JP2011053266A - Top coat composition for liquid repellent-lyophilic patterning - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a top coat composition of high liquid repellent property enabling high definition display by an application process. <P>SOLUTION: The top coat composition for liquid repellent-lyophilic patterns is prepared by solving fluorine polymer (A) containing at least 70 wt.% or more of α position substitution acrylate having 1-6C fluoroalkyl group, wherein an α position substitution group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX<SP>1</SP>X<SP>2</SP>group (where, X<SP>1</SP>and X<SP>2</SP>are independently a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, a 1-20C direct chain or branched fluoroalkyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group or a 2-20C direct chain or branched alkyl group, in a solvent (B), and can form the liquid repellent-lyophilic patterns having a liquid repellent region of a PGMEA contact angle of 70 degrees or more. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a top coat composition for liquid repellent-lyophilic patterning and a method for forming a liquid repellent-lyophilic pattern using the composition.

  In order to manufacture devices such as display pixels and biochips using a coating process typified by inkjet technology, it is necessary to pattern the substrate in advance on the lyophobic and lyophilic areas on the μm scale by photolithography. is there. In order to form a lyophilic-liquid repellent pattern on a substrate, a (meth) acrylate polymer containing a fluoroalkyl group having 4 to 6 carbon atoms (hereinafter abbreviated as Rf group) in a normal resist composition is used as a liquid repellent. Is disclosed in Patent Document 1. However, this Rf group-containing (meth) acrylate structure has a problem that sufficient liquid repellency cannot be imparted to the liquid repellency region. In order to solve this problem, the inventors have developed a special acrylate polymer containing an Rf group having 6 or less carbon atoms, and in which the α-position of normal (meth) acrylate is substituted with a bulky functional group such as a chlorine atom. A method for internally adding coalescence was invented (Patent Document 2).

  However, in the method of internally adding a liquid repellent to the resist composition, the liquid repellent area has insufficient liquid repellency, which is a cause of narrowing the application range of device fabrication by the coating process. In the internal addition method, the contact angle with propylene glycol methyl ether acetate (hereinafter abbreviated as PGMEA), which is widely used as an ink solvent, is 60 ° or less, and pixel formation by the inkjet process is a large display with roughly 40 pixels or more with coarse pixels. It was applicable only to.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2000-180841) discloses that in Example 1, a chromium film is sputtered onto a glass substrate and a positive resist is applied thereon to a film thickness of 6 μm. An ink-repellent treating agent obtained by diluting a acrylate homopolymer containing 0.1% by weight with perfluoro (2-butyltetrahydrofuran) is applied onto a positive resist film by spin coating to prepare a two-layer film. A method of forming a black matrix having a thickness of 6 μm is disclosed. Patent Document 3 is a method in which a black matrix that is much taller than the normal height (1-2 μm) is used as a substrate gap control spacer with a liquid repellent bank function. Although the fluoropolymer described in Patent Document 3 does not have good liquid repellency, pixels can be formed by an inkjet method because the black matrix is tall. However, it has been difficult to form good pixels with a normal height black matrix.

If even higher liquid repellency can be realized, for example, pixels for high-definition displays such as 32-inch televisions, mobile personal computers, and mobile phones can be formed by the inkjet process.

  In Patent Document 4 (Japanese Patent Laid-Open No. 2007-264459), the liquid is filled between the lens on the light source side and the photoresist layer (that is, a liquid for immersion exposure, usually pure water is used), and the resolution is And a solvent-soluble topcoat composition used in a method for improving the depth of focus (so-called immersion lithography). This invention uses in part a material similar to the present invention. However, in Patent Document 4, in order to carry out microfabrication on the scale of several tens of nanometers for semiconductor applications, the photoresist layer is protected from the water of the immersion exposure liquid with a solvent-soluble topcoat layer, and further for immersion exposure. The object is to improve the followability of water to the lens. Therefore, Patent Document 4 does not suggest that the substrate, which is the object of the present invention, is patterned into a lyophobic region and a lyophilic region on a μm scale by a photolithography method. Patent Document 4 is intended to improve water repellency, while the present invention is also greatly different in that it aims to improve liquid repellency represented by PGMEA.

JP2005-315984 WO / 2006/129800 JP2000-180841 JP2007-264459

  In view of the above situation, an object of the present invention is to provide a topcoat composition having a lyophobic-lyophilic pattern having a lyophobic region having a contact angle with respect to PGMEA of 70 ° or more, and a lyophobic-lyophilic using the composition. It is to realize a liquid pattern forming method.

  In the present invention, a “topcoat composition prepared by dissolving a specific fluorine-based polymer in a fluorine-based solvent” is coated on a “regular resist film” in two layers, whereby a repellent property with a PGMEA contact angle of 70 ° or more is obtained. Forming a lyophobic-lyophilic pattern having a liquid region. Thereby, the pixel formation by the coating process can be developed to a display with higher definition than before.

The present invention
(A) α-substituted acrylate having a fluoroalkyl group having 1 to 6 carbon atoms
[However, the substituent at the α-position is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, A linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 2 to 20 carbon atoms. . ]
There is provided a topcoat composition for liquid repellent-lyophilic patterning, comprising a fluorine-containing polymer containing at least 70% by weight and (B) a solvent.

The present invention also provides a method for producing a lyophobic-lyophilic pattern by patterning a two-layer film obtained by coating a topcoat composition on a photosensitive coating film by a photolithography method. .
In the present invention, a two-layer film obtained by further coating a two-layer topcoat composition on a photosensitive resin layer uniformly formed on a substrate was repelled in a pattern by a photolithography method. A method of manufacturing a color filter for display or a light emitting substrate, characterized by forming a bank, is also provided.

According to the present invention, a liquid repellent bank having a contact angle of 70 ° or more with respect to propylene glycol methyl ether acetate produced by a photolithography method using a top coat composition for liquid repellent-lyophilic patterning is obtained.
According to the present invention, formed on a transparent substrate,
(I) a layer of a liquid repellent-lyophilic patterning topcoat composition, and (ii) a two-layer film comprising a photosensitive resin layer.

  The topcoat composition and the liquid repellent-lyophilic pattern forming method of the present invention have the above-described configuration, so that a liquid repellent-lyophilic pattern having a liquid repellent region with a PGMEA contact angle of 70 ° or more is formed. it can.

FIG. 1 is a result of comparison of contact angles of PGMEA with a fluorine-containing polymer-added resist thin film and a resist / topcoat bilayer thin film.

  The present invention is described in detail below.

● Fluoromonomer (a) used for production of fluoropolymer (A)
The fluorine-based monomer (a) for producing the fluorine-based polymer (A), which is a constituent component of the topcoat composition of the present invention, is an α-substituted acrylate having a C 1-6 fluoroalkyl group. The number of carbon atoms of the fluoroalkyl group is preferably 4-6. The α-position substituent is fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom), cyano group, carbon number 1 A -20 linear or branched fluoroalkyl group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 2 to 20 carbon atoms.

［式中、Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、あるいは炭素数２〜２０の直鎖状または分岐状アルキル基。
Ｙは、直接結合、酸素原子を有していてもよい炭素数１〜１０の脂肪族基、酸素原子を有していてもよい炭素数６〜１０の芳香族基、環状脂肪族基または芳香脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）、−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、または、-(CH₂)_nSO₂-基（nは1〜10）である。
Ｒｆは炭素数１〜６の直鎖状または分岐状のフルオロアルキル基である。］
であることが好ましい。 α-substituted acrylate is
formula:

[Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom) ), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 2 to 20 carbon atoms or Branched alkyl group.
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms), a —CH ₂ CH (OY ¹ ) CH ₂ — group ( However, Y ¹ is a hydrogen atom or an acetyl group), or, -. a group (n is _{1~10) - (CH 2) n} SO 2.
Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. ]
It is preferable that

  Rf is preferably a C 1-6 perfluoroalkyl group, particularly a C 4-6 perfluoroalkyl group.

Examples of the α-substituted acrylate are as follows.

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S−Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) ₂ −Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
[Wherein, Rf represents a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. ]

The fluorine-based monomer (a) used in the production of the fluorine-based polymer (A) may be polymerized with a homopolymer using only the above-mentioned α-substituted acrylate, or may be copolymerized with the comonomer (b) to be alkali-soluble. May be improved.
The comonomer (b) is preferably alkali-soluble, such as methacrylic acid. The comonomer (b) generally does not contain a fluorine atom.

  Examples of comonomers (b) are (b1) unsaturated organic acids and (b2) high softening point monomers.

  The unsaturated organic acid (b1) is a monomer having at least one carbon-carbon double bond and at least one acid group [eg, carboxyl group (COOH group)], and the acid value of the fluoropolymer (A). Is copolymerized so as to be 40 to 200 mg KOH / g. The acid value is defined in JIS 0070. 2.1 and refers to the number of mg of potassium hydroxide required to neutralize free fatty acid, resin acid, etc. contained in 1 g of a sample. Particularly preferred examples of unsaturated organic acids are unsaturated carboxylic acids, such as free unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. Examples of unsaturated organic acids (b1) are (meth) acrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, phthalic anhydride, tetrahydrophthalic anhydride and silicic acid. Cinnamic acid. The unsaturated organic acid (b1) imparts crosslinkability with a crosslinking agent in the electromagnetic wave irradiation region and solubility with an alkali developer in the electromagnetic wave non-irradiation region to the fluoropolymer (A).

The high softening point monomer (b2) is generally
A monomer having a glass transition point or melting point of 100 ° C. or higher, particularly 120 ° C. or higher in a homopolymer state.
The high softening point monomer (b2)
CH ₂ = C (R ¹ ) COOR ²
[R ¹ is H or CH ₃ , R ² : a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more. ]
It is preferable that Examples of R ² are isobornyl, bornyl, phensil (all of which are C ₁₀ H ₁₇ , carbon atom / hydrogen atom = 0.58), adamantyl (C ₁₀ H ₁₅ , carbon atom / hydrogen atom = 0.66), Examples thereof include bridged hydrocarbon rings such as norbornyl (C ₇ H ₁₂ , carbon atom / hydrogen atom = 0.58). These crosslinked hydrocarbon rings may have a hydroxyl group or an alkyl group (carbon number, for example, 1 to 5).

  Examples of the high softening point monomer (b2) are methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, and adamantyl (meth) acrylate. Examples of norbornyl (meth) acrylate are 3-methyl-norbornylmethyl (meth) acrylate, norbornylmethyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3-trimethyl-norbornyl (meth) acrylate , Miltanylmethyl (meth) acrylate, isopinocamphanyl (meth) acrylate, 2-{[5- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] norbornyl } (Meth) acrylate. Examples of adamantyl (meth) acrylate are 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 1-adamantyl-α -Trifluoromethyl (meth) acrylate.

  The weight ratio of the fluorine-based monomer (a) / comonomer (b) is in the range of 100/0 to 70/30, particularly 99.5 / 0.5 to 85/15.

Production of Fluoropolymer (A) The fluoropolymer (A) can be produced as follows. A method in which the monomer and necessary components are dissolved in a solvent, and after substitution with nitrogen, a polymerization catalyst is added and the mixture is stirred in the range of 20 to 120 ° C. for 1 to 20 hours is employed.

  As the solvent used for the polymerization, an organic solvent, a water-soluble organic solvent, water or the like can be used. Hydrofluoroether may be used because the solubility of the fluoropolymer after polymerization and the environmental load are small. The solvent is used in the polymerization composition in the range of 10 to 90% by weight.

  Chain transfer agents such as mercaptans and alkyl halides may be added to adjust the molecular weight of the fluoropolymer. As mercaptans, n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, isooctyl mercaptoate, thioglycolic acid, 3-mercaptopropionic acid , Methoxybutyl thioglycolate, silicone mercaptan (KF-2001 manufactured by Shin-Etsu Chemical Co., Ltd.), and alkyl halides include chloroform, carbon tetrachloride, carbon tetrabromide and the like. These may be used alone or in combination of two or more.

  The fluoropolymer after polymerization may be used as a topcoat composition as it is when the solvent for topcoat composition (B) described below is used as the polymerization solvent, and in order to remove unreacted monomers, You may refine | purify by mixing. As the poor solvent, hexane, methanol, ethanol or the like is used. Alternatively, the polymerization solvent may be distilled off using a rotary evaporator or the like.

  The weight average molecular weight of the fluoropolymer is 3,000 to 500,000, preferably 10,000 to 200,000. The weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (in terms of standard polystyrene). When the fluorine-based polymer does not dissolve in tetrahydrofuran, which is widely used as a solvent for GPC, the molecular weight may be measured with a polymer obtained by copolymerizing 5% by weight of methacrylic acid for convenience.

● Manufacture of Topcoat Composition The topcoat composition is preferably a concentration of 0.01 to 5% by weight, particularly 0.02 to 0.5% by weight of the above-mentioned fluoropolymer (A) in the solvent (B). Dissolve and prepare. When the content is 0.01 to 5% by weight, sufficient liquid repellency is exhibited and development is clear.

As the solvent (B), a solvent that dissolves the fluorine-based polymer (A) and does not dissolve the underlying resist film is selected, and a fluorine-based solvent is usually used.
The solvent (B) is preferably a hydrofluoroether. Hydrofluoroethers have the formula:
_{C n F 2n + 1 -O-} C x H 2x + 1 (1)
[Wherein, n is a number from 1 to 6, and x is a number from 1 to 6. ]
It is preferable that it is a compound shown by these.
Hydrofluoroether (hereinafter abbreviated as HFE) is preferable in that it has good solubility of the fluorine-based polymer and does not give a burden to the environment. Novec HFE7100 (Chemical Formula C ₄ F ₉ OCH ₃ ), 7200 (Chemical Formula C) of 3M USA ₄ F ₉ OC ₂ H ₅ ), 7300 (Chemical Formula C ₆ F ₁₃ OCH ₃ ), 7500 (Chemical Formula C ₃ HF ₆ —CH (CH ₃ ) OC ₃ HF ₆ ) and the like are used, and HFE 7100 is particularly preferable.

In order to improve the solubility of the fluoropolymer, the solvent (B) may also contain a non-fluorine solvent.
Examples of non-fluorinated solvents are alcohols such as isopropyl alcohol (hereinafter abbreviated as IPA), ketones such as acetone, ethers such as diethyl ether, and the like.

  The mixing weight ratio of the fluorinated solvent (for example, HFE) and the non-fluorinated solvent is preferably 100/0 to 90/10, particularly preferably 100/0 to 98/2. In the case of 100/0 to 90/10, the water repellent bank is satisfactorily formed without dissolution of the lower layer. In the mixture of the fluorinated solvent and the non-fluorinated solvent, the mixing weight ratio of the fluorinated solvent (for example, HFE) and the non-fluorinated solvent may be 99.9 / 0.1 to 90/10. When the non-fluorinated solvent is IPA, the mixing weight ratio of HFE / IPA is preferably in the range of 100/0 to 95/5, particularly preferably in the range of 100/0 to 99/1.

If necessary, an antifoaming agent, a light-absorbing agent, a storage stabilizer, a preservative, an adhesion assistant, a photoacid generator, and the like may be added to the topcoat composition.

-Resist composition used for lower layer It will not be specifically limited if it is a resist composition which can form the pattern of nm-micrometer scale, Negative type or positive type may be sufficient. For example,
"Polymer advanced material One Point 10 resist material" (author Hiroshi Ito), Kyoritsu Publishing Co., Ltd. (2005)
If it is the resist composition of description, it will not specifically limit.
The negative resist composition will be described below.

  The negative resist composition is composed of a photo-crosslinking catalyst, a solvent, a cross-linking agent, an alkali-soluble polymer, etc., which are coated on a substrate to form a photosensitive coating film and irradiated with electromagnetic waves through a photomask. As a result, only the irradiated region is cured and insolubilized in the alkali developer, and thus a pattern is formed by developing with the alkali developer.

-Photocrosslinking catalyst A radical photopolymerization initiator or a photoacid generator is used for the photocrosslinking catalyst.

The radical photopolymerization initiator is a compound that generates radicals by light. As a commercial product of radical photopolymerization initiator,
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one,
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone,
IRGACURE 2959: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one,
IRGACURE 127: 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one,
IRGACURE 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one,
IRGACURE 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
IRGACURE 379: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone,
IRGACURE 819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
IRGACURE 784: bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium,
IRGACURE OXE 01: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)],
IRGACURE OXE 02: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime),
IRGACURE261, IRGACURE369, IRGACURE500,
DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043,
IRGACURE 754 Oxyphenylacetic acid: a mixture of 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester,
IRGACURE 500: IRGACURE 184: Benzophenone = 1: 1 mixture,
IRGACURE 1300: IRGACURE 369: IRGACURE 651 = 3: 7 mixture,
IRGACURE 1800: mixture of CGI403: IRGACURE 184 = 1: 3,
IRGACURE 1870: A mixture of CGI403: IRGACURE 184 = 7: 3,
DAROCUR 4265: DAROCUR TPO: DAROCUR 1173 = 1: 1 mixture
Etc. are exemplified. Here, IRGACURE is made by Ciba and DAROCUR is made by Merck Japan.

  In addition, diethylthioxanthone and isopropylthioxanthone are used as sensitizers, and DAROCUR EDB (ethyl-4-dimethylaminobenzoate) and DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate) are used in combination as polymerization accelerators. Also good.

  A photoacid generator (PAG) is a material that generates acid by reacting with light. PAG consists of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. By irradiating light of a specific wavelength to a PAG with such a structure, the PAG is excited and the acid precursor part Generates acid. As commercial products of PAG, WPAG-145 [Bis (cyclohexylsulfonyl) diazomethane], WPAG-170 [Bis (t-butylsulfonyl) diazomethane], WPAG-199 [Bis (p-toluenesulfonyl) diazomethane], WPAG- 281 [Triphenylsulfonium trifluoromethanesulfonate], WPAG-336 [Diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate], WPAG-367 [Diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate], Ciba IRGACURE PAG103 [(5-propylsulfonyloxyimino-5H-thiophene) -2-ylidene)-(2-methylphenyl) acetonitrile], IRGACURE PAG108 [(5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile)], IRGACURE PAG121 [(5-p-toluenesulfonyloxyimino- 5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], IRGACURE PAG203, CGI725, Sanwa Chemical TFE-triazine [2- [2- (Furan-2-yl) ethenyl] -4,6- bis (trichloromethyl) -s-triazine], TME-triazine [2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine] MP-triazine [2- (Methoxyph enyl) -4,6-bis (trichloromethyl) -s-triazine], dimethoxytriazine [2- [2- (3,4-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine] Can be used.

Solvent The solvent is a water-soluble organic solvent, an organic solvent, water, etc. Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate ( PGMEA), dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butylene glycol Diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, cellosolve acetate, Tilcellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol, etc., as organic solvents, chloroform, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran 1,4-dioxane, methyl isobutyl ketone, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. It is done. These solvents may be used alone or in combination of two or more.

・ Crosslinking agent
The crosslinking agent is a monofunctional or preferably a compound having two or more functional groups, preferably a type that is cured by radical polymerization reaction, and may be a type that is cured by cationic polymerization reaction. The former is an unsaturated double bond group acryloyl group or vinyl group is a functional group, the latter is an epoxy group, vinyl ether group, oxetane group is a functional group,
(a) Urethane (meth) acrylate
(b) Epoxy (meth) acrylate
(c) Polyester (meth) acrylate
(d) Polyether (meth) acrylate
(e) Silicone (meth) acrylate
(f) (Meth) acrylate monomer
(g) Epoxy monomer
(h) Vinyl ether monomer
(i) Classified as oxetane monomer. (a) to (f) are types that are cured by radical polymerization reaction, and (g) to (i) are types that are cured by cationic polymerization reaction.

(a) to (e) are obtained by adding a (meth) acryloyl group to a resin, and are often expressed as oligomers, base resins, prepolymers, and the like.
(f) The (meth) acrylate monomer is a monofunctional or polyfunctional alkyl (meth) acrylate or a low-viscosity polyether (meth) acrylate having a viscosity of 500 mPas (25 ° C.) or less, such as methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n- Pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl ( (Meth) acrylate, benzyl ( ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6 -Hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, (1,1-dimethyl-3-oxobutyl) (Meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, neopentyl glycol mono (meth) acrylate 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1 , 10-decanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate (Aronix M-450 manufactured by Toagosei), dipentaerythritol hexaacrylate (Aronix M-405 manufactured by Toagosei) and the like.

  When a photoacid generator is used as the photocrosslinking catalyst, an acid crosslinking agent may be used as the crosslinking agent. The acid crosslinking agent is a plurality of (for example, 2 to 10) reactive groups that crosslink with an acidic group in one molecule (for example, carboxylic acid, hydroxyl group, amino group, isocyanate group, N-methylol group, alkyl etherified N-methylol). Group, an epoxy group, etc.) or a polyvalent metal salt of acetic acid, and examples thereof include amino resins, epoxy compounds, oxazoline compounds, and aluminum acetate.

  Amino resins include compounds in which some or all of the amino groups such as melamine compounds, guanamine compounds, and urea compounds are hydroxymethylated, or some or all of the hydroxyl groups of the hydroxymethylated compounds are methanol, ethanol A compound etherified with n-butyl alcohol, 2-methyl-1-propanol, etc., for example, hexamethoxymethyl methylol melamine, and various amino resins such as alkyl type, methylol type and imino type manufactured by Nippon Cytec Industries It is done.

-Alkali-soluble polymer An alkali-soluble polymer means a polymer having a functional group that forms a water-soluble salt when neutralized with an alkali such as carboxylic acid, hydroxyl group, and sulfonic acid. It is preferred that the alkali-soluble polymer is non. Non-, for example, phenol resin partially converted to cyclic alcohol structure by hydrogenation, resin in which a part of OH group of polyvinylphenol is protected with alkyl group, polyvinylphenol resin copolymerized with styrene, (meth) acrylate monomers And a polyvinylphenol resin copolymerized with styrene, a resin having a carboxy group, and a (meth) acrylate copolymer containing a hydroxyl group or a carboxylic acid group. Those having a fluorene skeleton described in Japanese Patent No. 2820553, Japanese Patent No. 3148429, and Japanese Patent Application Laid-Open No. 2004-35685 are particularly preferable.

-Base material The base material used for the board | substrate of this invention is a silicon wafer, a synthetic resin, glass, a metal, a ceramic. The substrate is preferably transparent, but may be non-transparent.
The synthetic resin may be either a thermoplastic resin or a thermosetting resin. For example, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified Polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS Resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. Polyester, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoro Various thermoplastic elastomers such as ethylene, polyvinylidene fluoride, other fluorine resins, styrene, polyolefin, polyvinyl chloride, polyurethane, fluororubber, chlorinated polyethylene, ethoxy resin, phenol resin, urea resin, melamine Resins, unsaturated polyesters, silicone resins, polyurethanes, etc., and copolymers, blends, polymer alloys, etc. mainly composed of these, and one or more of these are combined. Can be used Align Te (for example, as a laminate of two or more layers). If a synthetic resin substrate is used, the substrate can be provided with features such as light weight, transparency, low cost, and bending.

Examples of the glass include silicate glass (quartz glass), alkali silicate glass, soda lime glass, potassium lime glass, lead (alkali) glass, barium glass, and borosilicate glass.
Examples of the metal include gold, silver, copper, iron, nickel, aluminum, and platinum.
Ceramics include oxides (eg, aluminum oxide, zinc oxide, titanium oxide, silicon oxide, zirconia, barium titanate), nitrides (eg, silicon nitride, boron nitride), sulfides (eg, cadmium sulfide), carbides (For example, silicon carbide) and the like, and a mixture thereof may be used.

  Regardless of which substrate is used, pretreatment such as plasma treatment or UV ozone treatment may be performed. By these pretreatments, lyophilic functional groups (for example, OH groups, COOH groups, NH groups) can be introduced on the substrate surface.

● Method of two-layer coating The resist composition is uniformly treated on the surface of the substrate by a coating process. As the treatment method, a known coating method can be adopted as long as the film thickness can be controlled. For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted. Can be selected in consideration of the controllability and controllability of the film thickness. For example, after a resist composition is applied to a substrate by spin coating to form a lower resist film, a top coat composition is subsequently applied by spin coating to form an upper layer. The humidity when applying the top coat composition is preferably 50% or less, particularly preferably 40% or less. When the humidity is 50% or less, the orientation of the Rf group after film formation is good, and the frequency of adversely affecting the liquid repellency is low.

  After the two-layer coating is completed in this way, a pre-bake for drying the solvent is performed. The pre-bake is heated at 70 to 150 ° C. for 1 second to 10 minutes (for example, 110 ° C. for 1 minute). The thickness of the lower resist film is generally 50 nm to 100 μm, for example 100 nm to 10 μm, in particular 500 nm to 5 μm. The thickness of the topcoat film may generally be 1 nm to 100 nm, for example 2 nm to 80 nm, in particular 3 nm to 50 or 20 nm.

Next, the two-layered coating film is subjected to lyophobic-lyophilic patterning using a photolithography method. A plurality of regions having different surface free energies [(1) a region having a propylene glycol methyl ether acetate (PGMEA) contact angle of 70 ° or more, particularly a region having a contact angle of 80 ° or more, and (2) a region having a PGMEA contact angle of 10 ° or less, particularly 5 A pattern substrate composed of a region below ° is prepared.
A bank composed of a topcoat film and a resist film is formed by photolithography. The bank generally has a top coat film on the top surface of the bank, and does not have a top coat film on the side surface of the bank. The upper surface of the bank preferably has a PGMEA contact angle of 70 ° or more. It is preferable that the PGMEA contact angle is 10 ° or less on the side surface of the bank and the bottom surface without the bank (for example, the substrate surface).
In order to pattern the two-layered coating with a liquid repellent-lyophilic pattern by photolithography, an electromagnetic wave is irradiated.

● Electromagnetic wave (exposure)
The electromagnetic wave irradiated to the bilayer film in the present invention is light having a wavelength of 10 to 400 nm, ultraviolet (UV, 200 to 400 nm), vacuum ultraviolet (VUV, 150 to 200 nm), extreme ultraviolet (EUV, 10 to 120 nm) Etc. are exemplified. When VUV is used, a commercially available xenon excimer lamp capable of emitting VUV having a wavelength of 172 nm can be used as the light source. When UV is used, a mercury xenon lamp, mercury lamp, xenon lamp, or xenon excimer lamp can be used as the light source. Further, a 248 nm KrF excimer laser, a 193 nm ArF excimer laser, and a 157 nm F2 excimer laser may be used. Exposure amount 1~10,000mJ / cm ^2, may be a particularly 1~1000mJ / cm ^2.
In addition to light, electromagnetic waves of X-rays having a wavelength of 0.1 to 10 nm, electron beams having a wavelength of 0.001 to 0.01 nm, and laser beams having a wavelength of 10 to 300 nm may be used.

When photolithography is performed using light or X-rays, the film may be irradiated with light through a photomask, or a Micro Electro such as DMD (digital micromirror device) developed by Texas Instruments, USA Mechanics (MEMS) may be used to irradiate light in a pattern without a mask. The DMD is a device in which 480,000 to 1.31 million movable mirrors (micromirrors) of 10 μm scale are arranged in a lattice shape, and the lamp light is reflected on the mirror to irradiate the film with light in a pattern.
On the other hand, with an electron beam or a laser beam, a pattern is drawn on a substrate that has been uniformly surface-treated directly without a photomask using a commercially available drawing apparatus. Exposure of the electron beam 10~10,000μC / cm ² in raster drawing, especially 100~1,000μC / cm ^2, a shot draw 100~100,000fC / dot, may in particular 1,000~10,000fC / dot.

  After exposure, baking (post-exposure baking) may be performed. Post-exposure baking can be performed by heating at 70 to 150 ° C. for 1 second to 10 minutes (for example, at 80 ° C. for 1 minute).

Development In the present invention, a step of removing a solvent-soluble region, so-called “development”, is performed using the contrast of solubility in a solvent after irradiation with the electromagnetic wave. As the solvent (developer) used for development, an alkaline aqueous solution is usually used. The alkaline aqueous solution is an inorganic alkaline aqueous solution such as sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine, methyldiethylamine and N-methylpyrrolidone; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxy A quaternary ammonium salt such as TMAH, tetraethylammonium hydroxide, choline, etc .; an organic alkali aqueous solution composed of alkalis of cyclic amines such as pyrrole and piperidine is used. These may be used alone or in combination of two or more. Further, a surfactant may be added. Examples of alkaline developer products include Hoechst's P3 Disperse series.
The developing method may be performed in the range of 10 seconds to 10 minutes by an immersion method, a liquid filling method, a shower method, a paddle method, an ultrasonic method, or the like.
In the present invention, in order to enhance the wetting contrast of the lyophobic / lyophilic pattern, a treatment such as plasma treatment or UV ozone treatment may be performed after pattern formation. Further, heat treatment may be performed after these treatments. This heat treatment can be performed by heating at 70 to 150 ° C. for 1 second to 10 minutes (for example, at 110 ° C. for 1 minute).

Positive Resist Composition In the case of a positive resist composition, a compound (for example, a polymer) that increases the solubility in a developer when exposed to light is used. The exposed portion is removed by the developer, and a pattern is formed.

● Liquid repellent-shape of lyophilic pattern The shape of the liquid repellent-lyophilic pattern may be selected according to the purpose of the final device to be manufactured, such as circle, square, triangle, straight line, curve, etc. Illustrated. Mutual patterns may be in contact or separated. For example, in the case of a line and space, the line width and the line interval may be 0.5 to 100 μm, for example, 1 to 20 μm. The line width may be equally spaced or the width may change. The shape of the line may be a straight line or a curve. When the shape of the lyophilic region is rectangular, the length of the rectangle may be 0.5 to 500 μm, for example, 10 to 100 μm. The line width of the liquid repellent region may be 0.5 to 500 μm, for example, 10 to 100 μm.

Application of Functional Compound Solution to Substrate Formed with Liquid-Repellent-Liquid Pattern In the present invention, a functional compound solution or dispersion is applied to the substrate formed with the liquid-repellent-lyophilic pattern. The functional compound solution can be applied by spin coating, dip coating, casting, roll coating, printing, transfer, ink jet [P. Calvert, Chem. Mater., 13, 3299 (2001)]. , Nozzle printing method, barcode method, capillary method and the like.

  The functional compound layer can be formed by applying a solution obtained by dissolving the functional compound in a solvent on the pattern surface and removing the solvent. When the functional compound solution is applied to a plurality of regions having different surface free energies, the functional compound solution avoids a region having a PGMEA contact angle of 70 ° or more, particularly 80 ° or more, and a PGMEA contact angle of 10 ° or less, particularly Wet and spread only in the region of 5 ° or less. Thus, a layer of functional compound is formed on the lyophilic region patterned on the substrate.

Examples of functional compounds are semiconductor compounds, conductive compounds, dyes or pigments for forming display pixels, photochromic compounds, thermochromic compounds, lens materials, life science drugs, and the like.
As the semiconductor compound, an organic compound is preferable, and examples thereof include a pentacene derivative, a polythiophene derivative, a phthalocyanine derivative, a polyfluorene derivative, a poly p-phenylene vinylene, and a layered herbskite compound.

The conductive compound has a conductivity of 10 ² S / cm 2 or more at room temperature. For example, in an organic system, polyacetylene derivatives, polythiophene derivatives, polypyrrole, poly p-phenylene vinylene, polyaniline and the like can be mentioned. Conductivity may be improved by doping these compounds. In the metal system, a material in which nanoparticles such as gold, silver and copper are dispersed in a liquid can be used.

  Examples of the black pigment include carbon black, graphite, titanium black, iron oxide, bismuth sulfide, and perylene black. Examples of pigments other than black include, for example, azo lakes, insoluble azos, phthalocyanines, quinacdrines, dioxazines, isoindolinones, verinones, anthraquinones, perylenes, and mixtures thereof, miloli blue, and oxidation. Iron, cobalt-based, manganese-based, ultramarine, bitumen, cobalt blue, cerulean blue, pyridian, emerald green, cobalt green, and mixtures thereof. These pigments are preferably dispersed in a particle diameter of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color the coating film while maintaining the transparency of the coating film. Has an average particle size of 0.2 to 0.3 μm. Examples of the dye include a high-molecular or low-molecular coating type light-emitting material developed for organic EL.

The photochromic compound is preferably an organic compound, and examples thereof include azobenzene derivatives, spiropyran derivatives, fulgide derivatives, and diarylethene derivatives.
The thermochromic compound is a general term for compounds whose color changes reversibly with changes in temperature. For example, salicylideneanilines, polythiophene derivatives, tetrahalogeno complexes, ethylenediamine derivative complexes, dinitrodiammine copper complexes, Examples include 1,4-diazacyclooctane (daco) complex, hexamethylenetetramine (hmta) complex, and saltylaldehyde (salen) complex.
The thickness of the functional compound layer may be 0.1 nm to 100 μm, for example 1 nm to 1 μm.

Examples of the solvent that dissolves the functional compound are an organic solvent, a water-soluble organic solvent, and water. When the functional compound is hardly soluble in water, it must be dissolved in an organic solvent or a water-soluble organic solvent.
In the present invention, the solvent for dissolving the functional compound is preferably an organic solvent having a surface tension of 40 mN / m or less, for example, 30 mN / m or less. When the surface tension is 40 mN / m or less, the solution can easily spread in the lyophilic region along the pattern shape.

  Examples of the organic solvent include alcohols, esters, ketones, ethers, hydrocarbons (eg, aliphatic hydrocarbons and aromatic hydrocarbons), and the organic solvent may or may not be fluorinated. . Specific examples of the organic solvent include perfluorodecalin, hydrofluoroether, HCFC225, chloroform, 1,1,2,2-tetrachloroethane, tetrachloroethylene, chlorobenzene, butyl acetate, hexane, isopentane, toluene, xylene, anisole, tetrahydrofuran and the like. Can be mentioned. Specific examples of water-soluble organic solvents include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol Propylene glycol, tripropylene glycol, dimethylformamide, dimethyl sulfoxide, methyl cellosolve, ethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, monoglyme, diglyme, triglyme, isopropyl alcohol, methanol, ethanol, etc. Can be mentioned.

  When water is used, the surface tension may be lowered by adding a surfactant, the above water-soluble organic solvent, or the like.

  The concentration of the functional compound in the functional compound solution may be 0.1 to 30% by weight, for example 1 to 20% by weight.

  The solvent can be removed by evaporation or the like. The removal of the solvent can be performed by heating the substrate (for example, 60 to 200 ° C.). The solvent removal may be performed under reduced pressure (for example, 0.01 to 100 Pa).

  The present invention can be used for a wide range of devices such as electronic, optical, medical, and chemical analyses. For example, the electronic device can be used for an integrated circuit such as a transistor, a memory, a light emitting diode (EL), a laser, or a solar cell. From these devices, flexible displays, wireless tags, wearable computers and the like are manufactured. Also, as optical devices, display pixels (for example, light-emitting substrates) such as color filters of liquid crystal displays and organic EL, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photo elements It can be used for nick crystals, lens arrays, etc., and as medical devices, for biochips such as DNA arrays and protein arrays. The chemical analysis device can be used for a microchemical chip such as a microchemical plant or a microchemical analysis system.

● Liquid repellency of liquid repellency bank The topcoat composition of the present invention is extremely useful for repellency of a liquid repellency bank which is necessary when a color filter for display or a light emitting substrate is produced by an ink jet method. The liquid repellent bank is arranged in a matrix in a color filter or a light emitting substrate, and separates a pigment or a light emitting material (for example, a semiconductor material). The upper surface of the bank has liquid repellency, while the side surface of the bank and the portion without the bank (for example, the surface of the substrate) do not have liquid repellency. Thus, the dye or the luminescent material is sufficiently separated by the banks and further spreads without gaps in the spaces formed between the banks.
The liquid repellent bank can be usefully used in a color filter of a liquid crystal display and a light emitting substrate of an organic EL display.
(I) Black matrix liquid repellency in color filter The topcoat composition of the present invention is extremely useful for liquid matrix repellency required when producing a color filter for display by an inkjet method. The inkjet method is expected as a technology for manufacturing color filters at a low cost, but the inkjet technology alone has sufficient landing accuracy to accurately print red, green, and blue ink in the black matrix (pixel part). being insufficient. For this reason, it is necessary to make the upper part of the black matrix liquid repellent and draw ink droplets that have been accidentally removed back into the pixels. Further, when red, green, and blue inks are injected to an amount exceeding the height of the black matrix in order to increase the pixel film thickness, it is essential to make the upper portion of the black matrix liquid repellent. The contact angle with PGMEA is often selected as the liquid repellency index.
(Ii) Liquid repellent of bank matrix in light emitting substrate In a light emitting substrate used in an organic EL, a liquid repellent bank is used in a matrix. By using the topcoat composition of the present invention, a liquid repellent bank having good liquid repellency can be formed.

Hereinafter, a method for making a black matrix liquid repellent using the top coat composition of the present invention will be described.
After the topcoat composition of the present invention is uniformly applied on the photosensitive resin black layer uniformly formed on the lyophilic transparent substrate, it is made lyophobic on the lyophilic transparent substrate by photolithography. This is a method for forming a black matrix. As an example of the black resist composition at this time, for example,
Alkali-soluble polymer 0-20% by weight
Crosslinker 1-10% by weight
Photocrosslinking catalyst 0.5-5% by weight
Black pigment 5-20% by weight
Solvent balance (100% by weight in total)
Is mentioned.

  A color filter can be manufactured at an extremely low cost by applying a red, green, and blue pigment dispersion for a color filter on a transparent substrate having a lyophobic black matrix by an ink jet method and removing the solvent.

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
In the examples and comparative examples, each measurement was performed by the following method. Unless otherwise specified, all operations were performed at 25 ° C.

Evaluation of developability The developability was evaluated in five stages by observing the pattern developed after exposure with a mask aligner with an optical microscope. The term “developability” as used herein refers to a comprehensive evaluation of the pattern shape of the UV exposed area remaining after development and the film removability of the UV unexposed area. >×> ××
It was evaluated.

● Evaluation of color pattern splitting ability By observing the shape of the color pattern on the formed lyophilic liquid-repellent pattern with the ink-jet method using an optical microscope, the color pattern splitting ability is divided into five levels. It was evaluated with. ◎ ＞ ○ ＞ △ ＞ × ＞ XX in order of good splitting
It was evaluated.

The contact angle was measured by the following method using a fully automatic contact angle meter DropMaster700 (manufactured by Kyowa Interface Science). 2 μL of propylene glycol methyl ether acetate (PGMEA) was dropped from a microsyringe onto a horizontally placed substrate, and a still image one second after dropping was photographed with a video microscope.
Polymers of the following production examples and comparative production examples were synthesized. A detailed synthesis method will be described below.

Production Example 1 [Rf (C4) α-Cl homopolymer for top coat]
Fluoroacrylate CH ₂ ═C (Cl) COO—CH ₂ CH in which the α-position of the Rf group having 4 carbon atoms is substituted with chlorine in a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer ₂ C ₄ F ₉ [abbreviation Rf (C4) α-Cl] 4 g, HFE7200 16 g, 2,2′-azobisisobutyronitrile (abbreviation AIBN) 0.04 g were added, heated to 70 ° C., and nitrogen was added for 12 hours. Stir under a stream of air. By analyzing the Rf (C4) α-Cl monomer remaining in the reaction solution by gas chromatography, it was confirmed that the conversion rate was 95% or more. The obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer.

Production Example 2 (Rf (C4) α-Cl / MAA = 95 / 5mass copolymer for top coat)
Fluoroacrylate CH ₂ ═C (Cl) COO—CH ₂ CH in which the α-position of the Rf group having 4 carbon atoms is substituted with chlorine in a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer ₂ C ₄ F ₉ [abbreviation Rf (C4) α-Cl] 3.8 g, methacrylic acid (abbreviation MAA) 0.2 g, HFE7200 16 g, AIBN 0.04 g were added, heated to 70 ° C. and then under nitrogen flow for 12 hours. Stir with. By analyzing the Rf (C4) α-Cl monomer remaining in the reaction solution by gas chromatography, it was confirmed that the conversion rate was 95% or more. The obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer. When the molecular weight of the obtained product was measured by GPC, the weight average molecular weight was 35,000.

Production Example 3 [Rf (C6) α-Cl homopolymer for top coat]
Rf (C4) α-Cl of Production Example 1 was replaced with fluoroacrylate CH ₂ ═C (Cl) COO—CH ₂ CH ₂ C ₆ F ₁₃ [abbreviation Rf (C6 ) Fluoropolymer was produced in exactly the same manner except that it was replaced with α-Cl].

Comparative Production Examples 1-4 [Conventional Topcoat Fluoro (meth) acrylate Homopolymer]
Rf (C4) α-Cl of Production Example 1 was converted to fluoroacrylate CH ₂ ═C (H) COO—CH ₂ CH ₂ C ₄ F ₉ [abbreviation Rf (C4) α-H] (comparative) with Rf group carbon number 4 production example 1), fluoro methacrylate Rf group having a carbon number _{4 CH 2 = C (CH 3} ) COO-CH 2 CH 2 C 4 F 9 [ abbreviation Rf (C4) α-CH3] ( Comparative production example 2), Rf group 6 carbon fluoro methacrylate _{CH 2 = C (CH 3)} COO-CH 2 CH 2 C 6 F 13 [ abbreviation Rf (C6) α-CH3] ( Comparative production example 3), fluoroacrylate CH of Rf group having a carbon number 8 ₂ ═C (H) COO—CH ₂ CH ₂ C ₈ F ₁₇ [abbreviation Rf (C8) α-H] (Comparative Production Example 4) A fluoropolymer was produced in exactly the same manner.

Comparative Production Example 5 [Fluoropolymer Rf (C4) α-Cl / MAA / iBMA = 60/15/25 mass% for resist internal addition]
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 2.4 g of Rf (C4) α-Cl, 0.6 g of MAA, 1 g of isobornyl methacrylate (abbreviated iBMA), n-dodecyl Mercaptan, 10 mol% of monomer and 16 g of methoxybutyl acetate were added, heated to 70 ° C., and stirred for 30 minutes under a nitrogen stream. To this, 1 mol% of AIBN with respect to the monomer was added and polymerized for 12 hours. By analyzing the Rf (C4) α-Cl monomer remaining in the reaction solution by gas chromatography, it was confirmed that the conversion rate was 95% or more. The obtained reaction solution was precipitated with hexane and vacuum-dried to isolate the fluoropolymer. When the obtained molecular weight was measured by GPC, the weight average molecular weight was 5,000 (polystyrene conversion).

Comparative Production Examples 6 to 9 [Conventional Fluoropolymer for Internal Addition of Resist]
Rf (C4) α-Cl of Comparative Production Example 5 was replaced with Rf (C4) α-H (Comparative Production Example 6), Rf (C4) α-CH3 (Comparative Production Example 7), Rf (C6) α-CH3 ( Fluoropolymer for resist addition having a conventional structure was produced in exactly the same manner except that it was replaced with Comparative Production Example 8) and Rf (C8) α-H (Comparative Production Example 9).

Production Example 4 (Alkali-soluble polymer)
In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 10.5 g of MAA, 42 g of 2-hydroxyethyl methacrylate, 47.5 g of iBMA, mercaptoethanol with respect to 10 mol% of monomer, 232 g of PGMEA The mixture was heated to 70 ° C. and stirred for 30 minutes under a nitrogen stream. To this, 1 mol% of AIBN with respect to the monomer was added and polymerized for 12 hours. The obtained reaction solution was precipitated with hexane and vacuum-dried to isolate an alkali-soluble polymer. When the molecular weight of the obtained polymer was measured by GPC, the weight average molecular weight was 5,000 (polystyrene conversion).

Example 1 (Topcoat)
First, 20% by weight of an alkali-soluble polymer (Production Example 4), 4% by weight of Cymel 300 (Nippon Cytec Industries' melamine resin), 1% by weight of IRGACURE PAG103 (Ciba photoacid generator), 75% by weight of PGMEA A negative resist composition having the following composition was spin-coated at 2000 rpm (lower film thickness: 800 nm), and immediately without any heat treatment, the topcoat composition [Rf (C4) α-Cl homopolymer of Production Example 1 was added to HFE7100 by 0.05]. The solution diluted to have a weight%] was spin-coated at 2000 rpm (upper layer thickness 5 nm). The film thickness of the upper layer and the lower layer was measured with an atomic force microscope by preparing a sample obtained by cutting a film formed on a silicon wafer alone with a razor. The concentration of the top coat composition was selected as a concentration capable of achieving both developability and liquid repellency.
Next, pre-baking 80 ° C. → exposure without photomask (mixture of g, h, i lines) 200 mJ / cm 2 → post-exposure baking (PEB) 80 ° C. → alkali development (stock solution of P3 disperse M made by Hoechst) → post-baking 110 A uniform liquid repellent coating film was produced on the silicon wafer of the substrate at 0 ° C., and the contact angle with PGMEA was measured.

Comparative Examples 1-4 (Topcoat)
The fluorine polymer used in the topcoat composition of Example 1 was replaced with Comparative Production Examples 1 to 4, and the contact angle with PGMEA was measured.

Comparative Examples 5 to 9 (internal addition)
The fluoropolymer internally added to the resist composition is a fluoro (meth) acrylate copolymer of Comparative Production Examples 5 to 9. MAA was copolymerized to impart alkali solubility, and iBMA was copolymerized to impart solubility in a resist solvent. A negative comprising 1% by weight of this fluoropolymer (= 4% by weight in terms of solid content), 19% by weight of alkali-soluble polymer (Production Example 4), 4% by weight of Cymel 300, 1% by weight of IRGACURE PAG103, and 75% by weight of PGMEA Spin coating 2000 rpm → Pre-baking 80 ° C. → Exposure 200 mJ / cm 2 → PEB 80 ° C. → Alkaline development (P3 disperse M diluted to 10%) → Post-baking 110 ° C. A film was prepared (film thickness 800 nm). Fluoropolymer 4% by weight (based on solid content) was selected as a concentration that can achieve both developability and liquid repellency.
The results are shown in Table 1 below and FIG.

Table 1. Comparison of PGMEA static contact angle of top coat and internal additive

  Table 1 shows the results of comparing the contact angles of the fluorine-based polymer internally added resist thin film (hereinafter abbreviated as “internal addition”) and the resist / topcoat bilayer thin film (hereinafter abbreviated as “topcoat”) with respect to PGMEA. The repeating unit names of fluoro (meth) acrylate shown in Table 1 indicate that the internal addition indicates the fluoro (meth) acrylate used for the copolymer, and the top coat indicates the fluoro (meth) acrylate used for the homopolymer. Yes. In both cases of the top coat and internal addition, α-Cl was overwhelmingly superior in C4. This is probably because the molecular mobility of the Rf (C4) α-Cl repeating unit in the polymer is suppressed at room temperature. With some exceptions, the top coat exhibited higher liquid repellency than internal addition. In the internal addition, in order to impart alkali solubility and resist solubility to the fluorine-based polymer, methacrylic acid and iBMA must be copolymerized, and thus liquid repellency has been sacrificed. On the other hand, the top coat does not need to dissolve the fluorine-based polymer in the resist, so it may be a homopolymer and can exhibit the highest liquid repellency possessed by fluoro (meth) acrylate. The alkali solubility may be adjusted by adjusting the homopolymer concentration in the hydrofluoroether used in the second layer, and 0.05% by weight was optimal. This optimum concentration varies depending on the coating method and the like.

Examples 2 and 3 (top coat)
The fluorine polymer of the topcoat composition of Example 1 was replaced with Production Example 2 (Example 2) and Production Example 3 (Example 3), and the contact angle with PGMEA was measured. It was 7 °. However, in Example 3, the solvent for dissolving Production Example 3 was HFE7100 / isopropyl alcohol = 99/1 weight ratio.

  The present invention can be used for a wide range of devices such as electronic, optical, medical, and chemical analyses. For example, the electronic device can be used for an integrated circuit such as a transistor, a memory, a light emitting diode (EL), a laser, or a solar cell. From these devices, flexible displays, wireless tags, wearable computers and the like are manufactured. Optical devices include display pixels such as color filters for liquid crystal displays and organic EL, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, etc. In addition, the medical device can be used for biochips such as DNA arrays and protein arrays. The chemical analysis device can be used for a microchemical chip such as a microchemical plant or a microchemical analysis system.

Claims (13)

(A) α-substituted acrylate having a fluoroalkyl group having 1 to 6 carbon atoms
[However, the substituent at the α-position is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, a fluorine atom or a chlorine atom), a cyano group, A linear or branched fluoroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl group having 2 to 20 carbon atoms. . ]
A top coat composition for liquid-repellent-lyophilic patterning, comprising: a fluorine-containing polymer containing at least 70% by weight of (A), and (B) a solvent.   The topcoat composition for lyophobic-lyophilic patterning according to claim 1, wherein the concentration of the fluoropolymer (A) is in the range of 0.01 to 5% by weight.   The topcoat composition for lyophobic-lyophilic patterning according to claim 1 or 2, wherein the solvent (B) is a mixed solvent having a mixing weight ratio of hydrofluoroether and non-fluorinated solvent of 100/0 to 90/10. . Solvent (B) is
_{C n F 2n + 1 -O-} C x H 2x + 1 (1)
[Wherein, n is a number from 1 to 6, and x is a number from 1 to 6. ]
The topcoat composition for lyophobic-lyophilic patterning according to any one of claims 1 to 3.   The topcoat composition for lyophobic-lyophilic patterning according to any one of claims 1 to 4, wherein the topcoat film formed from the topcoat composition has a thickness of 1 nm to 100 nm.   A method for producing a lyophobic-lyophilic pattern, wherein a two-layer film obtained by coating the top coat composition according to claim 1 on a photosensitive coating film is patterned by a photolithography method.   A two-layer film obtained by coating two layers of the topcoat composition according to any one of claims 1 to 3 on a photosensitive resin black layer uniformly formed on a transparent substrate. A method for producing a color filter for a display, which comprises forming a black matrix having a liquid repellency in a pattern by a lithography method.   A color filter for display manufactured by the manufacturing method according to claim 7.   The two-layer film obtained by further coating the topcoat composition according to claim 1 on the photosensitive resin layer uniformly formed on the substrate is repelled in a pattern by a photolithography method. A method for manufacturing a display light-emitting substrate, characterized in that a formed bank is formed.   A light-emitting substrate for display manufactured by the manufacturing method according to claim 9.   A liquid repellent bank having a contact angle of 70 ° or more with respect to propylene glycol methyl ether acetate produced by a photolithography method using the top coat composition for liquid repellent-lyophilic patterning according to claim 1. Formed on a transparent substrate,
(I) A layer of a topcoat composition for liquid-repellent-lyophilic patterning according to claim 1, and (ii) a two-layer film comprising a photosensitive resin layer.   The bilayer film according to claim 12, wherein the thickness of the layer of the topcoat composition is 1 nm to 100 nm.

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