A copolymer of two or more monomers having the structure of the above formula (1),
(c) A copolymer of a monomer having the structure of the above formula (1) (one or more) and a monomer having an unsaturated double bond such as an acrylic acid ester, a methacrylic acid ester, styrene, or a derivative thereof. Included.
The polymer of the component (A) (hereinafter, also referred to as a specific copolymer) may be a polymer having such a structure, and the skeleton of the main chain and the type of side chains of the polymer constituting the polymer may be used. There is no particular limitation.

The polymer of the component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and more preferably 3,000 to 100,000. Is even more preferable. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 1,000 and is too small, heat may be deteriorated. At the time of curing, the curing may be insufficient and the solvent resistance and heat resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. Hereinafter, the same shall apply hereinafter in this specification.

^{R 2} in formula (1) represents a desorbable fluorine-containing group with an oxygen atom to which it is attached.
Preferably, R ² represents a fluorine-substituted hydrocarbon group.
The hydrocarbon group may be branched and / or cyclized. Further, the hydrocarbon group may be interrupted by an aromatic ring, -O-, -S-, -CO-, -CS-, -NH-, or a combination thereof. Examples of such interrupting groups include, but are not limited to, phenylene, naphthylene, biphenylene, ether, thioether, carbonyl, carboxyl, amide, urea and the like.
The number of carbon atoms in R ² is preferably 2 or more, more preferably 2 to 18, most preferably from 2 to 10.

^{When R 2} in the formula (1) is a hydrocarbon group substituted with fluorine, ^{one of the typical R 2} is a fluoroalkyl group.
The number of carbon atoms of the fluoroalkyl group is preferably 2 or more, 2 to 50, 2 to 30, 2 to 18, 2 to 10, 4 to 10, 4 to 8. These may be branched and / or cyclized.
Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, and 3-perfluorobutyl group. -2-Hydroxypropyl group, 2- (perfluorohexyl) ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2- (perfluorooctyl) ethyl group, 3-perfluorooctyl-2-hydroxypropyl group , 2- (Perfluorodecyl) ethyl group, 2- (perfluoro-3-methylbutyl) ethyl group, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl group, 2- (perfluoro-5-methyl) Hexyl) Ethyl Group, 2- (Perfluoro-5-Methylhexyl) -2-Hydroxypropyl Group, 2- (Perfluoro-7-Methyloctyl) Ethyl Group, and 2- (Perfluoro-7-Methyloctyl)- 2-Hydroxypropyl group, etc. may be mentioned.

^{When R 2} in the formula (1) is a hydrocarbon group substituted with fluorine and the hydrocarbon group may be interrupted by −O− ^{, one of the representative R 2} is a fluoroalkyl ether group. Is.
For example, an Rf group (a) having a polyfluoroether structure represented by the following formula 1 can be mentioned.
− (X—O) _n− Y ・ ・ ・ Equation 1
In formula 1, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorolated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and is for each unit enclosed by n. Indicates the same group or a different group, where Y is a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y) and a monovalent saturated carbon dioxide having 1 to 20 carbon atoms. It represents a hydrogen group or a fluorolated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. However, the total number of fluorine atoms in Equation 1 is 2 or more.

As an aspect of X and Y in the formula 1, preferably, X is a fluorolated alkylene group except for one hydrogen atom having 1 to 10 carbon atoms or a perfluorolated alkylene having 1 to 10 carbon atoms. It is a group and indicates the same group or a different group for each unit enclosed by n, and Y is an alkyl group or a fluorocarbonized group having 1 carbon atom except for 1 hydrogen atom having 1 to 20 carbon atoms. Those showing up to 20 perfluorolated alkyl groups can be mentioned.

More preferably, X is a perfluorolated alkylene group having 1 to 10 carbon atoms, and the same group or a different group is used for each unit enclosed by n. In this case, Y indicates a perfluorolated alkyl group having 1 to 20 carbon atoms.

In Equation 1, n represents an integer of 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, the liquid-repellent group is likely to be detached in the exposed portion, and the liquid-friendly property becomes good.

Further, the total number of carbon atoms in the Rf group (a) having the polyfluoroether structure represented by the formula 1 is 2 or more, 2 to 50, 2 to 30, 2 to 18, 2 to 10, 4 to 10, 4 to The order of 8 is preferable. In this range, the polymer which is the component (A) exhibits good liquid repellency.

Examples of _{X, -CF 2 -, - CF} 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, - CF ₂ CF ₂ CF (CF ₃ )-and CF ₂ CF (CF ₃ ) CF _2- .

Specific examples of Y include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ ,-(CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ , and (CF ₂ ) ₁₁ CF ₃ ,-(CF ₂ ) ₁₅ CF ₃ can be mentioned.

A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by the formula 1 is the Rf group (a) represented by the formula 2.

-C _p-1 F _{2 (p-1)} -O- (C _p F _2p- O) _n-1 -C _q F _{2q + 1} ... Equation 2
In Equation 2, p represents an integer of 2 or 3, and each unit enclosed by n has the same group, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

Specifically, as the Rf group (a) represented by the formula 2,
−CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2-9),
-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₆ F ₁₃ (n is 2 to 6),
-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 6)
Is preferably mentioned from the viewpoint of ease of synthesis.

The Rf groups (a) in the polymer as the component (A) may all be the same or different.

As described above, the portion of the polymer which is the component (A) exposed to ultraviolet rays by the acid generated from the photoacid generator (details will be described later) contained in the resin composition according to the present invention is of the formula (1). The structure releases fluorine-containing groups (eg, as alcohol molecules) to cause cross-linking.
In addition to the structure of the formula (1), the polymer of the component (A) is heated between the polymers of the component (A) or between the polymer of the component (A) and the polymer of the component (B). A structural unit derived from the second monomer having a group (group (x)) capable of forming a covalent bond between them can be further contained (Note that the cross-linking agent which may be added separately is described in the section of component (D)). Explained in).

（式中、Ｒ^３はアルキル基、アルコキシ基、またはフェニル基を表す。）
これらのうち、ヒドロキシ基、カルボキシル基またはアミド基が好ましい。Preferably, the group (x) is at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the following formula (2). Is.

(In the formula, R ³ represents an alkyl group, an alkoxy group, or a phenyl group.)
Of these, a hydroxy group, a carboxyl group or an amide group is preferable.

These thermally reactive sites can form a covalent bond with another polymer of the component (A) or a polymer of the component (B) via a direct bond or a linking group, and as such a linking group, , A divalent group selected from a linear alkylene group having 1 to 15 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, and a phenylene group. Alternatively, it is a group in which a plurality of the divalent groups are bonded. In this case, the bond between the divalent groups constituting the linking group and the bond between the linking group and the thermoreactive site include a single bond, an ester bond, an amide bond, a urea bond or an ether bond. When there are a plurality of divalent groups, the divalent groups may be the same or different, and when there are a plurality of bonds, the bonds may be the same or different.

Examples of the linear alkylene group having 1 to 15 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group and an n-octylene. Examples thereof include a group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, an n-tetradecylene group and an n-pentadecylene group.

Examples of the branched alkylene group having 3 to 20 carbon atoms include an i-propylene group, an i-butylene group, an s-butylene group, a t-butylene group, a 1-methyl-n-butylene group and a 2-methyl-butylene group. n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl -N-propylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n- Butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3 -Dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene In addition to groups such as 1-ethyl-1-methyl-n-propylene group and 1-ethyl-2-methyl-n-propylene group, an alkylene having a carbon atom number of up to 20 and branched at any position. The group etc. can be mentioned.

Examples of the cyclic alkylene group having 3 to 20 carbon atoms include a monocyclic alkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group and a cyclooctylene group, and a norbornylene. Examples thereof include a polycyclic alkylene group such as a group, a tricyclodecylene group, a tetracyclododecylene group and an adamantylene group.

In the above formula (2) ^{, examples of the alkyl group represented by R 3} include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferable.
Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and n-pentyl group. , 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group Group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl- n-Butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2 -Trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl Group, n-octyl group, n-nonyl group, n-decanyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Examples thereof include a group, an n-octadecyl group, an n-nonadecil group, an n-eicosyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
Among them, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group and the like are preferable.

In the above formula (2) ^{, examples of the alkoxy group represented by R 3} include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and an n-pentoxy group. , 1-Methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-Dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl- n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2 , 2-Dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2, -trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n- Propoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group Group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadesyloxy group, n-eicosadeciloxy group, cyclopropoxy group, cyclobutoxy group, Cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group and the like can be mentioned.
Among them, a methoxy group, an ethoxy group, an n-propoxy group and the like are preferable.

In addition to the structural unit derived from the first monomer represented by the formula (1), between the polymers of the component (A) or between the polymers of the component (A) and the polymer of the component (B) by heat. A group (group (x)) capable of forming a covalent bond between them, preferably a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and the above formula (2). As a method for synthesizing a copolymer containing a structural unit derived from a second monomer having at least one group (x) selected from the group consisting of the groups to be formed, a first monomer having a structure of the formula (1) and heat are used. A group (group (x)) capable of forming a covalent bond between the polymers of the component (A) or between the polymer of the component (A) and the polymer of the component (B). Has at least one group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). The method of polymerizing with a monomer is simple.

As a monomer having at least one group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). , For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3 -Dihydroxypropyl methacrylate, glycerin monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) acrylate, poly (propylene glycol) acrylate , Poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2 Monoxy group-containing monomers such as −carboxylic-6-lactone; acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, Also monomers having a carboxyl group such as N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylicamide, and N- (carboxyphenyl) acrylamide; hydroxystyrene, N- (hydroxyphenyl) methacrylicamide, N- (hydroxy) Monomers having a phenolic hydroxy group such as phenyl) acrylamide, N- (hydroxyphenyl) maleimide, and N- (hydroxyphenyl) maleimide; acrylamide, methacrylicamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N Monomonos with amide groups such as −diethylacrylamide; 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane Monomer having an alkoxysilyl group such as silane; Monomer having a group represented by the above formula (2) such as 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate (ethylene glycol monoacetate acetate monomethacrylate); 2- Monomer having an isocyanate group such as acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate; 2-(0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, 2-[(3,5-dimethyl) Examples thereof include monomers having a blocked isocyanate group such as pyrazolyl) carbonylamino] ethyl methacrylate and diethyl2-((2- (methacryloyloxy) ethyl) carbamoyl) malonate.

Further, the component (A) contained in the resin composition for forming a cured film of the present invention is a structural unit derived from a monomer represented by the formula (1), a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, and an isocyanate. It has a structural unit derived from a monomer having at least one group (x) selected from the group consisting of a group, a blocked isocyanate group, and a group represented by the above formula (2), and a structural unit derived from a monomer other than the above. It can also be a copolymer.

Examples of the method for synthesizing such a copolymer include a monomer represented by the formula (1), a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and the above formula (2). A monomer having at least one group (x) selected from the group consisting of the groups represented by (hereinafter, hydroxy group, carboxyl group, amide group, alkoxysilyl group, isocyanate group, blocked isocyanate group, and the above formula (2). The group represented by) is also referred to as a specific functional group 1), and a method of polymerizing a monomer other than the above (hereinafter, also referred to as a third monomer) is convenient.

The monomer represented by the formula (1) and the monomer having at least one group (x) are as described above. The above-mentioned third monomer means a monomer other than the first and second monomers.
Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds and vinyl compounds.
Hereinafter, specific examples of the third monomer will be given, but the present invention is not limited thereto.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-. Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 Examples thereof include −propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-. Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ Examples thereof include −butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinylcarbazole, allylglycidyl ether, and 3-ethenyl-7-oxabicyclo [4.1.0] heptane.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

The amount of each monomer used to obtain the specific copolymer is 10 to 90 mol% of the monomer represented by the formula (1), a hydroxy group, a carboxyl group, an amide group, based on the total amount of all the monomers. It is preferable that 10 to 90 mol% of the monomer has at least one group (x) selected from the group consisting of an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). .. If the content of the monomer having the specific functional group 1 is less than 10 mol%, it may be difficult to impart sufficient thermosetting property, and it may be difficult to maintain the solvent resistance of the obtained cured film.
When the third monomer is used in combination to obtain the specific copolymer, the amount used is preferably 90 mol% or less based on the total amount of all the monomers.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, but for example, in a solvent in which the first and second monomers, the third monomer and the polymerization initiator and the like coexist, if desired, at 50 to 110 ° C. Obtained by polymerization reaction under temperature. At that time, the solvent used is not particularly limited as long as it dissolves the first and second monomers, the third monomer used if desired, the polymerization initiator and the like. Specific examples will be described in <Solvent> described later.
The specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained by the above method is put into diethyl ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. It can be dried at room temperature or heat-dried to obtain a powder of a specific copolymer. By the above operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the present invention, the specific copolymer may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.

Further, in the present invention, the specific copolymer of the component (A) may be a mixture of a plurality of types of specific copolymers.

2. Component (B) The component (B) contained in the cured film-forming composition of the present invention is a polymer other than the component (A), and the fluorine content based on the total weight of the polymer is the component (A). Less polymer. The component (B) is a fluorine-poor polymer that does not contain or has a trace amount of fluorine atoms even if it is contained, and when the present resin composition is applied onto the substrate, it is relatively high on the substrate side of the coating layer. It is present in concentration. Preferably, the fluorine content of the component (B) in the polymer is less than 5% by weight based on the total weight of the polymer.

Even if the component (B) contained in the resin composition for forming a cured film of the present invention contains a structural unit derived from a monomer having the structure of the above formula (1), the content rate in terms of weight is (A). ) It is a polymer with less than the components.

The resin composition for forming a cured film of the present invention takes the form of a so-called polymer blend by mixing another polymer as a component (B) in addition to the component (A).
By appropriately adjusting the structure and the like of the polymer (component (A), component (B), and other polymers) contained in this polymer blend, in the thickness direction in the film when a cured film is formed. Since it is possible to generate a concentration gradient of each polymer, it can be used as a useful means.

For example, the change in liquid repellent property is a problem only on the film surface. Therefore, from this viewpoint, if the polymer having a fluoroalkyl group of the present invention is present only in the upper layer (surface layer) of the cured film. Good.
The blending ratio of each component will be described in the section "Preparation of cured film forming composition".

By performing the above polymer blending, the amount of the fluorine-containing compound, which is generally expensive, can be reduced, and an inexpensive material having sufficient performance can be obtained. Further, by selecting the component (B) having an appropriate structure, effects such as improvement of film forming property and improvement of adhesion to the substrate can be imparted.

As described above, in order to form the lower layer of the cured film as a low liquid repellent layer and the upper layer as a pro-liquid repellent conversion layer, it is possible to prepare these layers by sequentially laminating them, but the operation is complicated. ..
At this time, the low-liquidity material and the material of the pro-liquid-repellent conversion layer (that is, the polymer of the component (A) of the present invention) are mixed, and at that time, the polarity or molecular weight of the upper layer material is changed to that of the lower layer. If the size is smaller than that of the above-mentioned one, the above-mentioned concentration gradient (here) because the material of the upper layer moves to the surface and forms a layer while the mixed liquid is applied to the substrate and dried to evaporate the solvent. (Layer separation) can be easily controlled.

The most preferable material for forming the film capable of forming the lower layer is an acrylic polymer.
Other materials that can be used as the underlayer material include general organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinylphenol, polyisobutylene, polyester, and polyimide.

Further, when the polymer blend is used for an application requiring a film thickness of about 400 nm, for example, in order to prevent the in-plane variation in the surface physical properties of the cured film from becoming large, the polymer of the component (A) is used. It is preferably contained at least 5% by weight or more.

As the component (B), a polymer having an N-alkoxymethyl group and a polymerizable group containing a C = C double bond as a unit structure is preferable.

The N of the N-alkoxymethyl group, that is, the nitrogen atom, is the position adjacent to the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom of the nitrogen-containing heterocycle. Examples thereof include nitrogen atoms bonded to. Therefore, the N-alkoxymethyl group includes nitrogen bonded to the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom of the nitrogen-containing heterocycle. Examples thereof include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

The monomer giving the N-alkoxymethyl group may be any monomer having the above group, and preferably, for example, a compound represented by the following formula (b1) can be mentioned.

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.)

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and 1-methyl-n. -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl Group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl- n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl -N-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2- Ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl- n-Butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n -Heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2- Dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl -N-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methy. Examples thereof include ru-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. ..

Specific examples of such monomers include hydroxymethyl groups such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Alternatively, an acrylamide compound or a methacrylamide compound substituted with an alkoxymethyl group can be mentioned. Note that (meth) acrylamide means both methacrylamide and acrylamide.

The polymer of the component (B) has a structure derived from a monomer having a group (group (x)) capable of forming a covalent bond with another polymer of the component (B) or a polymer of the component (A) by heat. Can contain units.
For example, the component (B) contained in the cured film-forming composition of the present invention includes a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and the above formula (2). A compound having at least two groups (x) (hereinafter, also referred to as specific functional group 2) selected from the group consisting of the groups to be treated can be contained.

Examples of the polymer compound as the component (B) include acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and polyalkyleneimines. , Polyallylamine, celluloses (cellulose or derivatives thereof), polymers having a linear structure or branched structure such as phenol novolac resin, cyclic polymers such as cyclodextrins and the like.

Preferred examples of the polymer compound as the component (B) include acrylic polymers, cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and phenol novolac resins.

The acrylic polymer which is a preferable example of the polymer compound of the component (B) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, and vinyl compound. , A polymer obtained by polymerizing a monomer containing the group (x) or a mixture thereof, and the type of the main chain skeleton and side chains of the polymer constituting the acrylic polymer is not particularly limited.

As a monomer having at least one group (x) selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the above formula (2). , For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3 -Dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate , Hydroxy group-containing monomers such as 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornen-2-carboxylic-6-lactone; acrylic acid, Methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylicamide, and Monomers having a carboxyl group such as N- (carboxyphenyl) acrylamide; hydroxystyrene, N- (hydroxyphenyl) methacrylicamide, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) maleimide, and N- (hydroxyphenyl) ) Monomer having a phenolic hydroxy group such as maleimide; Monomer having an amide group such as acrylamide, methacrylicamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide; 3-acryloyloxytrimethoxysilane , 3-Acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane and other monomers having an alkoxysilyl group; 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl A monomer having a group represented by the above formula (2) such as methacrylate (ethylene glycol monoacetate acetate monomethacrylate); a monomer having an isocyanate group such as 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate; 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, diethyl2-((2- (methacryloyloxy) ethyl)) Examples thereof include monomers having a blocked isocyanate group such as carbamoyl) malonate.

Further, in the present invention, when synthesizing the acrylic polymer which is an example of the component (B), a monomer having no specific functional group 2 can be used in combination as long as the effect of the present invention is not impaired.

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds and vinyl compounds.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Examples thereof include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Examples thereof include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.

The amount of the monomer having a specific functional group 2 used to obtain the acrylic polymer which is an example of the component (B) is based on the total amount of all the monomers used to obtain the acrylic polymer which is the component (B). 2, 2% by weight to 100% by weight is preferable. If the monomer having the specific functional group 2 is too small, the coatability of the obtained cured film may be insufficient.
When a monomer having no specific functional group 2 is used in combination when obtaining an acrylic polymer, the amount used is preferably 98% by weight or less based on the total amount of all the monomers.

The method for obtaining the acrylic polymer as an example of the component (B) is not particularly limited, and for example, a monomer having a specific functional group 2, a monomer having no specific functional group 2 if desired, a polymerization initiator and the like can be used. It is obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a coexisting solvent. At that time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group 2, a monomer having no specific functional group 2 used as desired, a polymerization initiator and the like. Specific examples will be described in the section <Solvent> described later.

The acrylic polymer, which is an example of the component (B) obtained by the above method, is usually in the state of a solution dissolved in a solvent.

Further, the solution of the acrylic polymer, which is an example of the component (B) obtained by the above method, is put into diethyl ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then the precipitate is filtered and washed. It can be dried at room temperature or heat-dried under normal pressure or reduced pressure to obtain a powder of an acrylic polymer which is an example of the component (B). By the above operation, the polymerization initiator and the unreacted monomer coexisting with the acrylic polymer which is an example of the component (B) can be removed, and as a result, the acrylic polymer which is an example of the purified component (B) can be removed. Powder is obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

The acrylic polymer, which is a preferable example of the component (B), preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and 5,000 to 100. It is more preferably 000. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 3,000 and too small, heat may be deteriorated. At the time of curing, the curing may be insufficient and the solvent resistance and heat resistance may decrease.

Cyclodextrins which are preferable examples of the high molecular compound of the component (B) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin; methyl-α-cyclodextrin and methyl-β-cyclo. Dextrin, and methylated cyclodextrins such as methyl-γ-cyclodextrin; hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-Hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-Hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β Examples thereof include -cyclodextrin and hydroxyalkylcyclodextrin such as 2,3-dihydroxypropyl-γ-cyclodextrin, and for example, hydroxyalkylcyclodextrin is preferable.

As preferred examples of the polymer compound of the component (B), hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose and Examples thereof include cellulose, and for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

Next, as a preferred example of the polymer compound of the component (B), as a polyether polyol, polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, and sorbitol, and propylene oxide and polyethylene glycol are used. , Polypropylene glycol and the like are added. Specific examples of the polyether polyol include ADEKA's ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series, and Nichiyu Uniox (registered trademark) HC-40, HC-60, ST. -30E, ST-40E, G-450, G-750, Uniol® TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB- 400, Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.

As a polyester polyol which is a preferable example of the polymer compound of the component (B), a polyvalent carboxylic acid such as adipic acid, sebacic acid and isophthalic acid and a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol are used. Can be mentioned. Specific examples of the polyester polyol include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, and OD-X-668 manufactured by DIC. , OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD -X-2555, OD-X-2560, Kuraray Polyesters P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, Examples thereof include F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

Examples of the polycarbonate polyol which is a preferable example of the polymer compound of the component (B) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include Daicel Chemical's Praxel (registered trademark) CD205, CD205PL, CD210, CD220, Kuraray's polycarbonate diols C-590, C-1050, C-2050, C-2090, C-3090 and the like. ..

Examples of the polycaprolactone polyol which is a preferable example of the polymer compound of the component (B) include ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include Polylite® OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC, and Praxel® 205, L205AL, 205U, 208, 210 manufactured by Daicel Chemical Co., Ltd. , 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.

Examples of the phenol novolac resin, which is a preferable example of the polymer compound of the component (B), include a phenol-formaldehyde polycondensate.

In the resin composition for forming a cured film of the present invention, the compound of the component (B) may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.

Further, in the resin composition for forming a cured film of the present invention, the component (B) may be a single component or a mixture of a plurality of types of the compounds exemplified as the component (B).

The content of the component (B) in the resin composition for forming a cured film of the present invention is 5 to 95 parts by mass, 30 to 95 parts by mass, 50 to 95 parts by mass, 60 parts by mass with respect to 10 parts by mass of the component (A). It is preferable in the order of to 95 parts by mass and 80 to 95 parts by mass. When the content of the component (B) is excessive, there is a problem that the image forming ability is lowered. If it is too small, there is a problem that the film forming property is lowered.

3. 3. Component (C) The resin composition for forming a cured film of the present embodiment further contains a photoacid generator as a component (C) in addition to the component (A), the component (B) and the solvent.

The photoacid generator of the component (C) is not particularly limited as long as it is a compound that photodecomposes to generate an acid when irradiated with ultraviolet rays.

Examples of the acid generated when the photoacid generator is photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-. Toluene sulfonic acid, campha sulfonic acid, trifluoromethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylen sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid and other sulfonic acids Examples thereof include acid or its hydrate and salt.

Examples of compounds that generate acid by light include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-. P-toluenetris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate , N-ethyl-p-toluenesulfoneamide, compounds represented by the following formulas [PAG-1] to [PAG-41], and the like.

The content of the component (C) in the resin composition for forming a cured film of the present invention is preferably 0 when the total mass of the polymer of the component (A) and the polymer of the component (B) is 100 parts by mass. .1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass, further preferably 1 part by mass to 15 parts by mass, and most preferably 5 parts by mass to 15 parts by mass. If the content of the component (C) is more than 20 parts by mass, the storage stability of the composition may decrease.

4. Component (D) The resin composition for forming a cured film according to the present invention may further contain a compound having two or more groups per molecule capable of thermally reacting with the group (x) as the component (D). The component (D) is a cross-linking agent, which is optionally introduced into the composition. For example, it is a compound having a structure capable of forming a bridging structure by a thermal reaction with a hydroxy group or the like contained in the components (A) and (B).

Specific examples will be given below, but the present invention is not limited to these. The heat cross-linking agent is, for example, a (D-1) phenoplast-based compound, (D-2) epoxy-based compound, (D-3) a cross-linking compound having two or more isocyanate groups or blocked isocyanate groups per molecule. (D-4) A crosslinkable compound having two or more merdrumic acid structures per molecule is preferable. When the group (x) is an isocyanate group, a blocked isocyanate group, or an alkoxysilyl group, a compound having two or more groups (x) per molecule can be used as the cross-linking agent. These cross-linking agents can be used alone or in combination of two or more.

Specific examples of the (D-1) phenoplast-based compound include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, and 2,6-bis (hydroxymethyl) -4. -Methoxyphenol, 3,3', 5,5'-tetrakis (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4' -(1-Methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) bis [2,6-bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol, 2,6-bis (methoxy) Methyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3', 5,5'-tetrakis (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis ( 2-methoxy-5-methylbenzene methanol), 4,4'-(1-methylethylidene) bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxymethyl] Phenol], 4,4'-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol], etc. Be done. It is also available as a commercially available product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( As mentioned above, Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.

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

（式中、ｋは２〜１０の整数、ｍは０〜４の整数を示し、Ｒ^２１はｋ価の有機基を表す）Further, the resin composition for forming a cured film of the present invention can contain an epoxy compound as the component (D-2).
As the epoxy compound, for example, a crosslinkable compound represented by the formula (d2) can be contained.

(In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R ²¹ represents a k-valent organic group.)

Such a component is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (d2). Specific examples thereof include the following formulas D-2-1 and D-2-2, and commercially available products shown below.

Commercially available products include Epolide GT-401, GT-403, GT-301, GT-302, Selokiside 2021, Selokiside 3000 (trade name manufactured by Daicel Chemical Industry Co., Ltd.), and Denacol, which is an alicyclic epoxy resin. EX-252 (trade name manufactured by Nagase Chemutex Co., Ltd.), CY175, CY177, CY179 (above, product name manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 ( Above, CIBA-GEIGY AG product name), Epicron 200, 400 (Product name by DIC Co., Ltd.), Epicoat 871, 872 (Product name by Yuka Shell Epoxy Co., Ltd.), ED-5661, ED-5662 (all, trade names manufactured by Ceranies Coating Co., Ltd.), and the like can be mentioned. Further, a polymer obtained by using Cyclomer M-100 (trade name manufactured by Daicel Corporation) or the like as a raw material can be used.

Further, as the epoxy compound, for example, a compound having a partial structure of the following formula (D-2-3) can be used.

（式中、ｐは２〜１０の整数を示し、Ｒ^３１はｐ価の有機基を表す。）

(In the formula, p represents an integer of 2 to 10 and R ³¹ represents a p-valent organic group.)

The compound has no particular limitation as long as it has an oxylan structure represented by the formula (D-2-3). Specific examples thereof include the following formula (D-2-4) and commercially available products shown below.

As commercially available products, examples of the bisphenol A type epoxy resin include "Epicoat 828", "Epicoat 834", "Epicoat 1001", "Epicoat 1004" (trade names, all manufactured by Japan Epoxy Resin), and "Epiclon 850". , "Epoxylon 860", "Epoxylon 4055" (trade name, all manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like. Examples of the bisphenol F type epoxy resin include "Epicoat 807" (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) and "Epiclon 830" (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.). Examples of the phenol novolac type epoxy resin include "Epiclon N-740", "Epiclon N-770", "Epiclon N-775" (trade name, all manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Epicort 152". , "Epicoat 154" (trade name, both manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Examples of the cresol novolac type epoxy resin include "Epiclon N-660", "Epiclon N-665", "Epiclon N-670", "Epiclon N-673", "Epiclon N-680", and "Epiclon N-695". , "Epoxy N-665-EXP", "Epoxy N-672-EXP" (trade name, all manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like. Examples of the glycidylamine type epoxy resin include "Epiclon 430", "Epiclon 430-L" (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), "TETRAD-C", and "TETRAD-X" (trade name). , All manufactured by Mitsubishi Gas Chemical Company, Inc., "Epicoat 604", "Epicoat 630" (trade name, all manufactured by Japan Epoxy Resin Co., Ltd.), "Sumiepoxy ELM120", "Sumiepoxy ELM100", "Sumiepoxy ELM434" , "Sumiepoxy ELM434HV" (trade name, all manufactured by Sumitomo Chemical Co., Ltd.), "Epototo YH-434", "Epototo YH-434L" (trade name, all manufactured by Toto Kasei Co., Ltd.), "Araldite MY" -720 ”(trade name, manufactured by Asahi Ciba Co., Ltd.) and the like. Further, a polymer obtained by using glycidyl methacrylate or the like as a raw material can be used.

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

The component (D-3) is not particularly limited as long as it is a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule. Specific examples thereof include commercially available products shown below.
Commercially available products include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, and B-5010 (above, Mitsui Chemicals (above, Mitsui Chemicals). (Manufactured by Asahi Kasei Chemicals Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like.
Further, obtained from a monomer having a blocked isocyanate group such as Calends (registered trademark) AOI, Calends MOI, Calends MOI-BM, Calends MOI-BP, Calends MOI-DEM (all manufactured by Showa Denko KK) as a raw material. The polymer to be used can be used.

The component (D-4) is a crosslinkable compound having two or more Meldrum's acid structures per molecule. Among these, the compound represented by the following formula [A] is preferable.

（式中、Ｗ_１はｋ_１価の有機基を表す。Ｖ_１は、−Ｈ、−ＯＨ、−ＳＲ、−ＯＲまたは−ＮＨＲを表し、Ｒは、ベンゼン環、シクロヘキサン環、ヘテロ環、フッ素、エーテル結合、エステル結合、アミド結合を任意の場所に含んでいてもよい炭素原子数が１〜３５の一価の有機基を表す。ｋ_１は、１〜８の整数を表す。）

(Wherein, _{W 1} is _.V 1 representing a _{k 1} monovalent organic group represents -H, -OH, -SR, an -OR or -NHR, R is a benzene ring, a cyclohexane ring, a hetero ring, fluorine , Ether bond, ester bond, amide bond may be contained at any place. The number of carbon atoms represents a monovalent organic group of ₁ to 35. K 1 represents an integer of 1 to 8.)

When k ₁ is 2, W ₁ is preferably a linear, branched or cyclic alkylene of C _{2 to} C _10. Such compounds, including methods of manufacture, are described in WO2012 / 091089, International Patent Application Publication No. WO2012 / 091089.

As such a compound, a compound represented by the following formula D4 is particularly preferable.

The cross-linking agent represented by the above formula [A] may be used alone or in combination of two or more.

When the group (x) is an isocyanate group, a blocked isocyanate group, or an alkoxysilyl group, a compound having two or more groups (x) per molecule can be used as the cross-linking agent.
Specific examples thereof include pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, adipic acid, adipamide, 1-(4- (2- (4- (3-oxo-butyl) -phenoxy)-. Ethoxy) -phenyl) -butane-1,3-dione, 1,4-butanediol diacetacetate and the like can be mentioned.
Further, among the polymers defined as the component (B) as the polymer compound having two or more groups (x) per molecular chain, the polymer having two or more groups (x) per molecular chain shall be used. You can also.

Among these, blocked isocyanate obtained from a monomer of diethyl2-((2- (methacryloyloxy) ethyl) carbamoyl) malonate, a crosslinkable compound having a Meldrum's acid structure from the viewpoint of reactivity and solvent resistance, as a raw material. A polymer having a group is preferable.

When the component (D) is added as the cross-linking agent, the content is 3 to 50 parts by mass, preferably 7 to 40 parts by mass, more preferably 7 to 40 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Is 10 to 30 parts by mass. When the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so that the effect of improving the solvent resistance after pattern formation may not be obtained. On the other hand, when it exceeds 50 parts by mass, an uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are lowered, and the resin for forming a cured film is formed. The storage stability of the composition may deteriorate.

5. Other Additives The resin composition for forming a cured film according to the embodiment of the present invention may contain other additives as long as the effects of the present invention are not impaired.
As other additives, for example, a sensitizer can be contained. The sensitizer is effective in promoting the photoreaction when forming the cured film of the embodiment of the present invention from the cured film forming composition of the present embodiment.

Examples of the sensitizer include derivatives such as benzophenone, anthracene, anthraquinone and thioxanthone, and nitrophenyl compounds. Of these, N, N-diethylaminobenzophenone, which is a derivative of benzophenone, and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacetylene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrophenyl compounds, which are nitrophenyl compounds. Nitrostilbene, 4-nitrobenzophenone and 5-nitroindole are particularly preferred.
These sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more compounds.

In the embodiment of the present invention, the ratio of the sensitizer used is 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A), the component (B) and the component (C). It is preferable, and more preferably 0.2 parts by mass to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if it is too large, the transmittance of the formed cured film may decrease or the coating film may become rough. I have something to do.

In addition, the cured film-forming composition of the embodiment of the present invention contains silane coupling agents, surfactants, rheology modifiers, pigments, dyes, and storage stability as other additives as long as the effects of the present invention are not impaired. It can contain agents, antifoaming agents, antioxidants and the like.

6. Solvent The resin composition for forming a cured film according to the embodiment of the present invention is often used in a solution state dissolved in a solvent. The solvent used at that time dissolves the component (A), the component (B) and the component (C), the component (D) if necessary, and / or other additives, and such The type and structure of the solvent are not particularly limited as long as they have a dissolving ability.

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether. Acetate, propylene glycol propyl ether acetate, cyclopentyl methyl ether, isopropyl alcohol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , 2-Hydroxypropionate, 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and Examples thereof include N-methylpyrrolidone.

These solvents can be used alone or in combination of two or more. Of these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 3-methoxypropion. Ethyl phosphate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferable because they have good film-forming properties and high safety.

When the component obtained by removing the solvent from the resin composition for forming a cured film according to the present invention is regarded as a solid content, the ratio of the solid content to the composition is, for example, 1% by mass or more and 30% by mass or less.

7. Preparation of Cured Film Forming Composition The cured film-forming resin composition according to the present invention contains a polymer (B) containing a structural unit derived from the first monomer having the structure of the above formula (1) as a component (A). ) A polymer other than the component (A) having a fluorine content lower than that of the component (A) based on the total weight of the polymer, a photoacid generator as the component (C), and a solvent. And contains. In addition, a cross-linking agent can be contained as the component (D). Then, other additives can be contained as long as the effects of the present invention are not impaired.

The mixing ratio of the component (A) and the component (B) is preferably 5:95 to 45:55 in terms of mass ratio. When the content of the component (B) is excessive, there is a problem that the image forming ability is lowered. If it is too small, there is a problem that the film forming property is lowered.

Preferred examples of the resin composition for forming a cured film according to the present invention are as follows.

[1]: A polymer containing a structural unit derived from a first monomer having the structure of the above formula (1) as a component (A), and a polymer other than the component (A) as a component (B). A polymer having a fluorine content lower than that of the component (A) based on the total weight of the polymer is contained in a mass ratio of the component (A): the component (B) of 5-15: 85-95.
Contains 0.1 to 20 parts by mass of the photoacid generator of component (C) and a solvent with respect to 100 parts by mass of the total amount of the polymer of component (A) and the polymer of component (B). Resin composition for forming a cured film.

[2]: A polymer containing a structural unit derived from a first monomer having the structure of the above formula (1) as a component (A), and a polymer other than the component (A) as a component (B). A polymer having a fluorine content lower than that of the component (A) based on the total weight of the polymer is contained in a mass ratio of the component (A): the component (B) of 5-15: 85-95.
0.1 part by mass to 20 parts by mass of the photoacid generator of the component (C) with respect to 100 parts by mass of the total amount of the polymer of the component (A) and the polymer of the component (B).
A resin composition for forming a cured film containing 3 to 40 parts by mass of the component (D) and a solvent.

The blending ratio, preparation method, etc. when the cured film-forming composition according to the present invention is used as a solution will be described in detail below.
The proportion of the solid content in the cured film-forming composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in the solvent, but is preferably 1% by mass to 80% by mass. It is 3% by mass to 60% by mass, more preferably 5% by mass to 40% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all the components of the cured film forming composition.

The method for preparing the cured film-forming composition of the present embodiment is not particularly limited. As a preparation method, for example, a method of mixing the component (A), the component (C), and the component (D) in a predetermined ratio with a solution of the component (B) dissolved in a solvent to obtain a uniform solution, or At an appropriate stage of this preparation method, a method of further adding and mixing other additives as needed can be mentioned.

In the preparation of the cured film-forming composition of the present embodiment, the solution of the specific copolymer obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (A), the component (C), the component (D) and other optional components are added to the solution prepared with the component (B) acrylic polymer to prepare a uniform solution. At this time, an additional solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the process of preparing the component (B) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.

Further, it is preferable that the prepared solution of the cured film-forming composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.

8. Method for manufacturing coating film and cured film The resin composition for forming a cured film of the present invention is placed on a general-purpose plastic substrate such as polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, polyether sulfone, polyethylene naphthalate, or polyimide, or a glass substrate. , Dip method, spin coating method, transfer printing method, roll coating method, inkjet method, spray method, brush coating, etc., and then the coating film is dried and heat-treated with a hot plate or oven to obtain an image. A cured film for patterning that can be used as a lower layer film for formation or an insulating film is formed.

The method of the heat treatment is not particularly limited, and examples thereof include a method of performing the heat treatment in an appropriate atmosphere, that is, in an atmosphere, an inert gas such as nitrogen, or in a vacuum, using a hot plate or an oven.
The firing temperature is preferably 200 ° C. or lower in order to suppress the structure of the formula (1) of the component (A) and the decomposition of the photoacid generator of the component (C).
The firing may be subject to a temperature change of two or more steps. The uniformity of the film obtained by firing step by step can be further improved.

When the cured film of the present invention produced as described above is used as an image-forming underlayer film, if the film thickness is too thin, the patterning property after ultraviolet irradiation is deteriorated, and if it is too thick, the surface uniformity is impaired. Therefore, the film thickness is preferably 5 nm to 1,000 nm, more preferably 10 nm to 800 nm, and most preferably 20 nm to 500 nm.

Further, the cured film of the present invention can also function as an insulating film when the insulating property is sufficiently high. In that case, the cured film is arranged directly on the gate electrode and used as a gate insulating film in, for example, an organic FET element. At that time, it is desirable that the film thickness of the cured film is thicker than that when it is used as the above-mentioned underlayer film for image formation for the purpose of ensuring insulating properties. The film thickness is preferably 20 nm to 1,000 nm, more preferably 50 nm to 800 nm, and most preferably 100 nm to 500 nm.

As described above, in the cured film of the present invention, the resin composition according to the present invention has two layers or a concentration gradient of a rich fluorine polymer (component (A)) and a poor fluorine polymer (component (B)). It is coated on a substrate so as to be formed, and this undried coated film is dried by heating to form a cured film for patterning. At this time, rich fluorine polymers, poor fluorine polymers, or rich fluorine are used. Cross-linking occurs between the polymer and the poor fluorine polymer, the cured film for patterning becomes insoluble in the image forming liquid, and the poor fluorine polymer and the rich fluorine polymer are fixed in a state of being unevenly distributed in the thickness direction of the film. Be made. There are circumstances in which it is impossible or approximately impractical to directly identify such a cured film by its structure or properties.

9. Use as a lower layer film for image formation: Method for manufacturing an electrode for image formation For image formation by irradiating the lower layer film for image formation of the present invention with ultraviolet rays in a pattern and then applying an image forming solution described later. Electrodes can be manufactured.

In the present invention, the method of irradiating the lower layer film for image formation in a pattern is not particularly limited, but for example, a method of irradiating through a mask on which an electrode pattern is drawn, an electrode pattern using laser light, etc. There is a method of drawing.
The material and shape of the mask are not particularly limited as long as the region requiring the electrode transmits ultraviolet rays and the other region is opaque to ultraviolet rays.

At this time, ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be generally used for irradiation, and it is desirable to appropriately select the wavelength through a filter or the like. Specific examples thereof include wavelengths such as 248 nm, 254 nm, 303 nm, 313 nm, and 365 nm. Particularly preferably, it is 365 nm.

The surface energy of the image-forming underlayer film of the present invention is gradually increased by irradiation with ultraviolet rays, and is saturated with a sufficient irradiation amount. This increase in surface energy results in a decrease in the contact angle of the image forming liquid, and as a result, the wettability of the image forming liquid in the ultraviolet irradiation portion is improved.

Therefore, when the image forming liquid is applied on the image forming lower layer film of the present invention after irradiation with ultraviolet rays, the image forming liquid self-structures along the pattern shape drawn as the difference in surface energy on the image forming lower layer film. A pattern can be formed to obtain an electrode having an arbitrary pattern shape.

Therefore, it is necessary to irradiate the lower layer film for image formation with an amount that sufficiently changes the contact angle of the image forming liquid, but from the viewpoint of energy efficiency and shortening of the manufacturing process, it is 40 J / cm ² or less. It is preferably 20 J / cm ² or less, and ^{most preferably 10 J / cm 2} or less.

In addition, the larger the difference in the contact angle of the image forming liquid between the ultraviolet-irradiated portion and the unirradiated portion of the image-forming underlayer film, the easier the patterning becomes, and it is possible to process the electrode into a complicated pattern or a fine pattern shape. Become. When a solution having a low surface tension is used, the contact angle difference between the exposed portion and the unexposed portion is preferably 5 ° or more, more preferably 10 ° or more, and most preferably 20 ° or more. However, it is better to optimize it appropriately in consideration of the method of applying the image forming liquid, the surface tension of the image forming liquid, the fineness of the image, and the flatness of the film.
For the same reason, the contact angle of the image forming liquid is preferably 30 ° or more in the ultraviolet-irradiated portion and 20 ° or less in the ultraviolet-irradiated portion.

The image-forming liquid in the present invention is a coating liquid that can be used as a functional thin film by evaporating a solvent contained therein after coating on a substrate. For example, a charge-transporting substance is at least one kind. Examples thereof include those dissolved or uniformly dispersed in a solvent. Here, charge transportability is synonymous with conductivity, and means any of hole transportability, electron transportability, and both hole and electron charge transportability.

The above-mentioned charge-transporting substance is not particularly limited as long as it has conductivity capable of transporting holes or electrons. Examples include metal microparticles such as gold, silver, copper and aluminum, inorganic materials such as carbon black, fullerenes and carbon nanotubes, and organic π-conjugated polymers such as polythiophene, polyaniline, polypyrrole, polyfluorene and derivatives thereof. And so on.
Further, for the purpose of improving the charge transporting ability of the charge transporting substance, halogen, Lewis acid, ammonium acid, and transition metal compounds (specific examples are Br ₂ , I ₂ , Cl ₂ , FeCl ₃ , MoCl ₅ , BF ₄ , AsF _6). , SO ₄ , HNO ₄ , H ₂ SO ₄ , polystyrene sulfonic acid, etc.), or alkali metals, alkylammonium ions (specific examples: Li, Na, K, Cs, tetraethyleneammonium, tetoabutyl) A charge-donating substance such as ammonium) may be further added to the image forming solution as a dopant.

The solvent of the image forming liquid is not particularly limited as long as it dissolves or uniformly disperses the above-mentioned charge-transporting substance or dopant. From the viewpoint of obtaining an accurate electrode image (pattern), the surface tension of the image forming liquid is preferably 25 mN / m to 50 mN / m. If the surface tension is too lower than the above range, it does not show a sufficiently large contact angle with respect to the ultraviolet-irradiated part, and if the surface tension is too high than the above range, the contact angle of the ultraviolet-irradiated part becomes high and the ultraviolet rays are exposed. It is not preferable because the irradiation amount increases.

The solvent of the image forming liquid is not particularly limited, but various organic solvents such as alcohols, ketones, ethers, esters, aromatic hydrocarbons, and glycols can be used. Examples of alcohols include methanol, isopropanol, normal butanol, isobutanol, secondary butanol, isoamyl alcohol, octanol and the like. Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone / diacetone alcohol and the like. Examples of ethers include ether / isopropyl ether, dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve and the like. Examples of the esters include ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, cellosolve acetate, fatty acid methyl ester and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like. Examples of aliphatic hydrocarbons include normal hexane, isohexane, cyclohexane, mineral tarpen, normal pentane and the like. Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether and the like.

In addition, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactum, dimethyl. Polar solvents such as sulfoxide and tetramethylurea are also preferable from the viewpoint of excellent solubility of organic charge-transporting substances, but these are preferably used within a range in which damage to the image-forming lower layer film of the present invention is small. ..
Further, although it is possible to use a solvent having a particularly large surface tension such as water, it is preferable to adjust the surface tension by adding a surfactant or the like.

The concentration of the charge transporting substance in the image forming liquid is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, and most preferably 1 to 5% by mass.

Specific examples of the image forming liquid according to the present invention include a conductive polymer solution such as Baytron (registered trademark) P (polyethylene dioxythiophene, manufactured by Bayer), Dotite XA-9609 (manufactured by Fujikura Kasei), and W4A (Sumitomo). Examples thereof include silver fine particle dispersions such as those manufactured by Denko) and NPS-J (manufactured by Harima Kasei Co., Ltd.).

The electrode according to the present invention is produced by applying the image forming liquid on the image forming lower layer film of the present invention, forming an image, and then evaporating the solvent. The method for evaporating the solvent is not particularly limited, but a uniform film-forming surface is evaporated by using a hot plate or an oven in an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum. It is possible to obtain.

The temperature at which the solvent is evaporated is not particularly limited, but is preferably 40 to 250 ° C. From the viewpoint of maintaining the shape of the underlayer film for image formation and achieving the uniformity of the film thickness, the temperature may be changed in two or more steps.

In the image-forming lower layer film of the present invention, an unreacted photoacid generator and a non-desorbed liquid repellent group remain in the non-image-forming portion. In order to improve the reliability of the underlayer film for image formation, the reaction at the non-image forming portion of the underlayer film for image formation is carried out by applying the image forming liquid and then irradiating with ultraviolet rays, heating, or heating after the irradiation with ultraviolet rays. You may proceed.

The electrodes created from this image forming liquid are used not only as wiring for connecting electronic devices, but also as electrodes of electronic devices such as field effect transistors, bipolar transistors, various diodes, and various sensors.

The electronic device according to the present invention has an electrode made of an image forming liquid formed on the image forming lower layer film of the present invention.
Hereinafter, an example in which the image-forming lower layer film of the present invention is used for an organic FET element will be shown, but the present invention is not limited thereto.

First, a glass substrate having an ITO electrode formed on one side is prepared. It is preferable that the substrate is purified by liquid cleaning with detergent, alcohol, pure water or the like in advance, and surface treatment such as ozone treatment or oxygen-plasma treatment is performed immediately before use. The resin composition for forming a cured film of the present invention is formed on a substrate with an ITO electrode according to the procedure of the above-mentioned [Method for producing a coating film and a cured film]. The film thickness of the layer is most preferably 100 nm to 1000 nm in consideration of the balance between the driving voltage and the electrical insulation property. After that, ultraviolet rays are irradiated in a pattern by using a mask or the like.

Subsequently, an image forming liquid using a low surface tension solvent such as PGME is applied to the surface of the image forming lower layer film. The applied image-forming liquid quickly spreads to the lipophilic part (ultraviolet-irradiated part) so as to repel the liquid-repellent part (ultraviolet-irradiated part), stabilizes, and dries to pattern the source and drain electrodes. Is formed. The method for applying the image forming liquid is not particularly limited, such as a spin coating method and a casting method, but an inkjet printing method or a spray coating method in which the amount of the liquid can be easily controlled is preferable.

Finally, it is completed by forming an organic semiconductor material such as pentacene or polythiophene, which is an active layer of an organic FET. The method for forming an organic semiconductor material is not particularly limited, and examples thereof include a vacuum deposition method, a spin coating method for a solution, an inkjet printing method, and a spray coating method.

The organic FET produced in this way can significantly reduce the manufacturing process, and further, since an organic FET having a shorter channel than the mask vapor deposition method can be produced, an organic FET having low mobility as an active layer can be produced. Even when a semiconductor material is used, a large current can be taken out.

Hereinafter, the present embodiment will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Composition components used in Examples and their abbreviations]
The compositional components used in the following examples and comparative examples are as follows. The method for synthesizing FMAA and CL1 will be described later.

<Specific polymer raw material>
HPMA: 4-Hydroxyphenylmethacrylate HEMA: 2-Hydroxyethyl methacrylate EPEGA: Poly (ethylene glycol) methacrylate Average M _n 360 (manufactured by SIGMA-ALDRICH)
GLM: Glycerin monomethacrylate BMAA: N-butoxymethylacrylamide MOI-BP: 2-[(3,5-dimethylpyrazolyl) carbonylamino] Ethyl methacrylate AIBN: α, α'-azobisisobutyronitrile

<Other polymers>
HPC-SSL: Hydroxypropyl Cellulose (manufactured by Nippon Soda)

F9MAA: Compound represented by the following formula (A1)

F7MAA: Compound represented by the following formula (A2)

F13MAA: Compound represented by the following formula (A3)

<Crossing agent raw material>
Calends MOI-DEM (manufactured by Showa Denko KK): Compound represented by the following formula (D1)

＜架橋剤＞
ＣＬ１：下記式化（Ｄ２）で示される化合物

<Crosslinking agent>
CL1: Compound represented by the following formula (D2)

<Photoacid generator>
As the photoacid generator, Irgacure PAG103 (manufactured by BASF) represented by the formula (C1) and Irgacure PAG121 (manufactured by BASF) represented by the formula (C2) were used.

<Solvent>
Each of the cured film-forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM-P) and propylene glycol monomethyl ether acetate (PMA-P) were used as the solvent.

[Measurement of molecular weight of polymer]
The molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation as an apparatus and Shodex® KF-804L and 803L as columns under the following conditions.
Column oven: 40 ° C
Flow rate: 1 ml / min Eluent: tetrahydrofuran

<Synthesis example 1>
Synthesis of compound F9MAA represented by the formula (A1)

N-Hydroxymethylacrylamide [1] (10.0 g, 98.91 mmоl), 3,3,4,5,5,6,6,6-nonafluorohexane-1-ol in a 200 ml three-necked flask [2] (13.1 g, 49.46 mmоl), phosphoric acid (0.24 g, 2.47 mmоl), 2,6-di-terriary-butyl-4-methylphenol (0.11 g, 0.49 mmоl) Hexane (54.6 g) was added, and the mixture was stirred at 50 ° C. for 20 hours. After confirming the progress of the reaction by HPLC, hexane (300 g) was added to the obtained solution, and the mixture was washed 3 times with ion-exchanged water (100 g) using a separating funnel. Then, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (100 g) and concentrated with an evaporator to obtain 8.38 g of compound [3].

<Synthesis example 2>
Synthesis of compound F7MAA represented by the formula (A2)

N-Hydroxymethylacrylamide [1] (10.0 g, 98.91 mmоl), 2,2,3,3,4,5,4-heptafluoro-1-butanol [2] (9) in a 200 ml three-necked flask. .89 g, 49.46 mmоl), phosphoric acid (0.24 g, 2.47 mmоl), 2,6-di-terriary-butyl-4-methylphenol (0.11 g, 0.49 mmоl) and tetrahydrofuran (54.6 g) ) Was added, and the mixture was stirred at 50 ° C. for 20 hours. After confirming the progress of the reaction by HPLC, hexane (300 g) was added to the obtained solution, and the mixture was washed 3 times with ion-exchanged water (100 g) using a separating funnel. Then, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (100 g) and concentrated with an evaporator to obtain 6.83 g of compound [3].

<Synthesis example 3>
Synthesis of compound F13MAA represented by the formula (A3)

N-Hydroxymethylacrylamide [1] (10.0 g, 98.91 mmоl), 2- (perfluorohexyl) ethanol [2] (18.0 g, 49.46 mmоl), phosphoric acid (0. 24 g (2.47 mmоl), 2,6-di-terriary-butyl-4-methylphenol (0.11 g, 0.49 mmоl) and tetrahydrofuran (54.6 g) were added, and the mixture was stirred at 50 ° C. for 20 hours. .. After confirming the progress of the reaction by HPLC, hexane (300 g) was added to the obtained solution, and the mixture was washed 3 times with ion-exchanged water (100 g) using a separating funnel. Then, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (100 g) and concentrated with an evaporator to obtain 10.8 g of compound [3].

<Synthesis example 4>
Synthesis of compound CL1 represented by the formula (D2)

窒素雰囲気中、脱水塩化メチレン３９３ｍｌ、メルドラム酸３３．４ｇ（２３．２ｍｍоｌ）、及びＮ，Ｎ−ジメチル−４−アミノピリジン３６．７ｇ（３０．０ｍоｌ）を０℃にて仕込み、セバコイルクロリド２７．７ｇ（１１．６ｍоｌ）を６０ｍｌの脱水塩化メチレンに溶解させた溶液を滴下した。滴下終了後、徐々に温度を上げ室温で２０時間攪拌を行った。その後２規定塩酸７０ｍｌと水２０ｍｌの混合溶液で水洗を１回行った。得られた有機層を２規定塩酸２５ｍｌと水２００ｍｌの混合溶液で水洗を１回行い、有機層を硫酸マグネシウム１０ｇで乾燥した。その後、ろ過により硫酸マグネシウムを除去し、得られたろ液を濃縮して得た粗物をアセトン１１２ｇで加熱溶解させ、その後冷却して析出した結晶を乾燥させて薄黄色固体のＣＬ１を得た（２１．９ｇ（４．８１ｍоｌ）、収率４１．５％）。この化合物の構造は^１Ｈ−ＮＭＲ分析により以下のスペクトルデータを得て確認した。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ３．０６（ｔ，４Ｈ），１．７４−１．６６（ｍ，１６Ｈ），１．４３−１．３４（ｍ，８Ｈ）．

In a nitrogen atmosphere, 393 ml of dehydrated methylene chloride, 33.4 g (23.2 mmоl) of meldrum's acid, and 36.7 g (30.0 mL) of N, N-dimethyl-4-aminopyridine were charged at 0 ° C., and sebacoil chloride 27 was charged. A solution prepared by dissolving 7 g (11.6 mol) in 60 ml of dehydrated methylene chloride was added dropwise. After completion of the dropping, the temperature was gradually raised and stirring was performed at room temperature for 20 hours. After that, it was washed once with a mixed solution of 70 ml of 2N hydrochloric acid and 20 ml of water. The obtained organic layer was washed once with a mixed solution of 25 ml of 2N hydrochloric acid and 200 ml of water, and the organic layer was dried over 10 g of magnesium sulfate. Then, magnesium sulfate was removed by filtration, the obtained filtrate was concentrated and the obtained crude product was dissolved by heating with 112 g of acetone, and then cooled to dry the precipitated crystals to obtain CL1 as a pale yellow solid (CL1). 21.9 g (4.81 mL), yield 41.5%). The structure of this compound was ^{confirmed by 1} H-NMR analysis by obtaining the following spectral data. ^{1 1} H-NMR (CDCl ₃ ): δ3.06 (t, 4H), 1.74-1.66 (m, 16H), 1.43-1.34 (m, 8H).

<Polymerization example 1>
P1: F9MAA / HEMA 56/44
Acrylic copolymer solution (solid content concentration 10% by mass) was obtained by dissolving 2.56 g of F9MAA, 2.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 41.2 g of PMA-P and reacting at 80 ° C. for 20 hours. ) (P1) was obtained. The obtained acrylic copolymer had Mn of 5,872 and Mw of 8,555.

<Polymerization example 2>
P2: BMAA / HEMA 80/20
BMAA 8.0 g, HEMA 2.0 g, and AIBN 0.3 g as a polymerization catalyst were dissolved in PM-P 41.2 g and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 20% by mass). ) (P2) was obtained. The obtained acrylic copolymer had Mn of 3,789 and Mw of 7,514.

<Polymerization example 3>
P3: F9MAA / HPMA / HEMA 18/55/27
Acrylic copolymer solution (solid) by dissolving 1.28 g of F9MAA, 4.0 g of HPMA, 2.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 41.2 g of PMA-P and reacting at 80 ° C. for 20 hours. Mineral concentration 15% by mass) (P3) was obtained. The obtained acrylic copolymer had Mn of 7,020 and Mw of 7,971.

<Polymerization example 4>
P4: BMAA / HPMA / HEMA 40/40/20
An acrylic copolymer solution (solid content concentration) is obtained by dissolving 4.0 g of BMAA, 4.0 g of HPMA, 2.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 41.2 g of PM and reacting at 80 ° C. for 20 hours. 20% by mass) (P4) was obtained. The obtained acrylic copolymer had Mn of 10,103 and Mw of 25,498.

<Polymerization example 5>
P5: MOI-DEM 100
Karenz MOI-DEM (manufactured by Showa Denko) 10.0 g, AIBN 0.3 g as a polymerization catalyst is dissolved in PM 41.2 g, and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration 20). Mass%) (P5) was obtained. The obtained acrylic copolymer had Mn of 17,279 and Mw of 54,273.

<Polymerization example 6>
P6: F9MAA / PEGMA 56/44
Acrylic copolymer solution by dissolving 2.56 g of F9MAA, 2.0 g of PEGMA and 0.3 g of AIBN as a polymerization catalyst in 12.2 g of PM-P and 12.2 g of PMA-P and reacting at 80 ° C. for 20 hours. (Solid content concentration 20% by mass) (P6) was obtained. The obtained acrylic copolymer had Mn of 22,262 and Mw of 50,083.

<Polymerization example 7>
P7: F9MAA / GLM 56/44
Acrylic copolymer solution by dissolving 2.56 g of F9MAA, 2.0 g of GLM and 0.3 g of AIBN as a polymerization catalyst in 12.2 g of PM-P and 12.2 g of PMA-P and reacting at 80 ° C. for 20 hours. (Solid content concentration 20% by mass) (P7) was obtained. The obtained acrylic copolymer had Mn of 23,029 and Mw of 51,421.

<Polymerization Example 8>
P8: F7MAA / HEMA 56/44
Acrylic copolymer solution by dissolving 2.56 g of F7MAA, 2.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 12.2 g of PM-P and 12.2 g of PMA-P and reacting at 80 ° C. for 20 hours. (Solid content concentration 20% by mass) (P8) was obtained. The obtained acrylic copolymer had Mn of 14,352 and Mw of 28,460.

<Polymerization example 9>
P9: F13MAA / HEMA 56/44
Acrylic copolymer solution by dissolving 2.56 g of F13MAA, 2.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 12.2 g of PM-P and 12.2 g of PMA-P and reacting at 80 ° C. for 20 hours. (Solid content concentration 20% by mass) (P9) was obtained. The obtained acrylic copolymer had Mn of 12,074 and Mw of 19,702.

<Polymerization Example 10>
P10: F9MAA / MOI-BP / HEMA 40/40/20
Dissolve 4.0 g of F9MAA, 4.0 g of MOI-BP, 2.0 g of HEMA, and 0.5 g of AIBN as a polymerization catalyst in 20.6 g of PM-P and 20.6 g of PMA-P, and react at 80 ° C. for 20 hours. As a result, an acrylic copolymer solution (solid content concentration: 20% by mass) (P10) was obtained. The obtained acrylic copolymer had Mn of 14,475 and Mw of 43,907.

<Polymerization Example 11>
P11: BMAA / MOI-BP / HEMA 40/40/20
An acrylic copolymer solution by dissolving 4.0 g of BMAA, 4.0 g of MOI-BP, 4.0 g of HEMA, and 0.7 g of AIBN as a polymerization catalyst in 41.2 g of PM-P and reacting at 80 ° C. for 20 hours. (Solid content concentration 20% by mass) (P11) was obtained. The obtained acrylic copolymer had Mn of 20,277 and Mw of 133,030.

[Preparation of cured film forming composition]
The cured film-forming compositions of Examples and Comparative Examples were prepared according to the compositions shown in Table 1. However, the solid content concentration of each composition was 5% by weight. Next, each cured film forming composition was used to form a cured film, and the contact angle of each of the obtained cured films was measured and the solvent resistance to n-nоnone and PMA-P was evaluated. The composition ratio in Table 1 represents the ratio in terms of solid content.

[Solvent resistance evaluation]
Each of the cured film-forming compositions of Examples and Comparative Examples was rotationally coated on a silicon wafer at 850 rpm for 30 seconds using a spin coater, and then heat-dried on a hot plate at a temperature of 140 ° C. for 120 seconds to obtain a film thickness of 200 nm. A coating film was formed. The film thickness was measured using F20 manufactured by FILMETRIS. This coating film was divided into two regions, and one region was irradiated with ultraviolet rays having a light intensity of 100 mJ / cm ² at 365 nm for a certain period of time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., perpendicularly to the coating film surface. (Hereinafter, this region is referred to as an "exposed portion", and the other region is referred to as an "unexposed portion"). Then, post-baking was performed on a hot plate at 120 ° C. for 120 seconds. The unexposed and exposed parts of the obtained cured film were separately immersed in PMA-P for 1 minute to measure the film thickness before and after immersion, and the residual film ratio was calculated to evaluate the solvent resistance.

[Result of evaluation]
The results of the above evaluation are shown in Table 2 as described above.

Examples 1 to 15 and Comparative Examples 1 to 2 all showed high solvent resistance to n-nonane. Further, Examples 1 to 6, Examples 8 to 14, Comparative Example 1 to Comparative Example 2 in which the cross-linking agent of the component (D) was added, and Example 15 in which the cross-linking monomer was used as the component (A). Also showed high solvent resistance to PMA-P.
In addition, Examples 1 to 15 showed particularly excellent solvent resistance in the exposed portion due to the cross-linking effect of (liquid-repellent group). On the other hand, in Comparative Example 2, no difference in solvent resistance was observed between the exposed portion and the unexposed portion, and the solvent resistance of the exposed portion with respect to PMA-P was inferior to that of Examples 1 to 15.

[Contact angle measurement]
After each of the cured film forming compositions of Examples and Comparative Examples was applied onto a silicon wafer using a spin coater, it was heated and dried on a hot plate at a temperature of 140 ° C. for 120 seconds to form a coating film having a film thickness of 200 nm. did. The film thickness was measured using F20 manufactured by FILMETRIS. This coating film was divided into two regions, and one region was irradiated with ultraviolet rays having a light intensity of 100 mJ / cm ² at 365 nm for a certain period of time by the ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., perpendicularly to the coating film surface. .. Next, post-baking was performed on a hot plate at 120 ° C. for 120 seconds, and the contact angle between the unexposed portion and the exposed portion of the obtained coating film was measured (hereinafter, this region is referred to as the “exposed portion” and other regions. Is referred to as an "unexposed portion"). The contact angle was measured using a fully automatic contact angle meter CA-W (manufactured by Kyowa Interface Science Co., Ltd.) in a constant temperature and humidity environment (25 ° C ± 2 ° C, 50% RH ± 5%). The contact angles of PMA-P and n-nоnone were measured after resting for 5 seconds after landing.

[Result of evaluation]
The results of the above evaluation are shown in Table 3 as described above.

In each of Examples 1 to 15, there was a large difference in contact angle between the unexposed portion and the exposed portion with respect to n-nonane. In particular, in Examples 1 to 6 and 8 to 15 in which a cross-linking agent was used, a large contact angle difference was shown between the unexposed portion and the exposed portion with respect to PMA-P.
On the other hand, in Comparative Examples 1 and 2, no difference in contact angle was observed between the exposed portion and the unexposed portion.

As described above, the cured film obtained from the cured film-forming composition of the present invention exhibits excellent performance in both solvent resistance and liquid-repellent contrast, and various types such as n-nonane and PMA-P are exhibited. It was possible to exert an effect on various organic solvents.

Claims (13)

As the component (A), a polymer containing a structural unit derived from the first monomer having the structure of the following formula (1), and
As the component (B), a polymer other than the component (A) having a fluorine content lower than that of the component (A) based on the total weight of the polymer.
As a component (C), a photoacid generator and
A resin composition for forming a cured film, which comprises a solvent.

(In the formula, R ¹ represents a hydrogen or methyl group and represents
R ² represents a fluorine-containing group that can be eliminated with the oxygen atom to which it is attached. ) R ² is, may be branched and / or cyclization, aromatic ring, -O -, - S -, - CO -, - CS -, - NH-, or may be interrupted by combinations thereof The resin composition for forming a cured film according to claim 1, which represents a hydrocarbon group substituted with fluorine. Number of carbon atoms of R ² is 2 or more, the cured film-forming resin composition according to claim 1 or 2. The polymer of the component (A) is at least one selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the following formula (2). The resin composition for forming a cured film according to any one of claims 1 to 3, further containing a structural unit derived from a second monomer having a group (group (x)).

(In the formula, R ³ represents an alkyl group, an alkoxy group, or a phenyl group.) The polymer of the component (B) is at least one selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an alkoxysilyl group, an isocyanate group, a blocked isocyanate group, and a group represented by the following formula (2). The resin composition for forming a cured film according to any one of claims 1 to 4, which contains a structural unit derived from a monomer having a group (group (x)).

(In the formula, R ³ represents an alkyl group, an alkoxy group, or a phenyl group.) The resin composition for forming a cured film according to claim 4 or 5, further containing a compound having two or more groups capable of thermally reacting with the group (x) as a component (D). The resin composition for forming a cured film according to any one of claims 1 to 6, wherein the fluorine content of the component (A) in the polymer is 5% by weight or more based on the total weight of the polymer. The resin composition for forming a cured film according to any one of claims 1 to 7, wherein the fluorine content of the component (B) in the polymer is less than 5% by weight based on the total weight of the polymer. A cured film obtained by using the resin composition for forming a cured film according to any one of claims 1 to 8, wherein the ultraviolet-exposed portion is liquefied from the unexposed portion. The cured film according to claim 9, wherein the difference in contact angle between the ultraviolet exposed portion and the unexposed portion with respect to propylene glycol monomethyl ether acetate is 5 ° or more. A wiring forming auxiliary layer made of the cured film of claim 9 or 10. Use of the resin composition for forming a cured film according to any one of claims 1 to 8, for producing a cured film in which the ultraviolet exposed portion is liquefied from the unexposed portion. The use according to claim 12, wherein the difference in contact angle between the ultraviolet exposed portion and the unexposed portion with respect to propylene glycol monomethyl ether acetate is 5 ° or more.