JP4905563B2 - Resist composition and coating film thereof - Google Patents

Description

  The present invention relates to a resist composition and a coating film thereof.

  Conventionally, a resist composition has been used to form a mask for manufacturing a circuit such as a semiconductor integrated circuit (IC) and a thin film transistor (TFT) circuit for a liquid crystal display (LCD).

  On the other hand, the resist composition is used as a material for forming a permanent film such as a partition wall of a color filter, an ITO electrode partition wall of a liquid crystal display element, an organic EL display element partition wall, a circuit wiring board partition wall, etc. Is also attracting attention.

  For example, in the manufacture of color filters, a so-called inkjet method using an inkjet recording technology method in which R (red), G (green), and B (blue) inks are jetted and applied to minute pixels has been proposed. Here, the pixel pattern is formed by photolithography using a resist composition, and a coating film of the resist composition is used as a partition between pixels.

  In the production of liquid crystal display elements, an inkjet method in which an ITO solution is spray-coated at the time of forming an ITO (tin-doped indium oxide) electrode has been proposed, and the ITO electrode pattern is formed by photolithography using a resist composition. In practice, a coating film of a resist composition is used as a partition wall.

  Furthermore, in the manufacture of organic EL display elements, an inkjet method has been proposed in which a hole transport material and a solution of a light emitting material are sprayed and applied in order to form a hole transport layer, a light emitting layer, and the like in a minute pixel. Here, the pixel pattern is formed by photolithography using a resist composition, and a coating film of the resist composition is used as a partition between pixels.

  In manufacturing a circuit wiring board, an ink jet method has been proposed in which a metal solution is sprayed and applied when forming circuit wiring. Here, the circuit wiring pattern is formed from the resist composition by photolithography, and a coating film of the resist composition is used as a partition wall.

  In the ink-jet method, it is necessary to prevent the occurrence of ink color mixing between adjacent pixel regions and the phenomenon that the ITO solution or the metal solution clumps and sticks to a portion other than a predetermined region. Therefore, the partition wall is required to have a property of repelling water or an organic solvent which is an inkjet coating liquid, so-called water and oil repellency.

  Patent Document 1 discloses a photoresist composition containing a copolymer of a fluoroalkyl group-containing (meth) acrylate monomer and a silicone chain-containing ethylenically unsaturated monomer, and the copolymer Is added in an amount of 0.001 to 0.05 mass% with respect to the solid content of the photoresist composition.

  Patent Document 2 discloses a coating composition containing a vinyl polymer obtained by polymerizing a monomer composition containing a vinyl monomer having a fluoroalkyl group, a photosensitive resin, and an organic solvent. The vinyl polymer is a polymer containing 0.1 to 5% by mass of fluorine atoms, and the ratio of the vinyl polymer to the total mass of the vinyl polymer and the photosensitive resin. Is 0.25 to 2.0 mass%.

  However, the coating film formed from the composition consisting of the blending ratio of the copolymer described in Patent Document 1 and the composition consisting of the blending ratio of the vinyl polymer described in Patent Document 2 is insufficient in water and oil repellency. To do.

JP-A-9-54432 (Claim 1, paragraph 0086) JP 2004-2733 A (Claim 1)

  While the present invention is excellent in water and oil repellency, it has a good appearance and can form a coating film with high adhesion to a substrate, and also has a good alkali developability and allows fine pattern formation. It is an object to provide a resist composition and a coating film thereof.

The present invention provides the following means.
[1 -1] has a monomer unit formed from a monomer represented by Formula 1, having an ethylenic double bond, a fluorine-containing resin fluorine atom content is 7 to 35 mass% (A) and the resist composition containing the photosensitive component which reacts to the light of wavelength 100-600 nm, Comprising: The ratio of the said fluororesin (A) with respect to the total solid of the said resist composition is 0.1-30 mass % Of a resist composition.

CH ₂ = C (R ¹ ) COOXR ^f ... Formula 1
In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents an organic group not containing a divalent fluorine atom having 1 to 6 carbon atoms, and R ^f represents a perfluoro group having 4 to 6 carbon atoms. A fluoroalkyl group;
[1-2] A fluorine-containing resin (A) having a monomer unit formed from the monomer represented by Formula 1 and having a fluorine atom content of 7 to 35% by mass and a wavelength of 100 to 600 nm A resist composition used for forming partition walls, containing a photosensitive component that reacts with light, wherein the ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 30% by mass. There is provided a resist composition.
CH ₂ = C (R ¹ ) COOXR ^f ... Formula 1
In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents an organic group not containing a divalent fluorine atom having 1 to 6 carbon atoms, and R ^f represents a perfluoro group having 4 to 6 carbon atoms. A fluoroalkyl group;
[1-3] A fluorine-containing resin having a monomer unit formed from the monomer represented by Formula 1, having an ethylenic double bond, and a fluorine atom content of 7 to 35% by mass (A) and a resist composition used for the formation of a partition containing a photosensitive component that reacts with light having a wavelength of 100 to 600 nm, the ratio of the fluororesin (A) to the total solid content of the resist composition Is a resist composition characterized by being 0.1 to 30% by mass.
CH ₂ = C (R ¹ ) COOXR ^f ... Formula 1
In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents an organic group not containing a divalent fluorine atom having 1 to 6 carbon atoms, and R ^f represents a perfluoro group having 4 to 6 carbon atoms. A fluoroalkyl group;
[2] The photosensitive component includes a photoacid generator (B), an alkali-soluble resin (C) having a carboxyl group and / or a phenolic hydroxyl group, and a group capable of reacting with a carboxyl group or a phenolic hydroxyl group by the action of an acid. The resist composition according to [1], comprising an acid crosslinking agent (D), which is a compound having two or more of.
[3] The resist composition according to [2], wherein the fluororesin (A) has a carboxyl group and / or a hydroxyl group.
[4] The resist according to [1], wherein the photosensitive component includes a photoradical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more ethylenic double bonds in one molecule. Composition.
[5] The resist composition according to [4], wherein the photosensitive component further includes a radical crosslinking agent (G) having two or more ethylenic double bonds and having no acidic group.
[6] The resist composition according to [4] or [5], wherein the fluororesin (A) has an ethylenic double bond.
[7] The alkali-soluble resin (F) has a carboxyl group and / or a hydroxyl group, and the photosensitive component is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group by the action of heat. The resist composition according to any one of [4] to [6], further comprising a crosslinking agent (H).
[8] A coating film obtained from the resist composition according to any one of [1-1] to [1-3] and [2 ] to [7].

  The fluorine-containing resin (A) of the present invention has a perfluoroalkyl group having 4 to 6 carbon atoms, has a fluorine atom content of 7 to 35% by mass, and contains a fluorine-containing resin in the total solid content of the composition ( When the ratio of A) is 0.1 to 30% by mass, the coating film exhibits sufficient water and oil repellency, has a good appearance, and has excellent substrate adhesion. That is, the fluororesin (A) has good compatibility with the other components of the composition, and the fluororesin (A) does not aggregate when the composition is applied to form a coating film. The coating film does not become cloudy. Therefore, there is no possibility that the resolution is lowered due to a decrease in the light transmittance of the coating film or the occurrence of irregular reflection of light during exposure. Since the fluorine-containing resin (A) has surface migration, the concentration of the fluorine-containing resin (A) on the surface of the coating film is relatively increased by transferring to the vicinity of the coating film surface during pre-baking. The concentration of the nearby fluororesin (A) is relatively decreased. Therefore, adhesiveness with a base material is high.

  The following are mentioned as a preferable aspect as the resist composition of this invention.

  First, a fluorine-containing resin (A), a photoacid generator (B), an alkali-soluble resin (C) having a carboxyl group and / or a phenolic hydroxyl group, and a carboxyl group and / or a phenolic hydroxyl group by the action of an acid A negative resist composition containing an acid crosslinking agent (D) which is a compound having two or more reactive groups capable of crosslinking is one of preferred embodiments. Hereinafter, it is referred to as “first composition” in the present specification.

  By irradiation with light having a wavelength of 100 to 600 nm, an acid is generated from the photoacid generator (B), and the alkali-soluble resin (C) and the acid cross-linking agent (D) are mainly cross-linked to become insoluble in alkali. In the subsequent alkali development step, the unexposed part is removed.

  In the first composition, the fluororesin (A) preferably has a carboxyl group and / or a hydroxyl group because the coating film is excellent in water and oil repellency durability. The carboxyl group and / or hydroxyl group of the fluorine-containing resin (A) undergoes a crosslinking reaction with the acid crosslinking agent (D), and the hydroxyl group is a hydrogen bond with the alkali-soluble resin (C) or the acid crosslinking agent (D). It is considered that the fluororesin (A) is immobilized on the surface of the coating film through other interactions.

  Next, a fluorine-containing resin (A), a photo radical initiator (E), an alkali-soluble resin (F) having two or more ethylenic double bonds and acidic groups, and two or more ethylenic doubles A negative resist composition containing a radical crosslinking agent (G) having a bond and no acidic group is one of preferred embodiments. Hereinafter, it is referred to as “second composition” in the present specification.

  Radiation is generated from the photoradical initiator (E) by irradiation with light having a wavelength of 100 to 600 nm, and a compound having an ethylenic double bond undergoes a crosslinking reaction. As a crosslinking reaction of a compound having an ethylenic double bond, a crosslinking reaction between alkali-soluble resins (F), a crosslinking reaction between radical crosslinking agents (G), or an alkali-soluble resin (F) and a radical crosslinking agent (G ) And the exposed portion becomes insoluble in alkali. In the subsequent alkali development step, the unexposed part is removed.

  In the second composition, the fluororesin (A) preferably has an ethylenic double bond because the coating film is excellent in water and oil repellency and durability. The fluorine-containing resin (A) is considered to be immobilized on the coating film surface by a crosslinking reaction with the alkali-soluble resin (F) and / or the radical crosslinking agent (G).

  In the second composition, since the heat resistance of the coating film is improved, the alkali-soluble resin (F) has a carboxyl group and / or a hydroxyl group and can react with the carboxyl group and / or the hydroxyl group by the action of heat. It is preferable to further include a thermal crosslinking agent (H) which is a compound having two or more groups. It is considered that the alkali-soluble resin (F) and the thermal crosslinking agent (H) undergo a crosslinking reaction by the heat treatment after development, and the crosslinking density of the coating film increases.

  According to the present invention, while being excellent in water and oil repellency, it is possible to form a coating film having good appearance and high adhesion to the substrate, and further having good alkali developability and fine pattern formation. A possible resist composition is obtained.

  In this specification, the resist composition refers to a composition capable of forming a pattern by photolithography, that is, by applying a composition to a substrate to form a coating film, and then exposing and developing.

  In the compound name of this specification, (meth) acrylate means acrylate and / or methacrylate. Similarly, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) acrylamide means acrylamide and / or methacrylamide.

  The negative resist composition of the present invention contains a fluororesin (A) having a monomer unit formed from the monomer represented by Formula 1.

CH ₂ = C (R ¹ ) COOXR ^f ... Formula 1
In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents a divalent organic group having 1 to 6 carbon atoms, and R ^f represents a perfluoroalkyl group having 4 to 6 carbon atoms. .

  The following are mentioned as an example of the monomer represented by the said Formula 1.

CH ₂ = C (R ¹ ) COOR ² R ^f
CH ₂ = C (R ¹ ) COOR ² NR ³ SO ₂ R ^f
CH ₂ = C (R ¹ ) COOR ² NR ³ COR ^{f
_{CH 2 = C (R 1)}} COOCH 2 CH (OH) R 4 R f
Here, R ² represents an alkylene group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a single bond or an alkylene group having 1 to 4 carbon atoms.

Specific examples of R _{^2, -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH _{2 CH 3) -, - CH} 2 CH 2 CH 2 CH 2 -, - CH (CH 2 CH 2 CH 3) -, - CH 2 (CH 2) 3 CH 2 -, - CH (CH 2 CH (CH 3 ) ₂ )-and the like.

Specific examples of R ³ include —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₂ CH _{3 and the} like.

Specific examples of R ⁴ _{are, -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH _{2 CH 3) -, - CH} 2 CH 2 CH 2 CH 2 -, - CH (CH 2 CH 2 CH 3) - , and the like.

  In the above formula 1, X is preferably an alkylene group having 2 to 4 carbon atoms from the viewpoint of availability.

  Specific examples of the monomer represented by the above formula 1 include perfluorohexylethyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, and the like.

  The monomer represented by Formula 1 may be used alone or in combination of two or more.

When R ^f is a C 4-6 perfluoroalkyl group, the fluororesin (A) has good compatibility with the other components of the resist composition, and the resist composition is applied to form a coating film. When the fluorinated resin (A) is formed, the fluororesin (A) does not aggregate. Therefore, the appearance is good without the coating film becoming cloudy, and the adhesion between the coating film and the substrate is enhanced. When ^Rf is a perfluoroalkyl group having 3 or less carbon atoms, the water / oil repellency of the coating film is lowered. On the other hand, when R ^f is a perfluoroalkyl group having 7 or more carbon atoms, the fluorine-containing resin has poor compatibility with other components of the resist composition, and when the coating film is formed by coating, As a result of agglomeration, the coating film becomes cloudy or the adhesion between the coating film and the substrate is lowered.

  When using a fluororesin (A) in the 1st composition of this invention, it is preferable that a fluororesin (A) has a carboxyl group and / or a hydroxyl group. This is because the fluororesin (A) is immobilized on the surface of the coating film, and the durability of water and oil repellency increases. The carboxyl group and / or hydroxyl group of the fluororesin (A) undergoes a crosslinking reaction with a reactive group capable of crosslinking with the carboxyl group and / or phenolic hydroxyl group of the acid crosslinking agent (D), and the hydroxyl group is a carboxyl group. And / or the fluorine-containing resin (A) is immobilized on the surface of the coating film by interacting with an alkali-soluble resin (C) having a phenolic hydroxyl group or an acid crosslinking agent (D) such as hydrogen bonding. Conceivable.

  The fluorine-containing resin (A) having a carboxyl group and / or a hydroxyl group is a monomer represented by the formula 1, an ethylenically unsaturated monomer having a carboxyl group, and / or an ethylenically unsaturated monomer having a hydroxyl group. It can be obtained by copolymerizing with the body.

  The fluororesin (A) having a carboxyl group and / or a hydroxyl group is obtained by copolymerizing the monomer represented by Formula 1 and an ethylenically unsaturated monomer having a specific reactive site. The polymer can also be obtained by a modification method in which a compound capable of reacting with the specific reactive site is reacted. As a method for introducing a carboxyl group, for example, (1) a method in which an ethylenically unsaturated monomer having a hydroxyl group is copolymerized in advance and then an acid anhydride is reacted; (2) an acid anhydride having an ethylenic double bond is used. A method in which a compound having a hydroxyl group is reacted later, (3) an ethylenically unsaturated monomer having an epoxy group is copolymerized in advance, and a compound having a carboxyl group is subsequently reacted; The method of reacting a thing is mentioned. Examples of the method for introducing a hydroxyl group include a method in which an ethylenically unsaturated monomer having an epoxy group is copolymerized in advance and a compound having a carboxyl group is reacted later.

  Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These may be used alone or in combination of two or more.

  Among the ethylenically unsaturated monomers having a hydroxyl group, ethylenically unsaturated monomers having an alcoholic hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 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, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, - hydroxyethyl allyl ether, N- hydroxymethyl (meth) acrylamide, N, N- bis (hydroxymethyl) (meth) acrylamide. These may be used alone or in combination of two or more.

The ethylenically unsaturated monomer having an alcoholic hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _k H (where k is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) k H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) k H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) k H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n H (where m is an integer from 0 to 100, n is an integer from 1 to 100, and m + n is 1 to 100. hereinafter the _{same.), CH 2 = C (} CH 3) COOC 2 H 4 O (C 2 H 4 O) m (C 3 H 6 O) n H , and the like.

  Among the ethylenically unsaturated monomers having a hydroxyl group, examples of the ethylenically unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and the like. More than one hydrogen atom is substituted with an alkyl group such as methyl, ethyl and n-butyl, one or more hydrogen atoms of an alkoxy group such as methoxy, ethoxy and n-butoxy, a halogen atom and an alkyl group. Examples include compounds substituted with a haloalkyl group, a nitro group, a cyano group, and an amide group. These may be used alone or in combination of two or more.

  Examples of the acid anhydride include acid anhydrides of compounds having two or more carboxyl groups in one molecule such as pivalic anhydride and trimellitic anhydride.

  Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride. Examples thereof include acid anhydrides having an ethylenic double bond, such as acid, cis-1,2,3,6-tetrahydrophthalic anhydride, and 2-buten-1-ylsuccinic anhydride.

  Examples of the compound having a hydroxyl group include the specific examples of the ethylenically unsaturated monomer having the hydroxyl group shown above, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and ethylene glycol, 2-methoxy Cellsorbs such as ethanol, 2-ethoxyethanol and 2-butoxyethanol; carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol Etc. Of these, compounds having one hydroxyl group are preferred.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

  Examples of the compound having a carboxyl group include the specific examples of the ethylenically unsaturated monomer having the carboxyl group shown above, and methanoic acid, ethanoic acid, propionic acid, pentanoic acid, 2-methylbutanoic acid, dodecanoic acid, cyclohexanecarboxylic acid. Saturated aliphatic carboxylic acids such as acids, 2-butenoic acid, cis-9-octadecenoic acid, unsaturated aliphatic carboxylic acids such as cis, cis-9,12-octadecadienoic acid, benzoic acid, m-toluic acid, Examples include aromatic carboxylic acids such as o-nitrobenzoic acid, 3-phenylpropanoic acid, 3- (p-chlorophenyl) butanoic acid, phthalic acid, isophthalic acid, and salicylic acid.

  When the fluororesin (A) is used in the second composition of the present invention, the fluororesin (A) preferably has an ethylenic double bond. This is because the fluorine-containing resin (A) undergoes a crosslinking reaction with the alkali-soluble resin (F) and the radical crosslinking agent (G) and is immobilized on the surface of the coating film, and the coating film is excellent in water and oil repellency durability.

  Examples of the ethylenic double bond include addition polymerizable unsaturated groups such as a (meth) acryloyl group, an allyl group, a vinyl group, and a vinyl ether group. A (meth) acryloyl group is preferred because of its high reactivity to ultraviolet rays.

  The fluororesin (A) having an ethylenic double bond is a polymer obtained by copolymerizing the monomer represented by Formula 1 and an ethylenically unsaturated monomer having a specific reactive site. Further, it can be obtained by various modification methods in which a compound capable of reacting with the specific reactive site is reacted.

  For example, (1) a method in which an ethylenically unsaturated monomer having a hydroxyl group is copolymerized in advance and then an acid anhydride having an ethylenic double bond is reacted; (2) an ethylenically unsaturated monomer having a hydroxyl group A method in which an ethylenically unsaturated monomer having an isocyanate group is reacted later, (3) an ethylenically unsaturated monomer having a hydroxyl group is copolymerized in advance, and an ethylenic group having an acyl chloride group is subsequently obtained. A method of reacting an unsaturated monomer, (4) a method of previously copolymerizing an acid anhydride having an ethylenic double bond, and subsequently reacting an ethylenically unsaturated monomer having a hydroxyl group, (5) a carboxyl group A method of copolymerizing an ethylenically unsaturated monomer having a prepolymer and later reacting with an ethylenically unsaturated monomer having an epoxy group, (6) epoxy It was preliminarily copolymerizing an ethylenically unsaturated monomer having a method of reacting an ethylenically unsaturated monomer having a carboxyl group after.

  Specific examples of an ethylenically unsaturated monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, an ethylenically unsaturated monomer having a carboxyl group, and an ethylenically unsaturated monomer having an epoxy group Specific examples described above can be given.

  Specific examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate.

  Specific examples of the ethylenically unsaturated monomer having an acyl chloride group include (meth) acryloyl chloride.

  The fluorine-containing resin (A) includes a monomer unit formed from the monomer represented by the above formula 1, a monomer unit having a carboxyl group, a monomer unit having a hydroxyl group, and an ethylenic double bond. You may have monomer units (other monomer units) other than the monomer unit to have.

  Other monomers that can form monomer units include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, Examples include (meth) acrylamides, aromatic vinyl compounds, chloroolefins, and conjugated dienes. These compounds may contain a functional group, and examples thereof include a carbonyl group and an alkoxy group. In particular, (meth) acrylic acid esters and (meth) acrylamides are preferable because they are excellent in heat resistance of a coating film formed from a resist composition.

  Specific examples of (meth) acrylic acid esters include 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, (1,1-dimethyl-3-oxobutyl) (meth) acrylate, 2-acetoacetoxyethyl (meth) Acrylate 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate.

  Specific examples of (meth) acrylamides include (meth) acrylamide, N-vinylacetamide, N-vinylformamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N-methoxymethyl (meta ) Acrylamide, N, N-bis (methoxymethyl) (meth) acrylamide and the like.

  The fluorine-containing resin (A) can be synthesized, for example, by a method in which a monomer component is dissolved in a solvent, heated as necessary, and a polymerization initiator is added to react. In the reaction, a chain transfer agent is preferably present as necessary. You may add a monomer component, a polymerization initiator, a solvent, and a chain transfer agent continuously.

  Examples of the solvent in the synthesis method include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol, ketones such as acetone, methyl isobutyl ketone, and cyclohexanone, 2-methoxyethanol, and 2-ethoxy. Cellsolves such as ethanol and 2-butoxyethanol, carbitols such as 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol and 2- (2-butoxyethoxy) ethanol, methyl acetate, ethyl Acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, glycerin Esters such as triacetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether.

  Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent.

  Examples of chain transfer agents include n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol and the like, chloroform, carbon tetrachloride, and four odors. And halogenated alkyls such as carbon halides.

  The fluorine atom content in the fluororesin (A) is 7 to 35% by mass, and the ratio of the fluororesin (A) in the total solid content of the composition is 0.1 to 30% by mass. Within such a range, the fluororesin (A) is excellent in the effect of lowering the surface tension of the coating film to be formed, and imparts high water and oil repellency to the coating film. On the other hand, if it is within the range, the fluorine-containing resin (A) has good compatibility with other components of the resist composition, and when the coating film is formed by coating, Will not agglomerate. Therefore, the appearance is good without the coating film becoming cloudy, and the adhesion between the coating film and the substrate is enhanced. The lower limit of the fluorine atom content in the fluororesin (A) is preferably 10% by mass, and the upper limit is preferably 30% by mass. The lower limit of the proportion of the fluororesin (A) in the total solid content of the composition is preferably 0.2% by mass, and the upper limit is preferably 20% by mass. In particular, when the ratio of the fluororesin (A) in the total solid content of the composition is 0.2% by mass or more, the coating film is excellent in water and oil repellency.

  When the fluorine-containing resin (A) contains a carboxyl group, the acid value of the fluorine-containing resin (A) is preferably 1 to 150 mgKOH / g, more preferably 5 to 120 mgKOH / g. When it is 1 mgKOH / g or more, the water and oil repellency persistence by immobilizing the fluororesin (A) on the coating film based on the crosslinking reaction with the acid crosslinking agent (D) becomes good. On the other hand, when it is 150 mgKOH / g or less, the solubility of the fluororesin (A) in the alkali developer does not become excessively large, and there is no fear that the alkali developer will wash away the coating film. The acid value is the mass (unit: mg) of potassium hydroxide required to neutralize 1 g of the fluororesin, and the unit is described as mgKOH / g in this specification.

  When the fluorine-containing resin (A) contains a hydroxyl group, the hydroxyl value of the fluorine-containing resin (A) is preferably 50 to 300 mgKOH / g, more preferably 100 to 250 mgKOH / g. When the hydroxyl value is within this range, the durability of water and oil repellency is improved by immobilizing the fluororesin (A) on the coating film based on the crosslinking reaction with the acid crosslinking agent (D). The hydroxyl value is the mass (unit: mg) of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxyl group contained in 1 g of resin. In this specification, the unit is mgKOH. / G.

  The proportion of other monomers in the monomer component is preferably 70% by mass or less, and more preferably 60% by mass or less. Within this range, the alkali developability of the resist composition will be good.

  As for the weight average molecular weight of a fluorine-containing resin (A), 4000-18000 are preferable. The lower limit is more preferably 5000, and the upper limit is more preferably 15000. Within this range, the resist composition containing the fluororesin (A) has good alkali developability. In the present specification, the alkali developability means that the resist composition of the present invention is applied, exposed to light having a wavelength of 100 to 600 nm through a photomask, and then immersed in an alkali developer to form a fine pattern. A possible property. When the weight average molecular weight is 18000 or less, there is an advantage that the solubility in a developing solution is high, the generation of a dissolution residue in an unexposed portion can be prevented, and the change in contrast due to exposure becomes large. On the other hand, when the weight average molecular weight is 4000 or more, the compatibility of the fluororesin (A) with the other components of the resist composition is good, and the fluororesin ( A) There is no aggregation between each other. Therefore, the appearance is good without the coating film becoming cloudy, and the adhesion between the coating film and the substrate is enhanced.

  As the photosensitive component that reacts with light having a wavelength of 100 to 600 nm, which is blended with the fluororesin (A) of the present invention, any known resist composition used in photolithography can be used regardless of whether it is negative or positive. Can be used without restriction. It is preferable that the photosensitive component does not substantially contain a fluorine atom.

<First composition>
Hereinafter, the 1st composition which is one of the preferable aspects as a resist composition of this invention is demonstrated.

  The first composition of the present invention contains a photoacid generator (B). The photoacid generator (B) is a compound that generates an acid by light. Examples of the photoacid generator (B) include diaryliodonium salts, triarylsulfonium salts, triazine compounds, sulfonyl compounds, sulfonic acid esters, and the like.

  Specific examples of the cation moiety of the diaryliodonium salt include diphenyliodonium, 4-methoxyphenylphenyliodonium, bis (4-t-butylphenyl) iodonium, and the like. Specific examples of the anion moiety of the diaryliodonium salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate and the like. The diaryliodonium salt consists of a combination of one of the cation moieties and one of the anion moieties. For example, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate.

  Specific examples of the cation moiety of the triarylsulfonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, diphenyl-2,4,6-trimethylphenylsulfonium, and the like. Specific examples of the anion moiety of the triarylsulfonium salt include specific examples of the anion moiety of the diaryl iodonium salt. A triarylsulfonium salt consists of a combination of one of the cation moieties and one of the anion moieties. For example, triphenylsulfonium trifluoromethanesulfonate.

  Specific examples of the triazine compound include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (2-furyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (5-methyl-2-furyl) ethenyl-bis (trichloromethyl)- 1,3,5-triazine, 2- (3,4-dimethoxyphenyl) ethenyl-bis (trichloromethyl) -1,3,5-triazine, 2- (1,3benzodioxol-5-yl)- Examples include 4,6-bis (trichloromethyl) -1,3,5 triazine.

  Specific examples of the sulfonyl compound include bis (phenylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like.

  Specific examples of the sulfonic acid esters include 2-nitrobenzyl p-toluenesulfonate, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, and the like.

  The proportion of the photoacid generator (B) in the total solid content of the composition is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass. Within this range, the alkali developability of the resist composition will be good.

  The 1st composition of this invention contains alkali-soluble resin (C) which has a carboxyl group and / or a phenolic hydroxyl group. Acid cross-linking agent (D) which is a compound having two or more groups which are soluble in an alkali developer by having a carboxyl group and / or a phenolic hydroxyl group, and which can react with a carboxyl group and / or a phenolic hydroxyl group And the coating film becomes insoluble in an alkaline developer.

  Examples of the alkali-soluble resin (C) include a vinyl polymer (C1) and a novolak resin (C2) containing a monomer unit having a carboxyl group and / or a monomer unit having a phenolic hydroxyl group. These resins are preferably substantially free of fluorine atoms.

  Specific examples of the monomer capable of forming a monomer unit having a carboxyl group and the monomer capable of forming a monomer unit having a phenolic hydroxyl group in the vinyl polymer (C1) include a fluororesin ( Specific examples of the ethylenically unsaturated monomer having a carboxyl group and the ethylenically unsaturated monomer having a phenolic hydroxyl group described in A) can be given.

  The vinyl polymer (C1) containing a monomer unit having a carboxyl group and / or a monomer unit having a phenolic hydroxyl group is other than a monomer unit having a carboxyl group and a monomer unit having a phenolic hydroxyl group. Monomer units (other monomer units) may be contained. Examples of other monomers that can form monomer units include specific examples of other monomers described in the fluororesin (A).

  In the vinyl polymer (C1), the proportion of other monomer units is preferably 70% by mass or less, more preferably 60% by mass or less in the polymer. Within this range, the alkali solubility and alkali developability of the resist composition are good.

  The vinyl polymer (C1) can be synthesized, for example, by a method in which a monomer component is dissolved in a solvent and heated, and a polymerization initiator is added to react. A chain transfer agent is preferably present as required. As the polymerization initiator, the solvent and the chain transfer agent, those exemplified for the fluororesin (A) can be used.

  The novolac resin (C2) is obtained by polycondensation of phenols with aldehydes. Specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol. , Catechol, resorcinol, hydroquinone, methyl hydroquinone, pyrogallol, phloroglicinol and the like. As the aldehyde, formaldehyde is preferable. As the novolak resin (C2), for example, phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde co-condensation resin and the like are preferable.

  10-600 mgKOH / g is preferable and, as for the acid value of alkali-soluble resin (C), 50-300 mgKOH / g is more preferable. Within this range, the alkali developability of the resist composition will be good.

  200-50000 are preferable and, as for the weight average molecular weight of alkali-soluble resin (C), 2000-30000 are more preferable. Within this range, the alkali developability of the resist composition will be good.

  10-90 mass% is preferable, and, as for the ratio of alkali-soluble resin (C) in the total solid of a composition, 30-80 mass% is more preferable. Within such a range, the alkali developability of the resist composition is good.

  The 1st composition of this invention contains the acid crosslinking agent (D) which is a compound which has two or more groups which can react with a carboxyl group and / or a phenolic hydroxyl group by the effect | action of an acid. Having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group causes a crosslinking reaction with the alkali-soluble resin (C) having a carboxyl group and / or a phenolic hydroxyl group, and the coating film is insoluble in an alkali developer. It becomes. Further, when the fluorine-containing resin (A) has a carboxyl group and / or a hydroxyl group, the fluorine-containing resin (A) is immobilized on the surface of the coating film, and the durability of water and oil repellency increases. The acid crosslinking agent (D) is preferably a compound that does not substantially contain a fluorine atom.

  The acid crosslinking agent (D) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, and oxazoline compounds. These compounds may be used alone or in combination of two or more.

  As the amino resin, a compound obtained by hydroxymethylating a part or all of an amino group such as a melamine compound, a guanamine compound or a urea compound, or a part or all of a hydroxyl group of the hydroxymethylated compound is methanol, A compound etherified with ethanol, n-butyl alcohol, 2-methyl-1-propanol, etc., for example, hexamethoxymethyl melamine, etc. may be mentioned.

  Epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol / novolak type epoxy resins, cresol / novolac type epoxy resins, trisphenol methane type epoxy resins, brominated epoxy resins and other glycidyl ethers, 3, Alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, glycidyl such as diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl phthalate Heterocycles such as esters, tetraglycidyldiaminodiphenylmethane, glycidylamines such as triglycidylparaaminophenol, and triglycidyl isocyanurate And epoxy resins.

  As the oxazoline compound, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl Examples thereof include copolymers of polymerizable monomers such as -4-methyl-2-oxazoline.

  1-50 mass% is preferable and, as for the ratio of the acid crosslinking agent (D) in the total solid of a composition, 5-30 mass% is more preferable. Within this range, the alkali developability of the resist composition will be good.

<Second composition>
Hereinafter, the 2nd composition which is one of the preferable aspects as a resist composition of this invention is demonstrated.

  The second composition of the present invention contains a photoradical initiator (E). The photo radical initiator (E) is a compound that generates radicals by light.

  Examples of the photo radical initiator (E) include benzyl, diacetyl, methylphenylglyoxylate, α-diketones such as 9,10-phenanthrenequinone, acyloins such as benzoin, benzoin methyl ether, and benzoin ethyl ether. , Acyloin ethers such as benzoin isopropyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4 -Thioxanthones such as diisopropylthioxanthone and thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophene Benzophenones such as acetone, acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, anthraquinone, 2-ethyl Quinones such as anthraquinone, camphorquinone, 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), 4-dimethylaminobenzoic acid Isoamyl, 4-dimethylamino Examples thereof include aminobenzoic acids such as 2-ethylhexyl benzoate, halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone, peroxides such as acylphosphine oxides and di-t-butyl peroxide.

  In particular, the aminobenzoic acids, the benzophenones and the like may be used together with other radical initiators to develop a sensitizing effect. In addition, aliphatic amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, and diethylaminoethyl methacrylate may also be used together with a radical initiator to exhibit a sensitizing effect. .

  0.1-50 mass% is preferable and, as for the ratio of the photoradical initiator (E) in the total solid of a composition, 0.5-30 mass% is more preferable. Within such a range, the alkali developability of the resist composition is good.

  The 2nd composition of this invention contains alkali-soluble resin (F) which has an acidic group and two or more ethylenic double bonds in 1 molecule. It is soluble in an alkali developer by having an acidic group. Further, by having two or more ethylenic double bonds, the alkali-soluble resin (F) cross-links with each other, or has an alkali-soluble resin (F) and two or more ethylenic double bonds, and It crosslinks with the radical crosslinking agent (G) having no acidic group, and the coating film becomes insoluble in an alkaline developer.

  Examples of the acidic group include at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group, or a salt thereof.

  Examples of the ethylenic double bond include addition polymerizable unsaturated groups such as a (meth) acryloyl group, an allyl group, a vinyl group, and a vinyl ether group. A (meth) acryloyl group is preferred because of its high reactivity to ultraviolet rays.

  Examples of the alkali-soluble resin (F) include a vinyl polymer (F1) containing a monomer unit having an acidic group and a monomer unit having an ethylenic double bond, and an ethylenic double bond introduced. A novolac resin (F2) may be mentioned. These resins are preferably substantially free of fluorine atoms.

  Among the ethylenically unsaturated monomers having an acidic group capable of forming a monomer unit having an acidic group in the vinyl polymer (F1), an ethylenically unsaturated monomer having a carboxyl group, a phenolic hydroxyl group. Specific examples of the ethylenically unsaturated monomer include the specific examples described in the fluororesin (A).

  Examples of the ethylenically unsaturated monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid 2-sulfoethyl. 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, Or the salt etc. are mentioned.

  Examples of the ethylenically unsaturated monomer having a phosphate group include 2- (meth) acryloyloxyethanephosphoric acid or a salt thereof.

  In the vinyl polymer (F1), the monomer unit having an ethylenic double bond is obtained by polymerizing an ethylenically unsaturated monomer having a specific reactive site to the specific reactivity. It can be formed by a modification method in which a compound capable of reacting with a site is reacted. Examples of the modification method and specific examples of the compound used in the modification method include the same specific examples as described for the fluororesin (A).

  The vinyl polymer (F1) may contain a monomer unit other than the monomer unit having an acidic group and the monomer unit having an ethylenic double bond (other monomer units). . Examples of other monomers that can form monomer units include the same specific examples as described for the fluororesin (A).

  In the vinyl polymer (F1), the proportion of other monomer units is preferably 70% by mass or less, more preferably 50% by mass or less in the polymer. Within this range, the alkali solubility and alkali developability of the resist composition are good.

  The novolak resin of the novolak resin (F2) introduced with the ethylenic double bond is at least selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol and hydroquinone, and alkyl-substituted or halogen-substituted aromatic compounds thereof. It is obtained by polycondensation of one kind of phenols with aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde, such as phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde co-condensation resin, etc. It is done. In particular, when a cresol / formaldehyde resin type is employed, the wettability of the substrate surface to the ink after washing and removing the composition by development is favorable.

  As a method for introducing an ethylenic double bond into the novolac resin, a method in which a compound having an epoxy group and an ethylenic double bond is reacted with a part of the phenolic hydroxyl group of the novolak resin, the phenolic hydroxyl group of the novolak resin is reacted. A method of reacting a compound having a carboxyl group and an ethylenic double bond with the epoxy group after an epoxy group is introduced into a novolak resin by reacting part or all with epichlorohydrin can be mentioned. Furthermore, a hydroxyl group formed by the reaction of the epoxy group and the carboxyl group can be reacted with an acid anhydride to introduce a carboxyl group into the novolak resin.

  Examples of commercially available novolak resins (F2) having an ethylenic double bond introduced include KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, TCR-1025, TCR-1064, TCR-1286, ZFR- 1122, ZFR-1124, ZFR-1185 (above, Nippon Kayaku Co., Ltd.) and the like.

  The alkali-soluble resin (F) preferably has 6 or more ethylenic double bonds in one molecule. Thereby, the difference in alkali solubility between the exposed portion and the unexposed portion is likely to be different, and a fine pattern can be formed with a smaller exposure amount.

  The alkali-soluble resin (F) preferably has a carboxyl group and / or a hydroxyl group as a group capable of undergoing a crosslinking reaction. When the second composition further contains a thermal crosslinking agent (H) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group, the alkali-soluble resin (F) is crosslinked with a heat treatment after development. This is because they react to increase the cross-linking density of the coating film and improve the heat resistance. A carboxyl group and a phenolic hydroxyl group that are acidic groups are groups that can undergo a crosslinking reaction. When the alkali-soluble resin (F) has a sulfonic acid group or a phosphoric acid group as an acidic group, it may have any one or more of a carboxyl group, a phenolic hydroxyl group, and an alcoholic hydroxyl group as a group capable of crosslinking reaction. preferable.

  10-300 mgKOH / g is preferable and, as for the acid value of alkali-soluble resin (F), 30-150 mgKOH / g is more preferable. Within such a range, the alkali developability of the resist composition is good.

  1000-50000 is preferable and, as for the weight average molecular weight of alkali-soluble resin (F), 2000-30000 is more preferable. Within this range, the alkali solubility and alkali developability of the resist composition are good.

  5-80 mass% is preferable and, as for the ratio of alkali-soluble resin (F) in the total solid of a composition, 10-50 mass% is more preferable. Within such a range, the alkali developability of the resist composition is good.

  It is preferable that the 2nd composition of this invention contains the radical crosslinking agent (G) which is a compound which has a 2 or more ethylenic double bond, and does not have an acidic group. Thereby, hardening of the resist composition by light irradiation is accelerated | stimulated, and hardening in a shorter time is attained.

  Specific examples of the radical crosslinking agent (G) include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Etc. These may be used alone or in combination of two or more.

  10-60 mass% is preferable and, as for the ratio of the radical crosslinking agent (G) in the total solid of a composition, 15-50 mass% is more preferable. Within this range, the alkali developability of the resist composition will be good.

  It is preferable that the 2nd composition of this invention further contains the thermal crosslinking agent (H) which is a compound which has two or more groups which can react with a carboxyl group and / or a hydroxyl group by the effect | action of a heat | fever. When the alkali-soluble resin (F) has a carboxyl group and / or a hydroxyl group, the heat-crosslinking agent (H) reacts with the alkali-soluble resin (F) by heating (for example, 120 to 250 ° C.) to reduce the crosslinking density of the coating film. It is possible to increase the heat resistance.

  The thermal crosslinking agent (H) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds. These compounds may be used alone or in combination of two or more.

  Specific examples of the amino resin, the epoxy compound, and the oxazoline compound include those shown for the acid crosslinking agent (D).

  As the polyisocyanate compound, the isocyanate group was blocked with a polyisocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate, a silyl isocyanate compound such as methylsilyl triisocyanate and / or a condensate or multimer thereof, or a blocking agent such as phenol. Examples thereof include blocked polyisocyanate compounds.

  The polycarbodiimide compound is obtained by a known carbon dioxide condensation reaction of organic diisocyanate. At this time, phosphoric acid compounds such as trimethyl phosphate and triethyl phosphate can be used as a known catalyst. In addition, a nonionic hydrophilic polycarbodiimide compound can be obtained by using a mixture of an organic diisocyanate and a hydroxyl group-containing polyethylene glycol.

  1-50 mass% is preferable and, as for the ratio of the thermal crosslinking agent (H) in the total solid of a resin composition, 5-30 mass% is more preferable. Within this range, the alkali developability of the resist composition will be good.

  Hereinafter, other components that can be commonly used in the first composition and the second composition will be described.

  In the resist composition of the present invention, it is preferable to use a silane coupling agent (I) as necessary. When a silane coupling agent is used, the substrate adhesion of the coating film formed from the composition is improved.

  Specific examples of the silane coupling agent (I) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl. Examples include trimethoxysilane, 3-mercaptopropyltrimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used alone or in combination of two or more.

  In the resist composition of the present invention, a diluent (J) can be used. Specific examples of the diluent (J) include the solvents exemplified as the synthesis solvent for the fluororesin (A). Other examples include chain hydrocarbons such as n-butane and n-hexane, cyclic saturated hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene, xylene, and benzyl alcohol. These may be used alone or in combination of two or more.

  In the resist composition of the present invention, a curing accelerator, a colorant, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber and the like can be used as necessary. Examples of the colorant include dyes, organic pigments, inorganic pigments, metallic pigments and the like.

  The resist composition mixed with the colorant can be used as a material for forming a light-shielding coating film. For example, as a partition material for a color filter, a resist composition capable of forming a black coating film is applied in order to increase the contrast of RGB emission colors.

  As the black colorant, carbon black, titanium black, and a black metal oxide pigment are preferable. A combination in which two or more organic pigments selected from red, blue, green, purple, yellow, cyan, magenta, and the like are mixed and blackened is also preferable.

Examples of carbon black include lamp black, acetylene black, thermal black, channel black, and furnace black. Titanium black is obtained by oxidation of titanium or reduction of titanium dioxide, and is at least one kind represented by Ti _u O _2u-1 (u is a number of 1 or more). Examples of black metal oxide pigments include copper, iron, chromium, manganese, and cobalt oxides. A composite metal oxide of at least two or more selected from the metal oxides is also preferable. Examples thereof include copper-chromium oxide, copper-chromium-manganese oxide, copper-iron-manganese oxide, and cobalt-iron-manganese oxide.

  Blue pigments are phthalocyanine pigments, red pigments are quinacridone pigments, perylene pigments, pyrrolo-pyrrole pigments, anthraquinone pigments, etc., and green pigments are halogenated phthalocyanine pigments, etc. Examples of pigments include dioxazine violet, fast violet B, methyl violet equine, indanthrene brilliant violet, and yellow pigments include tetrachloroisoindolinone pigments, Hansairo pigments, benzidine yellow pigments, azo pigments, Examples of cyan pigments include metal-free phthalocyanine and merocyanine, and examples of magenta pigments include dimethylquinacridone and thioindigo.

  The pigment may be dispersed together with a dispersant (for example, a polycaprolactone compound, a long-chain alkylpolyaminoamide compound, etc.) by a disperser such as a sand mill or a roll mill, and then added to the composition. The particle size is preferably 1 μm or less. Within such a range, the alkali developability of the composition becomes good.

  Hereinafter, a photolithography process using the composition of the present invention will be described.

  First, the composition of the present invention is applied to a substrate. The material of the substrate is not particularly limited. For example, various glass plates, polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, thermoplastics such as polycarbonate, polymethyl methacrylate, polysulfone, and polyimide. Examples thereof include a thermosetting plastic sheet such as a sheet, an epoxy resin, a polyester resin, and a poly (meth) acrylic resin. In particular, a heat-resistant plastic such as a glass plate or polyimide is preferably used from the viewpoint of heat resistance.

  Examples of the method for forming a coating film include a spray method, a roll coating method, a spin coating method, and a bar coating method.

  Next, the coating film is dried (hereinafter referred to as pre-baking). By pre-baking, the solvent is volatilized and a non-fluid coating film is obtained. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but it can be used in a wide range of preferably about 50 to 120 ° C. and about 10 to 2000 seconds.

Next, the heated coating film is exposed through a mask having a predetermined pattern. The light used is a light beam having a wavelength of 100 to 600 nm, preferably an electromagnetic wave having a distribution in the range of 300 to 500 nm, and particularly preferably i-line (365 nm), h-line (405 nm), and g-line (436 nm). Specific examples include laser light such as visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, and F ₂ excimer laser. However, when irradiating light with a short wavelength, since the energy is strong, the composition component of the exposed part may decompose | disassemble depending on irradiation time. Accordingly, light having an ultraviolet wavelength or more is preferable, and as such a light source, an ultra-high pressure mercury lamp widely used widely for exposure apparatus applications can be mentioned. Usually, it is preferable to expose in the range of the exposure amount of 5 to 1000 mJ / cm ² .

  Next, in the case of a chemically amplified resist composition such as the first composition of the present invention, an acid is diffused as necessary, and PEB treatment for accelerating the crosslinking reaction is performed. Develop and remove unexposed areas. The PEB treatment conditions vary depending on the type of each component, the blending ratio, and the like, but preferably can be used in a wide range of about 50 to 150 ° C. and about 10 to 2000 seconds.

  Then, it develops with a developing solution and an unexposed part is removed. As the developing solution, for example, an alkaline aqueous solution composed of alkalis such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts can be used.

  The development time is preferably 5 to 180 seconds. Further, the developing method may be either a liquid piling method or a dipping method. After development, the substrate is washed with running water and air-dried with compressed air or compressed nitrogen to remove moisture on the substrate. Subsequently, a pattern is formed by heat treatment (hereinafter referred to as post-bake treatment) for 5 to 90 minutes, preferably at 120 to 250 ° C., using a heating device such as a hot plate or oven.

  The resist composition of the present invention is preferably used for pattern formation of 100 μm or less, and is preferably used for pattern formation of 50 μm or less.

  The water / oil repellency of the coating film can be estimated by the contact angle of water and xylene. The contact angle of water is preferably 80 ° or more, more preferably 90 ° or more. The contact angle of xylene is preferably 30 degrees or more, and more preferably 35 degrees or more.

  Although it demonstrates based on a reference example (Examples 1-4), an Example (9-18), and a comparative example (Examples 5-8, 19-23) below, this invention is not limited to these. In the following, unless otherwise specified, the parts are based on mass.

  The weight average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.

  The content of fluorine atoms contained in the fluororesin was measured by the following method. The obtained fluorine-containing resin was completely burned and decomposed at 1200 ° C., and the generated gas was absorbed in 50 g of water. The amount of fluoride ions in the obtained aqueous solution was quantified, and the content of fluorine atoms contained in the fluororesin was calculated.

  The acid value (mgKOH / g), hydroxyl value (mgKOH / g), and the number of ethylenic double bonds in one molecule are theoretical values calculated from the blending ratio of the monomer components.

  The abbreviations of the compounds used in the following examples are shown below.

_{C4FMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF 2) 4 F
_{C6FMA: CH 2 = C (CH} 3) COOCH 2 CH 2 (CF 2) 6 F
_{C8FA: CH 2 = CHCOOCH 2 CH} 2 (CF 2) 8 F
MAA: methacrylic acid, 2-HEMA: 2-hydroxyethyl methacrylate, MMA: methyl methacrylate, CHMA: cyclohexyl methacrylate, IBMA: isobornyl methacrylate,
V-70: 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2-ME: 2-mercaptoethanol,
MOI: 2-methacryloyloxyethyl isocyanate, DBTDL: dibutyltin dilaurate, BHT: 2,6-di-t-butyl-p-cresol,
MP triazine: 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5 triazine TAZ-107: 2- (1,3benzodioxol-5-yl) -4, 6-bis (trichloromethyl) -1,3,5 triazine (manufactured by Midori Chemical Co., Ltd., trade name TAZ-107)
WPAG199: Bis (p-toluenesulfonyl) diazomethane (manufactured by Wako Pure Chemical Industries, trade name WPAG-199)
NW-100LM: Methyl etherified melamine copolymer (manufactured by Sanwa Chemical Co., Ltd., trade name Nicalak NW-100LM)
IR907: radical initiator (trade name IRGACURE-907, manufactured by Ciba-Geigy)
IR369: radical initiator (trade name IRGACURE-369, manufactured by Ciba-Geigy)
DEAB: 4,4′-bis (diethylamino) benzophenone DETX-S: isopropylthioxanthone (trade name DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
CCR1115: Cresol formaldehyde type copolymer (manufactured by Nippon Kayaku Co., Ltd., trade name CCR-1115: solid content 60 mass%, average number of ethylenic double bonds per molecule is 10)
D310: Dipentaerythritol pentaacrylate: (Nippon Kayaku Co., Ltd., trade name KAYARAD D-310)
157S65: Bisphenol A novolak type (Japan Epoxy Resin, trade name Epicoat 157S65)
KBM403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-403)
DEGDM: Diethylene glycol dimethyl ether CB: Carbon black (average particle size = 120 nm, propylene glycol monomethyl ether acetate solution, solid content 20% by mass).

[Synthesis Example 1]
<Synthesis of fluororesin (A-1)>
To a 1 L internal reaction vessel equipped with a stirrer, acetone (556.0 g), C6FMA (96.0 g), 2-HEMA (96.0 g), MMA (48.0 g), chain transfer agent 2-ME ( 6.2 g) and a polymerization initiator V-70 (4.5 g) were charged and polymerized at 40 ° C. for 18 hours while stirring in a nitrogen atmosphere to obtain a solution of the fluororesin (A-1). Water was added to the acetone solution of the obtained fluororesin (A-1) for reprecipitation purification, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain 238 g of fluororesin (A-1). . The weight average molecular weight was 5600.

[Synthesis Examples 2 to 12]
<Synthesis of fluororesin (A-2) to (A-9), (R-1) to (R-3)>
In the synthesis of the fluorine-containing resin (A-1), the fluorine-containing resins (A-2) to (A-9), fluorine-containing resin ( R-1) to (R-3) were obtained.

  Table 1 shows the fluorine atom content, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) in the fluorine-containing resin.

［合成例１３］
＜含フッ素樹脂（Ａ−１０）の合成＞
温度計、撹拌機、加熱装置を備えた内容量３００ｍＬのガラス製フラスコに、含フッ素樹脂（Ａ−１）（１００ｇ）、ＭＯＩ（４７．７ｇ）、ＤＢＴＤＬ（０．１９ｇ）、ＢＨＴ（２．４ｇ）及びアセトン（１００ｇ）を仕込み、撹拌しながら、３０℃で１８時間重合させ、含フッ素樹脂（Ａ−１０）の溶液を得た。得られた含フッ素樹脂（Ａ−１０）のアセトン溶液に水を加え再沈精製し、次いで石油エーテルにて再沈精製し、真空乾燥し、含フッ素樹脂（Ａ−１０）の１４５ｇを得た。重量平均分子量は８７００であった。

[Synthesis Example 13]
<Synthesis of fluororesin (A-10)>
In a 300 mL glass flask equipped with a thermometer, a stirrer, and a heating device, fluororesin (A-1) (100 g), MOI (47.7 g), DBTDL (0.19 g), BHT (2. 4 g) and acetone (100 g) were charged and polymerized at 30 ° C. for 18 hours with stirring to obtain a solution of a fluororesin (A-10). Water was added to the obtained fluororesin (A-10) in acetone solution for purification by reprecipitation, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain 145 g of fluororesin (A-10). . The weight average molecular weight was 8,700.

[Synthesis Examples 14 to 23]
<Synthesis of fluorinated resins (A-11) to (A-17) and fluorinated resins (R-4) to (R-6)>
In the synthesis of the fluorinated resin (A-10), the fluorinated resins (A-11) to (A-17) and (R-4) were prepared by the same polymerization reaction except that the composition of the raw materials was changed as shown in Table 2. To (R-6).

  Table 2 shows the fluorine atom content in the fluorine-containing resin, the number of ethylenic double bonds in one molecule, and the acid value (mgKOH / g).

［合成例２４］
＜アルカリ可溶性樹脂（Ｃ−１）の合成＞
撹拌機を備えた内容積１Ｌの反応槽に、アセトン（５５５．０ｇ）、ＭＡＡ（３３．６ｇ）、２−ＨＥＭＡ（１３４．４ｇ）、ＩＢＭＡ（７２．０ｇ）、連鎖移動剤２−ＭＥ（３．７ｇ）及び重合開始剤Ｖ−７０（５．４ｇ）を仕込み、窒素雰囲気下に撹拌しながら、４０℃で１８時間重合させ、アルカリ可溶性樹脂（Ｃ−１）の溶液を得た。得られたアルカリ可溶性樹脂（Ｃ−１）のアセトン溶液に水を加え再沈精製し、次いで石油エーテルにて再沈精製し、真空乾燥し、アルカリ可溶性樹脂（Ｃ−１）（２３９ｇ）を得た。重量平均分子量は１００００であり、酸価は９１ｍｇＫＯＨ／ｇであった。

[Synthesis Example 24]
<Synthesis of alkali-soluble resin (C-1)>
To a 1 L reaction vessel equipped with a stirrer, acetone (555.0 g), MAA (33.6 g), 2-HEMA (134.4 g), IBMA (72.0 g), chain transfer agent 2-ME ( 3.7 g) and a polymerization initiator V-70 (5.4 g) were charged and polymerized at 40 ° C. for 18 hours while stirring in a nitrogen atmosphere to obtain a solution of an alkali-soluble resin (C-1). Water is added to the obtained acetone solution of the alkali-soluble resin (C-1) for reprecipitation purification, then reprecipitation purification with petroleum ether, and vacuum drying to obtain an alkali-soluble resin (C-1) (239 g). It was. The weight average molecular weight was 10,000, and the acid value was 91 mgKOH / g.

[Synthesis Example 25]
<Synthesis of alkali-soluble resin (F-1)>
In a glass flask having a capacity of 300 mL equipped with a thermometer, a stirrer, and a heating device, an alkali-soluble resin (C-1) (100 g), MOI (66.8 g), DBTDL (0.27 g), BHT (3. 3 g) and acetone (100 g) were charged and polymerized at 30 ° C. for 18 hours with stirring to obtain a solution of an alkali-soluble resin (F-1). The weight average molecular weight of the alkali-soluble resin (F-1) was 17100. Water was added to the obtained acetone solution of the alkali-soluble resin (F-1) for reprecipitation purification, then reprecipitation purification with petroleum ether and vacuum drying to obtain 163 g of the alkali-soluble resin (F-1). . The acid value is 55 mgKOH / g, and the number of ethylenic double bonds in one molecule is 22.

[Examples 1 to 23]
<Evaluation of resist composition>
Fluorine-containing resin (A), fluorine-containing resin (R), photoacid generator (B), alkali-soluble resin (C), acid crosslinking agent (D), and silane coupling in the proportions (parts by mass) shown in Table 3. The negative resist composition was obtained by blending the agent (I) and the diluent (J).

  Fluorine-containing resin (A), fluorine-containing resin (R), photoradical initiator (E), alkali-soluble resin (F), radical crosslinking agent (G), thermal crosslinking agent in proportions (parts by mass) shown in Table 4 (H), a silane coupling agent (I), and a diluent (J) were blended to obtain a negative resist composition.

After applying a resist composition on a glass substrate using a spinner, it was pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Next, a mask (line / space = 20 μm / 20 μm) was brought into contact with the coating film and irradiated with 150 mJ / cm ² with an ultrahigh pressure mercury lamp. Next, in Examples 1 to 8, PEB treatment was performed at 100 ° C. for 2 minutes. Next, the unexposed portion was immersed in a 0.1 mass% tetramethylammonium hydroxide aqueous solution for 40 seconds for development, and the unexposed portion was washed away with water and dried. Subsequently, the glass substrate in which the pattern was formed was obtained by heating at 220 degreeC on a hotplate for 1 hour. About this, alkali developability, coating-film external appearance, base-material adhesiveness, and water / oil repellency were measured and evaluated by the method shown below. The evaluation results are shown in Tables 3 and 4.

[Alkali developability]
Those that could be completely developed were indicated as ◯, and those that did not develop were indicated as ×.

[Appearance of coating film]
Good appearance of the coating film ○, coating film is cloudy white, bubbles marks remain on the coating film, radial streaks remain on the coating film, film thickness is not uniform, etc. X was described.

[Base material adhesion]
Evaluation was made by the cross-cut tape method described in JIS K 5400. The coating film was scratched in a grid pattern so that the number of meshes was 25 at intervals of 2 mm with a cutter. Next, the adhesion state of the coating film after the adhesive tape was applied and peeled was evaluated by visually observing that the squares were not peeled off, and the case where the squares were almost peeled off as x.

[Water and oil repellency]
The water / oil repellency was evaluated by the contact angle (degree) of water and xylene on the surface of the coating film formed on the glass substrate. The contact angle is an angle formed by a solid surface and a tangent to the liquid surface at a point where the solid and the liquid are in contact, and is defined as an angle including the liquid. The larger the angle, the better the water / oil repellency of the coating film. A water contact angle of 80 ° or more was indicated as “◯”, and less than 80 ° as “X”. The contact angle of xylene of 30 degrees or more was indicated as ◯, and the angle less than 30 degrees as x.

例５は組成物の全固形分における含フッ素樹脂（Ａ）の割合が低すぎ、塗膜の撥水撥油性に劣る。例６は組成物の全固形分における含フッ素樹脂（Ａ）の割合が高すぎ、塗膜外観、基材密着性に劣る。例７は含フッ素樹脂（Ａ）におけるフッ素原子の含有率が高すぎ、塗膜外観、基材密着性に劣る。例８は含フッ素樹脂（Ａ）におけるフッ素原子の含有率が低すぎ、撥水撥油性に劣る。

In Example 5, the proportion of the fluororesin (A) in the total solid content of the composition is too low, and the water and oil repellency of the coating film is poor. In Example 6, the ratio of the fluororesin (A) in the total solid content of the composition is too high, and the coating film appearance and the substrate adhesion are inferior. In Example 7, the fluorine atom content in the fluororesin (A) is too high, and the coating film appearance and substrate adhesion are poor. In Example 8, the fluorine atom content in the fluororesin (A) is too low and the water and oil repellency is poor.

In Example 19, the ratio of the fluororesin (A) in the total solid content of the composition is too low, and the water / oil repellency of the coating film is poor. In Example 20, the proportion of the fluorine-containing resin (A) in the total solid content of the composition is too high, and the coating film appearance and substrate adhesion are poor. In Example 21, the perfluoroalkyl group (R ^f in the above formula 1) of the fluororesin (A) has too many carbon atoms and is inferior in coating film appearance and substrate adhesion. In Example 22, the fluorine atom content in the fluororesin (A) is too high, and the coating film appearance and substrate adhesion are poor. In Example 23, the fluorine atom content in the fluororesin (A) is too low, and the water and oil repellency is poor.

  The resist composition of the present invention can be applied to uses that require water and oil repellency. For example, it is suitably used for the formation of partition walls for color filter manufacturing, organic EL display element manufacturing, and circuit wiring board manufacturing using an inkjet recording technique.

Claims (14)

Fluorine-containing resin (A) having a monomer unit formed from the monomer represented by Formula 1, having an ethylenic double bond, and a fluorine atom content of 7 to 35% by mass and a wavelength A resist composition comprising a photosensitive component that reacts with light of 100 to 600 nm,
The ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 30% by mass,
The photosensitive composition comprises a photo radical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more ethylenic double bonds in one molecule.
CH ₂ = C (R ¹ ) COOXR ^f ... Formula 1
In the formula, R ¹ represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents an organic group not containing a divalent fluorine atom having 1 to 6 carbon atoms, and R ^f represents a perfluoro group having 4 to 6 carbon atoms. A fluoroalkyl group; A fluororesin (A) having a monomer unit formed from the monomer represented by Formula 1 and having a fluorine atom content of 7 to 35% by mass and photosensitivity that reacts with light having a wavelength of 100 to 600 nm A resist composition used for forming partition walls, which contains a sex component,
  The ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 30% by mass,
  The photosensitive composition comprises a photo radical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more ethylenic double bonds in one molecule.
  CH ₂ = C (R ¹ COOXR ^f ... Formula 1
  Where R ¹ Represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents an organic group containing no C1-C6 divalent fluorine atom, R ^f Represents a C 4-6 perfluoroalkyl group. Fluorine-containing resin (A) having a monomer unit formed from the monomer represented by Formula 1, having an ethylenic double bond, and a fluorine atom content of 7 to 35% by mass and a wavelength A resist composition used for forming partition walls, comprising a photosensitive component that reacts with light of 100 to 600 nm,
  The ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 30% by mass,
  The photosensitive composition comprises a photo radical initiator (E) and an alkali-soluble resin (F) having an acidic group and two or more ethylenic double bonds in one molecule.
  CH ₂ = C (R ¹ COOXR ^f ... Formula 1
  Where R ¹ Represents a hydrogen atom, a methyl group or a trifluoromethyl group, X represents an organic group containing no C1-C6 divalent fluorine atom, R ^f Represents a C 4-6 perfluoroalkyl group. The resist composition according to any one of claims 1 to 3, wherein the photosensitive component further includes a radical crosslinking agent (G) having two or more ethylenic double bonds and having no acidic group. The alkali-soluble resin (F) has a carboxyl group and / or a hydroxyl group,
The photosensitive component according to any one of claims 1 to 4 groups capable of reacting with a carboxyl group and / or hydroxyl groups, further comprising a thermal crosslinking agent (H) is a compound having two or more by the action of heat Resist composition. The resist composition according to any one of claims 1 to 5 , further comprising a colorant. The coating film obtained from the resist composition as described in any one of Claims 1-6.   The coating film according to claim 7, wherein the contact angle of water is 80 degrees or more.   The coating film according to claim 7 or 8, wherein the contact angle of xylene is 30 degrees or more. A method of forming a partition,
Applying the resist composition according to any one of claims 1 to 6 to a substrate to form a coating film;
Pre-baking the coating film;
Exposing the pre-baked coating film;
And a step of developing the exposed coating film.   The method of forming a partition according to claim 10, wherein the partition is a partition for producing a color filter.   The method of forming a partition according to claim 10, wherein the partition is a partition for manufacturing an organic EL display element. Applying the resist composition according to any one of claims 1 to 6 to a substrate to form a coating film;
Pre-baking the coating film;
Exposing the pre-baked coating film;
Developing the exposed coating film to form a partition pattern for forming pixels; and
And a step of forming pixels by spraying ink into the pattern of the partition wall by an ink jet recording technique. Applying the resist composition according to any one of claims 1 to 6 to a substrate to form a coating film;
Pre-baking the coating film;
Exposing the pre-baked coating film;
Developing the exposed coating film to form a partition pattern for forming pixels; and
And a step of forming a pixel by spray-coating a solution of a hole transport material or a light emitting material into the pattern of the partition wall by an ink jet recording technique.