JP2005315985A - Photosensitive resin composition and film cured object thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a film cured object excellent in ink repellency, ink dropping property, adhesion to a substrate and film appearance, capable of fine pattern formation, and ensuring ink wettability of a substrate surface freed of an unexposed portion after alkali development. <P>SOLUTION: The photosensitive resin composition contains a resin (A) obtained by polymerizing monomer components including a fluorine-atom-containing monomer, a resin (B) obtained by polymerizing monomer components including a silicon-atom-containing monomer, an alkali-soluble resin (C) having an acidic group and six or more ethylenic double bonds in one molecule, and a radical initiator (D), wherein a proportion of the resin (A) to the total solid content of the photosensitive resin composition is 0.05-30 mass% and a proportion of the resin (B) is 0.01-20 mass%. A film cured object of the composition is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition and a cured film thereof.

  Conventionally, a photosensitive resin composition has been used to create a mask for manufacturing a circuit such as a semiconductor integrated circuit (IC), a thin film transistor (TFT) circuit for a liquid crystal display (LCD), and a finer pattern structure. There is a need for photosensitive resin compositions that can be formed.

  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 production of a color filter, an inkjet method in which ink is sprayed and applied to a minute pixel has been proposed. However, a pixel pattern is formed from a photosensitive resin composition by photolithography, and a photosensitive resin composition is formed. A cured film is used as a partition between pixels.

  In the ink jet method, in order to prevent ink color mixing between adjacent pixel regions, the partition walls are required to have a property of repelling ink solvents such as water and organic solvents, so-called “ink repellency”. Yes. Further, since the ink ejected onto the partition wall slightly outside the pixel is accommodated in the target pixel, the partition wall is required to have “ink falling property”.

  Further, after the photosensitive resin composition is applied and the partition wall of the pixel pattern is formed through a photolithography process, the surface of the base material in the pixel may be removed before the ink is injected. For example, there is a step (hereinafter referred to as a cleaning step) of cleaning the substrate surface by irradiation with short wavelength ultraviolet rays such as a low-pressure mercury lamp or excimer UV, optical ashing treatment, or the like. It is required that the partition walls maintain ink repellency and ink tumbling properties even after irradiation with short-wavelength ultraviolet rays in this cleaning process.

  Patent Document 1 discloses a perfluoroalkyl group-containing α, β-unsaturated monomer having 3 or more carbon atoms, a polysiloxane chain-containing α, β-unsaturated monomer, a perfluoroalkyl group-free A composition containing a reactive surface modifier and a hydrocarbon monomer in which an acryloyl group or a methacryloyl group is introduced by a chemical bond to a polymer containing a siloxane chain-free α, β-unsaturated monomer as an essential constituent. Things are disclosed.

  However, the hydrocarbon monomer in the composition described in Patent Document 1 is unlikely to have a difference in alkali solubility between an exposed part and an unexposed part, and it is difficult to form a fine pattern from the composition. The mixing ratio of the reactive surface modifier to the hydrocarbon monomer is 50000: 1 by weight, and the cured film formed from the composition lacks ink repellency and ink tumbling property. On the other hand, in the composition in which the amount of the copolymer is simply increased, the coating film may become cloudy and the light transmittance may be lowered, or light may be irregularly reflected, resulting in a decrease in resolution. Moreover, there also existed a problem that a coating film was easy to peel from a base material.

  Patent Document 2 discloses a copolymer of unsaturated monomer components including an ethylenically unsaturated monomer having a silicon atom, and two or more ethylenically unsaturated groups and a carboxyl group in one molecule. An ultraviolet curable resin having a silicon atom, an epoxy compound having two or more epoxy groups in one molecule, a photopolymerization initiator, a diluent, and a leveling agent such as a fluorosurfactant Compositions containing are disclosed. 50% is exemplified as the blending ratio in the composition of the ultraviolet curable resin. However, with the above blending ratio, the wettability of the ink on the substrate surface after the unexposed portion of the coating film is removed by alkali development is insufficient, and the ink layer is difficult to spread within the pixel and the ink layer does not become flat. There is. In addition, when the exposure amount is small, there is a problem that curing failure occurs at the time of exposure, and the coating film is easily peeled off from the substrate during alkali development.

JP 61-275365 A (Claims) JP 11-279243 A (Claim 4, paragraph 0035)

  The present invention can form a cured film excellent in ink repellency, ink fall-off property, substrate adhesion, and coating film appearance, and can form a fine pattern. It is an object of the present invention to provide a photosensitive resin composition having good ink wettability of a base material portion after removal of an unexposed portion.

The present invention provides the following means.
[1] A resin (A) obtained by polymerizing a monomer component (a) containing an ethylenically unsaturated monomer (m1) having a group represented by the following formula 1; A resin (B) obtained by polymerizing a monomer component (b) containing an ethylenically unsaturated monomer (m2) having a group, an acidic group and 6 or more ethylenic duplexes in one molecule A photosensitive resin composition comprising an alkali-soluble resin (C) having a bond and a radical initiator (D),
The fluorine atom content in the monomer component (a) is 1 to 35% by mass with respect to the total amount of the monomer component (a), and the silicon atom content in the monomer component (b) is monomer. It is 0.1-30 mass% with respect to the whole quantity of a component (b), the ratio of resin (A) in the total solid of the photosensitive resin composition is 0.05-30 mass%, and the ratio of resin (B) is A photosensitive resin composition characterized by being 0.01 to 20% by mass.
-CFXR ^f Formula 1
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents an alkyl group having 20 or less carbon atoms in which at least one of the fluorine atom or the hydrogen atom is substituted with a fluorine atom (provided that the alkyl group Includes those having an etheric oxygen atom.)
_{^{- (SiR 1 R 2 -O)}} n -SiR 1 R 2 R 3 ··· Equation 2
(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents 1 to 200. Indicates an integer.)
[2] The photosensitive resin composition according to [1], further including a radical crosslinking agent (E) that is a compound having two or more ethylenic double bonds and no acidic group.
[3] The alkali-soluble resin (C) further includes a thermal crosslinking agent (F) which is a compound having a carboxyl group and / or a hydroxyl group and having two or more groups capable of reacting with the carboxyl group and / or the hydroxyl group. 1] or the photosensitive resin composition according to [2].
[4] The monomer component (a) further includes an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group. Photosensitive resin composition.
[5] The monomer component (b) further includes an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group [3] or [ 4]. The photosensitive resin composition as described in 4].
[6] A cured coating film obtained from the photosensitive resin composition according to any one of claims 1 to 5.

  In the photosensitive resin composition of the present invention, radicals are generated from the radical initiator (D) by light irradiation, and the alkali-soluble resin (C) undergoes a crosslinking reaction to form a cured coating film. Unirradiated parts are removed.

  In the resin (A), the group represented by the above formula 1 has surface migration, and in the resin (B), the group represented by the above formula 2 has surface migration. When the film is dried), the film moves to the vicinity of the coating surface at the air interface. The group represented by Formula 1 in the resin (A) mainly imparts ink repellency. The group represented by the above formula 2 in the resin (B) mainly imparts excellent ink falling property to highly polar ink. In addition, the group represented by the above formula 2 has excellent resistance to short wavelength ultraviolet irradiation, and when the coating film cured product is used as the partition wall of the pixel pattern, the group represented by the above formula 1 by the short wavelength ultraviolet irradiation during the cleaning process is used. It is possible to suppress deterioration of the group to be maintained and to maintain ink repellency even after irradiation with short wavelength ultraviolet rays. In addition, a washing | cleaning process is a process for making the ink wettability of the base-material surface after the coating-film unexposed part is removed by alkali image development favorable.

  When the fluorine atom content in the monomer component (a) and the ratio of the resin (A) in the total solid content of the photosensitive resin composition are within the above ranges, the cured coating film exhibits sufficient ink repellency. In addition, the substrate adhesion is excellent. That is, when the resin (A) moves to the vicinity of the coating surface during pre-baking, the concentration of the resin (A) on the surface of the cured coating film is relatively increased, and the concentration of the resin (A) near the substrate is relatively Therefore, while sufficient ink repellency is imparted to the surface of the cured coating film, it is possible to prevent a decrease in the substrate adhesion of the cured coating film.

  When the content of the silicon atom in the monomer component (b) and the ratio of the resin (B) in the total solid content of the photosensitive resin composition are in the above ranges, the cured coating film exhibits sufficient ink falling properties. In addition, it is excellent in ink wettability on the substrate surface after the unexposed portion of the coating film is removed by alkali development, and a flat ink layer can be formed. Since the ink wettability is excellent, the amount of short-wavelength ultraviolet irradiation in the cleaning step can be reduced.

  Since the alkali-soluble resin (C) has 6 or more ethylenic double bonds in the molecule, the difference in alkali solubility between the exposed portion and the unexposed portion of the coating film of the photosensitive resin composition is likely to be smaller and less. A fine pattern can be formed with an exposure amount.

  When the photosensitive resin composition further includes a radical crosslinking agent (E) that is a compound having two or more ethylenic double bonds and no acidic group, the photosensitive resin composition is cured by light irradiation. It is accelerated and can be cured in a shorter time.

  A thermal crosslinking agent (F), which is a compound in which the alkali-soluble resin (C) has a carboxyl group and / or a hydroxyl group, and the photosensitive resin composition has two or more groups capable of reacting with the carboxyl group and / or the hydroxyl group; When it contains, it crosslinks with alkali-soluble resin (C) by the heat processing after image development, the crosslinking density of coating-film cured | curing material increases, and heat resistance improves.

  When the monomer component (a) further contains an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group, the resin (A) is thermally crosslinked. It crosslinks with the agent (F) and is fixed near the surface of the cured film. Therefore, the ink repellency of the cured coating film is excellent in sustainability.

  When the monomer component (b) further contains an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group, the resin (B) is thermally crosslinked. It crosslinks with the agent (F) and is fixed near the surface of the cured film. Therefore, the ink falling property of the cured coating film is excellent in sustainability.

  According to the present invention, while being excellent in ink repellency and ink tumbling property, it is possible to form a cured coating film having good appearance and high adhesion to a substrate, and further capable of forming a fine pattern. Thus, a photosensitive resin composition having good ink wettability of the substrate portion from which the unexposed portion after alkali development has been removed is obtained.

  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 photosensitive resin composition of the present invention comprises a resin (A) obtained by polymerizing a monomer component (a) containing an ethylenically unsaturated monomer (m1) having a group represented by the following formula 1. Including.
-CFXR ^f Formula 1
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents an alkyl group having 20 or less carbon atoms in which at least one of the fluorine atom or the hydrogen atom is substituted with a fluorine atom (provided that the alkyl group Includes those having an etheric oxygen atom.)
As the ethylenically unsaturated monomer (m1) having a group represented by the following formula 1,
CH ₂ = CR ⁴ COOR ⁵ [1],
CH ₂ = CR ⁴ COOR ⁵ NR ⁶ SO ₂ [1],
CH ₂ = CR ⁴ COOR ⁵ NR ⁶ CO [1],
_{^{CH 2 = CR 4 COOCH 2 CH}} (OH) R 7 [1],
CH ₂ = CR ⁴ CR ⁴ = CF [1]
CF ₂ = CFO [1]
Etc. However, the ^{R 4} is a hydrogen atom or a methyl group, a ^{R 5} is an alkylene group having 1 to 6 carbon atoms, the ^{R 6} is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{R 7} represents a single bond or a carbon 1 And [1] represents a group represented by Formula 1 above.

Specific examples of R ⁵ _{include, -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 )-, etc.

Specific examples of R ⁶ 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 ⁷ _{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.

When R ^{f in} Formula 1 is an alkyl group having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, the alkyl group is a hydrogen atom substituted with a halogen atom other than a fluorine atom. The other halogen atom is preferably a chlorine atom. The etheric oxygen atom may be present between the carbon-carbon bonds of the alkyl group or may be present at the bond terminal.

  The group represented by the above formula 1 is preferably a perfluoroalkyl group or a polyfluoroalkyl group containing one hydrogen atom, and particularly preferably a perfluoroalkyl group (provided that the alkyl group is an etheric oxygen group). Including those having atoms). Thereby, the resin (A) exhibits good ink repellency. Moreover, it is preferable that the total carbon number of group represented by the said Formula 1 is 3-15. As a result, the resin (A) exhibits good ink repellency, particularly organic repellency. Moreover, the compatibility of the ethylenically unsaturated monomer (m1) having the group represented by the above formula 1 and other ethylenically unsaturated monomers is improved.

Specific examples of the group represented by the above formula 1 include
_{-CF 3, -CF 2 CF 3,} -CF 2 CHF 2, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, - (CF 2) 4 CF 3, - (CF 2) 5 CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ ,-(CF ₂ ) ₁₁ CF ₃ ,-(CF _{2) 15 CF 3, -CF 2} O (CF 2 CF 2 O) p CF 3 (p is 0-8),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) q (CF 2) 2 CF 3 (q is 0-5),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) r (CF 2) 5 CF 3 (r is 0-4), and the like.

  The ethylenically unsaturated monomer (m1) having a group represented by the above formula 1 may be used alone or in combination of two or more.

  The monomer component (a) preferably includes an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group. When the resin (A) contains a carboxyl group and / or a hydroxyl group, the resin (A) undergoes a crosslinking reaction with a thermal crosslinking agent (F) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group, It is fixed on the surface of the cured coating film, and the ink repellency and the ink falling property are improved.

  Examples of the ethylenically unsaturated monomer (m3) 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.

  Examples of the ethylenically unsaturated monomer (m4) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 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, 2-hydroxyethyl allyl ether, N-hydroxy Methyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, etc. , One or more hydrogen atoms of these benzene rings are one or more hydrogen atoms of an alkyl group such as methyl, ethyl or n-butyl, an alkoxy group such as methoxy, ethoxy or n-butoxy, a halogen atom or an alkyl group Haloalkyl group substituted with a halogen atom, a nitro group, a cyano group, a compound substituted with an amide group, and the like.

  The monomer component (a) includes an ethylenically unsaturated monomer (m1) having a group represented by the above formula 1, an ethylenically unsaturated monomer (m3) having a carboxyl group, and an ethylene having a hydroxyl group. Monomers other than the unsaturated unsaturated monomer (m4) (other monomers (m5)) may be contained.

  Other monomers (m5) include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (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 the photosensitive resin 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 resin (A) can be synthesized, for example, by a method in which the monomer component (a) is dissolved in a solvent, heated as necessary, and reacted by adding a polymerization initiator. In the reaction, a chain transfer agent is preferably present as necessary. You may add a monomer, 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 be used as a redox catalyst 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 monomer component (a) is 1 to 35% by mass relative to the total amount of the monomer component (a), and the ratio of the resin (A) in the total solid content of the photosensitive resin composition is It is 0.05-30 mass%. Within such a range, the resin (A) is excellent in the effect of lowering the surface tension of the cured coating film to be formed, and imparts high ink repellency to the cured coating film. On the other hand, if it is within this range, the compatibility of the resin (A) with the other components of the photosensitive resin composition is good, and the resins (A) aggregate when they are painted to form a coating film. There is nothing. Therefore, the developability of the photosensitive resin composition is good without causing the coating film to become cloudy, and the adhesion between the cured coating film and the substrate is enhanced. The lower limit of the fluorine atom content in the monomer component (a) is preferably 3% by mass, and the upper limit is preferably 30% by mass. As for the ratio of resin (A) in the total solid content of the photosensitive resin composition, the lower limit is preferably 2.5% by mass, more preferably 3% by mass, particularly preferably 4% by mass, and the upper limit is preferably 20% by mass, 10 mass% is more preferable. In particular, it was found that when the ratio of the resin (A) in the total solid content of the photosensitive resin composition is 2.5% by mass or more, the ink repellency after irradiation of the coating film cured product with short wavelength ultraviolet rays is excellent.

  When the monomer component (a) includes an ethylenically unsaturated monomer (m3) having a carboxyl group, the acid value of the resin (A) is preferably 1 to 100 mgKOH / g, and preferably 5 to 50 mgKOH / g. g is more preferable. When the acid value is within this range, the ink repellency of the cured coating film based on the crosslinking reaction between the resin (A) and the thermal crosslinking agent (F) becomes good. In addition, an acid value is the mass (unit mg) of potassium hydroxide required in order to neutralize 1 g of resin, and a unit is described in this specification as mgKOH / g.

  When the monomer component (a) contains an ethylenically unsaturated monomer (m4) having a hydroxyl group, the hydroxyl value of the resin (A) is preferably 50 to 300 mgKOH / g, and preferably 100 to 250 mgKOH / g. More preferably. When the hydroxyl value is within this range, the ink repellency of the cured coating film based on the crosslinking reaction between the resin (A) and the thermal crosslinking agent (F) is good. 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 the other monomer in the monomer component (a) is preferably 70% by mass or less, and more preferably 60% by mass or less. Within this range, the developability of the photosensitive resin composition will be good.

  The number average molecular weight of the resin (A) is preferably 500 to less than 20000. The lower limit is more preferably 1000, and particularly preferably 2000. The upper limit is more preferably 15000 and particularly preferably 12000. Within this range, there is an advantage that the change in contrast due to exposure is large and the sensitivity to light is high, while the solubility in the developer is high, and the generation of dissolved residues in the non-exposed area can be prevented.

The photosensitive resin composition of the present invention comprises a resin (B) obtained by polymerizing a monomer component (b) containing an ethylenically unsaturated monomer (m2) having a group represented by the following formula 2. Including.
_{^{- (SiR 1 R 2 -O)}} n -SiR 1 R 2 R 3 ··· Equation 2
(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents 1 to 200. Indicates an integer.)
As the ethylenically unsaturated monomer (m2) having a group represented by the above formula 2,
CH ₂ = CHCOOR ⁸ [2]
_{CH 2 = C (CH 3)} COOR 8 [2]
Etc. However, R ⁸ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and [2] represents a group represented by the above formula 2.

Specific examples of R ⁸ include —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.

In the above formula 2, R ¹ and R ² may be the same or different for each siloxane unit. R ¹ and R ² are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group because the resin (B) exhibits excellent ink falling properties, and a hydrogen atom or a methyl group or more preferably a phenyl group, and particularly preferably R ^1, R ² of all siloxane units are methyl groups. Moreover, when R < ³ > is an organic group, a nitrogen atom, an oxygen atom, etc. may be contained, and it is preferable that R < ³ > is a hydrogen atom or a C1-C5 hydrocarbon group. n is preferably an integer of 1 to 100.

  The ethylenically unsaturated monomer (m2) having a group represented by the above formula 2 may be used alone or in combination of two or more.

  The monomer component (b) preferably includes an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group. When the resin (B) contains a carboxyl group and / or a hydroxyl group, the resin (B) undergoes a crosslinking reaction with a thermal crosslinking agent (F) which is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group, It is fixed on the surface of the cured coating film, and the ink repellency and ink tumbling durability are good.

  Specific examples of the ethylenically unsaturated monomer (m3) having a carboxyl group and the ethylenically unsaturated monomer (m4) having a hydroxyl group are the same as those described for the resin (A).

  The monomer component (b) includes an ethylenically unsaturated monomer (m2) having a group represented by the above formula 2, an ethylenically unsaturated monomer (m3) having a carboxyl group, and an ethylene having a hydroxyl group. Monomers other than the unsaturated unsaturated monomer (m4) (other monomers (m5)) may be contained. Examples of the other monomer (m5) include the same specific examples as described for the resin (A).

  The resin (B) can be synthesized, for example, by a method in which the monomer component (b) is dissolved in a solvent, heated as necessary, and reacted by adding a polymerization initiator. In the reaction, a chain transfer agent is preferably present as necessary. You may add a monomer, a polymerization initiator, a solvent, and a chain transfer agent continuously. Specific examples of the solvent, polymerization initiator, and chain transfer agent in the synthesis are the same as those described for the resin (A).

  The content of silicon atoms in the monomer component (b) is 0.1 to 20% by mass with respect to the total amount of the monomer component (b), and the resin (B) in the total solid content of the photosensitive resin composition. A ratio is 0.01-30 mass%. Within such a range, the resin (B) imparts high ink tumbling property to the formed coating film cured product, and the ink repellency of the coated film cured product after irradiation with short wavelength ultraviolet rays is good. On the other hand, it is excellent in the ink wettability of the base-material surface after the unexposed part of a coating film is removed by alkali development. The lower limit of the silicon atom content in the monomer component (b) is more preferably 0.3% by mass, and particularly preferably 0.5% by mass. The upper limit is more preferably 15% by mass, and particularly preferably 10% by mass. The lower limit of the proportion of the resin (B) in the total solid content of the photosensitive resin composition is more preferably 0.05% by mass, and particularly preferably 0.1% by mass. The upper limit is more preferably 20% by mass, and particularly preferably 10% by mass.

  When the monomer component (b) includes an ethylenically unsaturated monomer (m3) having a carboxyl group, the acid value of the resin (B) is preferably 1 to 100 mgKOH / g, and preferably 5 to 50 mgKOH / g. g is more preferable. When the acid value is within this range, the durability of the ink falling of the cured coating film based on the crosslinking reaction between the resin (B) and the thermal crosslinking agent (F) becomes good.

  When the monomer component (b) includes an ethylenically unsaturated monomer (m4) having a hydroxyl group, the hydroxyl value of the resin (B) is preferably 50 to 300 mgKOH / g, and preferably 100 to 250 mgKOH / g. More preferably. When the hydroxyl value is within this range, the durability of the ink falling of the cured coating film based on the crosslinking reaction between the resin (B) and the thermal crosslinking agent (F) becomes good.

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

  The number average molecular weight of the resin (B) is preferably 500 to less than 20000. The lower limit is more preferably 1000, and particularly preferably 2000. The upper limit is more preferably 15000 and particularly preferably 12000. Within this range, there is an advantage that the change in contrast due to exposure is large and the sensitivity to light is high, while the solubility in the developer is high, and the generation of dissolved residues in the non-exposed area can be prevented.

  In the photosensitive resin composition containing the resin (A) and the resin (B), the group represented by the above formula 1 and the group represented by the above formula 2 are present in different molecules, and are represented by the above formula 1. And the photosensitive resin composition containing a resin in which the group represented by the above formula 2 is present in the same molecule tend to be excellent in ink repellency and ink tumbling property. The reason is not clear, but the group represented by the above formula 1 and the group represented by the above formula 2 have the property of being oriented on the surface of the coating film. This is considered to be due to the higher degree of freedom of the molecular chain and the easier orientation on the surface.

  The photosensitive resin composition containing the resin (A) and the resin (B) is a photosensitive resin containing a resin in which the group represented by the formula 1 and the group represented by the formula 2 are present in the same molecule. Compared to the composition, the cured film has a tendency to be excellent in ink repellency after short-wave ultraviolet irradiation. The reason is not clear, but in order to suppress deterioration of the group represented by Formula 1 due to short-wavelength ultraviolet irradiation, the group represented by Formula 2 having excellent resistance to short-wavelength ultraviolet irradiation is represented by Formula 1. It is considered that it exists in the vicinity of, and it is considered that it exists in a separate molecule rather than in the same molecule because the degree of freedom of the molecular chain is high and the orientation of the coating surface becomes desirable. .

  The photosensitive resin composition of the present invention contains an alkali-soluble resin (C) having an acidic group and 6 or more ethylenic double bonds in one molecule.

  Examples of the acidic group include at least one acidic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl 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 (C) include a vinyl polymer (C1) 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 (C2) may be mentioned. These resins are preferably substantially free of fluorine atoms.

  The monomer capable of forming a monomer unit having an acidic group in the vinyl polymer (C1) includes a monomer having a carboxyl group, a monomer having a sulfonic acid group, and a monomer having a phenolic hydroxyl group. And monomers having phosphoric acid groups, such as acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or salts thereof, such as vinyl Sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, (meth) acrylic acid 2-sulfoethyl, (meth) acrylic acid 2-sulfopropyl, (meth) acrylic acid 3-sulfopropyl, 2-hydroxy-3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamide-2-methyl Propanesulfonic acid or a salt thereof, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, etc. One or more hydrogen atoms of these benzene rings are alkyl groups such as methyl, ethyl, n-butyl, etc. An alkoxy group such as methoxy, ethoxy, n-butoxy, a halogen atom, a haloalkyl group in which one or more hydrogen atoms of an alkyl group are substituted with a halogen atom, a compound in which a nitro group, a cyano group, an amide group are substituted, etc. Examples include 2- (meth) acryloyloxyethanephosphoric acid or a salt thereof.

  The monomer unit having an ethylenic double bond of the vinyl polymer (C1) can be obtained by the following method. (1) A method in which a monomer having a hydroxyl group is polymerized in advance and then an acid anhydride having an ethylenic double bond is reacted. (2) A monomer having a hydroxyl group is polymerized in advance, followed by an isocyanate group and an ethylenic group. A method of reacting a compound having a double bond, (3) a method of previously polymerizing a monomer having a hydroxyl group, and a reaction of a compound having an acyl chloride group and an ethylenic double bond, and (4) an ethylenic double bond. A method in which an acid anhydride having a bond is polymerized in advance and a hydroxyl group and a compound having an ethylenic double bond are reacted; (5) a monomer having a carboxyl group is polymerized in advance; (6) A monomer having an epoxy group is polymerized in advance, and then a carboxyl group and an ethylenic compound A method of reacting a compound having a bond.

  Examples of the monomer having a hydroxyl group include 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, glycerin mono (meth) acrylate , 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) acryl Bromide, N, N-bis (hydroxymethyl) (meth) acrylamide or a monomer terminal having a polyoxyalkylene chain is a hydroxyl group are exemplified.

  Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, and 2-buten-1-ylsuccinic anhydride. Is exemplified.

  Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate.

  Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

  Examples of the compound having an epoxy group and an ethylenic double bond include glycidyl (meth) acrylate and (3,4-epoxycyclohexyl) methyl acrylate.

  The vinyl polymer (C1) may have a monomer unit other than a monomer unit having an acidic group and a monomer unit having an ethylenic double bond. Examples of the monomer that gives such a monomer unit include the other monomer (m5) exemplified for the resin (A).

  The vinyl polymer (C1) can be synthesized, for example, by a method in which a monomer is dissolved in a solvent and heated, 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, a polymerization initiator, a solvent, and a chain transfer agent continuously. As the polymerization initiator, the solvent and the chain transfer agent, those exemplified for the resin (A) can be used.

  As the solvent used in the modification reaction for introducing an ethylenic double bond into the polymer, the solvent used in the polymerization reaction described above can be used. In the modification reaction, it is preferable to add a polymerization inhibitor. As the polymerization inhibitor, a publicly known polymerization inhibitor can be used, and specific examples include 2,6-di-t-butyl-p-cresol.

  The novolak resin of the novolak resin (C2) introduced with the ethylenic double bond is at least selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, hydroquinone and the like, and alkyl-substituted or halogen-substituted aromatic compounds thereof. It is obtained by polycondensing 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 after washing and removal of the unexposed portion of the coating film by development is favorable and preferable.

  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 (C2) 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 (C) 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. If the number of ethylenic double bonds in one molecule is 5 or less, there is little difference in alkali solubility between exposed and unexposed areas, and it is difficult to form a fine pattern unless the exposure dose is increased. Or the resolution is reduced.

  The alkali-soluble resin (C) preferably has a carboxyl group and / or a hydroxyl group as a group capable of undergoing a crosslinking reaction. When the photosensitive resin composition further includes a thermal crosslinking agent (F) 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 (C) is crosslinked with a heat treatment after development. It is because it reacts, the crosslink density of the coating film cured product is increased, and the heat resistance is improved. 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 (C) 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.

  10-600 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, alkali solubility and developability are good.

  200-20000 are preferable and, as for the number average molecular weight of alkali-soluble resin (C), 2000-15000 are more preferable. Within this range, the alkali solubility and developability of the photosensitive resin composition are good.

  The proportion of the alkali-soluble resin (C) in the total solid content of the photosensitive resin composition is preferably 5 to 80% by mass, and more preferably 10 to 50% by mass. Within this range, the developability of the photosensitive resin composition is good.

  The photosensitive resin composition of this invention contains a radical initiator (D). The radical initiator (D) is a compound that generates radicals by light. Examples of the radical initiator (D) include benzyl, diacetyl, methylphenylglyoxylate, α-diketones such as 9,10-phenanthrenequinone, acyloins such as benzoin, benzoin methyl ether, 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) benzopheno Benzophenones such as acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4 Acetophenones such as-(methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, anthraquinone, 2-ethylanthraquinone Quinones such as camphorquinone and 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate 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 radical initiator (D) in the total solid of the photosensitive resin composition, 0.5-30 mass% is more preferable. Within this range, developability is good.

  It is preferable that the photosensitive resin composition further includes a radical crosslinking agent (E) that is a compound having two or more ethylenic double bonds and no acidic group. Thereby, hardening of the photosensitive resin composition by light irradiation is accelerated | stimulated, and hardening in a shorter time is attained.

  Specific examples of the radical crosslinking agent (E) 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 (E) in the total solid of the photosensitive resin composition, 15-50 mass% is more preferable. Within this range, the developability of the photosensitive resin composition will be good.

  It is preferable that the photosensitive resin composition further includes a thermal crosslinking agent (F) that is a compound having two or more groups capable of reacting with a carboxyl group and / or a hydroxyl group. When the alkali-soluble resin (C) has a carboxyl group and / or a hydroxyl group, the thermal cross-linking agent (F) reacts with the alkali-soluble resin (C) to increase the cross-linking density of the cured film and improve the heat resistance. be able to. Further, when the resin (A) contains a carboxyl group and / or a hydroxyl group, the resin (A) is cross-linked with the thermal crosslinking agent (F), and the resin (A) is immobilized on the surface of the cured coating film, thereby maintaining ink repellency. Property is improved. When the resin (B) contains a carboxyl group and / or a hydroxyl group, it undergoes a crosslinking reaction with the thermal crosslinking agent (F), and the resin (B) is immobilized on the surface of the cured coating film, and the ink falling property is maintained. Property is improved.

  The thermal crosslinking agent (F) 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.

  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 the hydroxyl group of the hydroxymethylated compound is methanol, ethanol , N-butyl alcohol, a compound etherified with 2-methyl-1-propanol, and the like, for example, hexamethoxymethylmelamine and the like.

  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.

  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 (F) in the total solid of the photosensitive resin composition, 3-30 mass% is more preferable. Within this range, the developability of the photosensitive resin composition will be good.

  In the photosensitive resin composition, it is preferable to use a silane coupling agent (G) as needed. When a silane coupling agent is used, the substrate adhesion of the cured coating film formed from the photosensitive resin composition is improved.

  Specific examples of the silane coupling agent (G) 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 photosensitive resin composition, a diluent (H) can be used. Specific examples of the diluent (H) include the solvents exemplified as the solvent for synthesizing the resin (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 photosensitive resin 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 photosensitive resin 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 photosensitive resin composition capable of forming a black coating film is applied 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 by a dispersing machine such as a sand mill or a roll mill together with a dispersant (for example, a polycaprolactone compound, a long chain alkyl polyaminoamide compound, etc.), and then added to the photosensitive resin composition. The particle size is preferably 1 μm or less. Within this range, the developability of the photosensitive resin composition will be good.

Hereinafter, the photolithography process using the photosensitive resin composition of the present invention will be described.
First, the photosensitive resin 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 preferably an electromagnetic wave having a distribution in the range of 100 to 600 nm, and specifically includes laser light such as visible light, ultraviolet light, far ultraviolet light, KrF excimer laser, ArF excimer laser, and F ₂ excimer laser. It is done. However, when irradiating light with a short wavelength, since the energy is strong, the composition material 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 exposes in the range of 5-1000 mJ / cm < ² > exposure amount.

  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 performing heat treatment (post-cure treatment) at 120 to 250 ° C. for 5 to 90 minutes with a heating device such as a hot plate or an oven.

  After the partition of the pixel pattern is formed through the above photolithography process, dirt on the surface of the base material in the pixel may be removed. For example, the process of washing | cleaning the base-material surface by irradiation of short wavelength ultraviolet rays, such as a low pressure mercury lamp and excimer UV, a photo ashing process, etc. is mentioned. The light ashing process is a process of irradiating short wavelength ultraviolet light in the presence of ozone gas. The short wavelength ultraviolet light is light having a main peak at a wavelength of 100 to 300 nm.

  The photosensitive resin 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.

  Ink repellency can be estimated by the contact angle of water and xylene in the cured film, and the contact angle of water is preferably 70 degrees or more, and more preferably 75 degrees or more. The contact angle of xylene is preferably 25 degrees or more, and more preferably 30 degrees or more.

  In the coated film cured product, the ink falling property can be estimated by the falling angle of water and xylene, and the falling angle of water is preferably 35 degrees or less, and more preferably 25 degrees or less. Further, the falling angle of xylene is preferably 30 degrees or less, and more preferably 20 degrees or less.

Although it demonstrates based on an Example (Examples 1-4) and a comparative example (Examples 5-9) below, this invention is not limited to these. In the following, unless otherwise specified, the parts are based on mass.
The number average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.
It is a theoretical value calculated from the acid value (mgKOH / g), the hydroxyl value (mgKOH / g), and the blending ratio of 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
X-174DX: Dimethyl silicone chain-containing methacrylate (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-174DX)
X-8201: Dimethyl silicone chain-containing methacrylate (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-24-8201)
MAA: methacrylic acid, 2-HEMA: 2-hydroxyethyl methacrylate, MMA: methyl methacrylate, IBMA: isobornyl methacrylate,
2-ME: 2-mercaptoethanol, DSH: n-dodecyl mercaptan,
V-70: 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name V-70, manufactured by Wako Pure Chemical Industries, Ltd.)
MOI: 2-methacryloyloxyethyl isocyanate, DBTDL: dibutyltin dilaurate, BHT: 2,6-di-t-butyl-p-cresol,
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 (manufactured by Nippon Kayaku Co., Ltd., trade name DETX-S)
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)
NW-100LM: Methyl etherified melamine copolymer (manufactured by Sanwa Chemical Co., Ltd., trade name Nicalak NW-100LM)
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 Resin (A-1)>
In a 1 L internal reaction tank equipped with a stirrer, acetone (558 g), C8FA (72.0 g), 2-HEMA (96.0 g), MMA (72.0 g), chain transfer agent 2-ME (3. 1 g) and a polymerization initiator V-70 (4.9 g) were charged and polymerized at 40 ° C. for 18 hours while stirring in a nitrogen atmosphere to obtain a resin (A-1) solution. Water was added to the obtained acetone solution of the resin (A-1) for reprecipitation purification, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain 238 g of resin (A-1). The number average molecular weight was 6000.

[Synthesis Examples 2 to 7]
<Resin (A-2), (A-3), (B-1), (B-2), (R-1), (R-2), (R-3), (R-4) Synthesis>
In the synthesis of the resin (A-1), the resin (A-2), the resin (A-3), the resin (B-1), Resin (B-2), resin (R-1), resin (R-2), resin (R-3), and resin (R-4) were obtained. In Table 1, the fluorine atom content in the monomer component (a), the silicon atom content in the monomer component (b), the acid value (mgKOH / g) of the resin, and the hydroxyl value (mgKOH / g). )showed that.

[Synthesis Example 10]
<Synthesis of alkali-soluble resin (C-1)>
In a 1 L reaction tank equipped with a stirrer, acetone (555 g), MAA (36.0 g), 2-HEMA (132.0 g), IBMA (72.0 g), chain transfer agent DSH (9.7 g) And polymerization initiator V-70 (5.4 g) were charged and polymerized at 40 ° C. for 18 hours with stirring in a nitrogen atmosphere to obtain a polymer solution. Water was added to the obtained polymer acetone solution for reprecipitation purification, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain a polymer (239 g). The number average molecular weight of the polymer was 5000, and the acid value was 98 mgKOH / g.

  Into a 300 mL glass flask equipped with a thermometer, stirrer and heating device, polymer (100 g), MOI (65.6 g), DBTDL (0.26 g), BHT (3.3 g) and acetone (100 g) And polymerized at 30 ° C. for 18 hours with stirring to obtain a solution of an alkali-soluble resin (C-1). The number average molecular weight of the alkali-soluble resin (C-1) was 8280. Water was added to the acetone solution of the obtained alkali-soluble resin (C-1) for reprecipitation purification, then reprecipitation purification with petroleum ether, and vacuum drying to obtain 163 g of alkali-soluble resin (C-1). . As a theoretical value calculated from the blending amount of raw materials, the acid value is 59.1 mgKOH / g, and the number of ethylenic double bonds in one molecule is 21.2.

[Synthesis Examples 11 and 12]
<Synthesis of alkali-soluble resins (C-2) and (C-3)>
In the synthesis of the alkali-soluble resin (C-1), an alkali-soluble resin (C-2) and an alkali-soluble resin (C-3) were obtained by the same polymerization reaction and modification reaction except that the blending of raw materials was changed as shown in Table 2. )

  Table 2 shows the acid value (mgKOH / g) of each resin and the number of ethylenic double bonds in one molecule.

[Examples 1 to 13]
<Evaluation of photosensitive resin composition>
Resin (A), resin (B), resin (R), alkali-soluble resin (C), radical initiator (D), radical crosslinking agent (E), thermal crosslinking agent in the proportion (parts by mass) shown in Table 3. (F), the silane coupling agent (G), and the diluent (H) were mix | blended and the photosensitive resin composition was obtained.

After applying the photosensitive resin 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, 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, developability, coating film appearance, substrate adhesion, ink repellency, ink tumbling property, ink repellency after short wavelength UV irradiation, ink tumbling property after short wavelength UV irradiation, unexposed part of coating film is removed The ink wettability of the substrate part after the measurement was measured and evaluated by the following method. The evaluation results are shown in Table 3.

[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.

[Ink repellency]
The ink repellency was evaluated by the contact angle (degree) of water and xylene on the surface of the cured 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 ink repellency of the coating film. A contact angle of water of 70 degrees or more was indicated as ◯, and a water contact angle of less than 70 degrees as ×. The contact angle of xylene of 25 ° or more was indicated as “○”, and the angle less than 25 ° was indicated as “x”.

[Ink fallability]
Ink fallability is determined by dropping 50 μL of water or 10 μL of xylene onto the surface of a cured coating film formed on a horizontally held glass substrate, lifting one side of the glass substrate, and gradually tilting it. The angle between the glass substrate surface and the horizontal plane when the drop began to fall was evaluated by the falling angle (degree). The smaller this angle is, the better the ink falling property of the coating film is. The falling angle of water of 35 degrees or less was indicated as “◯”, and the water falling angle exceeding 35 degrees was indicated as “X”. The falling angle of xylene of 30 degrees or less was indicated as ◯, and the falling angle of more than 30 degrees as x.

[Ink repellency after short wavelength UV irradiation]
A low-pressure mercury lamp was used as a light source, and evaluation was made based on contact angles of water and xylene after irradiating a short-wave ultraviolet ray for 2 minutes to a cured film formed on a glass substrate.

[Ink tumbling after short wavelength UV irradiation]
A low-pressure mercury lamp was used as a light source, and the film and cured product formed on the glass substrate were evaluated by the falling angles of water and xylene after irradiating short wavelength ultraviolet rays for 2 minutes.

[Ink wettability of substrate]
The ink wettability of the base material portion from which the unexposed portion of the coating film after alkali development was removed was evaluated by the contact angle of water. A water contact angle of less than 50 degrees was represented as ◯, and 50 degrees or more as x.

  In Example 5, the ratio of the resin (B) in the total solid content of the photosensitive resin composition is too low, and the coated film cured product is inferior in ink repellency and ink repellency / ink tumbling property after irradiation with short wavelength ultraviolet rays. In Example 6, the ratio of the resin (B) in the total solid content of the photosensitive resin composition is too high, and the developability, the coating film appearance, and the ink wettability of the substrate are inferior. In Example 7, the silicon atom content in the monomer component (b) of the resin (B) is too low, and the coated film cured product is inferior in ink repellency and ink repellency / ink tumbling property after irradiation with short wavelength ultraviolet rays. In Example 8, the silicon atom content in the monomer component (b) of the resin (B) is too high, and the developability, coating film appearance, and ink wettability of the substrate are poor. In Example 9, the number of ethylenic double bonds in one molecule of the alkali-soluble resin (B) is less than 6, and the developability is poor. In Example 10, the ratio of the resin (A) in the total solid content of the photosensitive resin composition is too low, and the ink repellency of the cured film is inferior. In Example 11, the ratio of the resin (A) in the total solid content of the photosensitive resin composition is too high, and the coating film appearance and substrate adhesion are poor. In Example 12, the fluorine atom content in the monomer component (a) of the resin (A) is too low, and the ink repellency of the cured film is poor. In Example 13, the fluorine atom content in the monomer component (a) of the resin (A) is too high, and the coating film appearance and substrate adhesion are poor.

The resist composition of the present invention can be applied to uses that require ink repelling properties. 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 (6)

A resin (A) obtained by polymerizing a monomer component (a) containing an ethylenically unsaturated monomer (m1) having a group represented by the following formula 1 and a group represented by the following formula 2 A resin (B) obtained by polymerizing a monomer component (b) containing an ethylenically unsaturated monomer (m2) having an acidic group and 6 or more ethylenic double bonds in one molecule A photosensitive resin composition comprising an alkali-soluble resin (C) and a radical initiator (D),
The fluorine atom content in the monomer component (a) is 1 to 35% by mass with respect to the total amount of the monomer component (a), and the silicon atom content in the monomer component (b) is monomer. It is 0.1-30 mass% with respect to the whole quantity of a component (b), the ratio of resin (A) in the total solid of the photosensitive resin composition is 0.05-30 mass%, and the ratio of resin (B) is A photosensitive resin composition characterized by being 0.01 to 20% by mass.
-CFXR ^f Formula 1
(In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R ^f represents an alkyl group having 20 or less carbon atoms in which at least one of the fluorine atom or the hydrogen atom is substituted with a fluorine atom (provided that the alkyl group Includes those having an etheric oxygen atom.)
_{^{- (SiR 1 R 2 -O)}} n -SiR 1 R 2 R 3 ··· Equation 2
(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and n represents 1 to 200. Indicates an integer.)   The photosensitive resin composition of Claim 1 which further contains the radical crosslinking agent (E) which is a compound which has two or more ethylenic double bonds, and does not have an acidic group.   The said alkali-soluble resin (C) has a carboxyl group and / or a hydroxyl group, and further contains the thermal crosslinking agent (F) which is a compound which has two or more groups which can react with a carboxyl group and / or a hydroxyl group. 2. The photosensitive resin composition according to 2.   The photosensitivity according to claim 3, wherein the monomer component (a) further comprises an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group. Resin composition.   The monomer component (b) according to claim 3 or 4, further comprising an ethylenically unsaturated monomer (m3) having a carboxyl group and / or an ethylenically unsaturated monomer (m4) having a hydroxyl group. Photosensitive resin composition. A cured coating film obtained from the photosensitive resin composition according to claim 1.