JP4415737B2 - Photosensitive resin composition and cured film thereof - Google Patents

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 photosensitive resin composition is a permanent material for resist materials for forming ITO electrodes such as LCD and organic EL displays, interlayer insulating films, circuit protective films, partition materials for color filters, and partition materials for organic EL displays. It is also attracting attention as a material. For example, in the manufacture of color filters, an inkjet method in which ink is sprayed and applied to minute pixels has been proposed, but pixel pattern formation is performed from a photosensitive resin composition by photolithography, and the photosensitive resin composition 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 photoresist composition containing a copolymer of a fluorinated alkyl group-containing (meth) acrylate monomer and a silicone chain-containing ethylenically unsaturated monomer. The addition amount of the polymer is 0.001 to 0.05% with respect to the solid content of the photoresist composition.

  However, a cured coating film formed from a composition having a copolymer blend ratio described in Patent Document 1 lacks ink repellency and ink tumbling properties.

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

  It is an object of the present invention to provide a photosensitive resin composition capable of forming a cured coating film excellent in ink repellency, ink falling property, substrate adhesion, and coating film appearance.

The present invention provides the following means.
(1) Including a monomer (a1) having a group represented by the following formula 1 and an ethylenic double bond and a monomer (a2) having a group represented by the following formula 2 and an ethylenic double bond It reacts with a copolymer (A) obtained by polymerizing the monomer composition, an alkali-soluble resin (B) having a carboxyl group and / or a phenolic hydroxyl group, and a carboxyl group and / or a phenolic hydroxyl group. A photosensitive resin composition for light having a wavelength of 100 to 600 nm, comprising a crosslinking agent (C) which is a compound having two or more groups to be obtained, and a photoacid generator (D),
-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 fluorine atom content in the monomer composition is 1 to 30% by mass, and the proportion of the copolymer (A) in the total solid content of the photosensitive resin composition is 1.5 to 30% by mass. A photosensitive resin composition.
(2) The photosensitive resin composition as described in (1) whose ratio in the total solid of the photosensitive resin composition of the said copolymer (A) is 2.5-30 mass%.
(3) The photosensitive resin composition as described in (1) or (2) whose content rate of the silicon atom in the said monomer composition is 0.1-10 mass%.
(4) The monomer composition further comprises a monomer (a3) having a carboxyl group and an ethylenic double bond or a monomer (a4) having a hydroxyl group and an ethylenic double bond (1) to ( The photosensitive resin composition in any one of 3).
(5) A cured coating film obtained from the photosensitive resin composition according to (1) to (4).

  In the photosensitive resin composition of the present invention, an acid is generated from the photoacid generator (D) by irradiation of light, an alkali-soluble resin (B) having a carboxyl group and / or a phenolic hydroxyl group, a carboxyl group and / or A cured coating film is formed by a crosslinking reaction with a crosslinking agent (C), which is a compound having two or more groups capable of reacting with a phenolic hydroxyl group, and a portion not irradiated with light can be removed by alkali development.

  In the copolymer (A), since the group represented by the above formula 1 and the group represented by the above formula 2 have surface migration properties, during prebaking (drying of the coating film), Moves to the vicinity of the coating surface. The copolymer (A) imparts ink repellency and ink falling properties to the cured film. The group represented by the above formula 1 in the copolymer (A) mainly imparts ink repellency, and the group represented by the above formula 2 mainly imparts excellent ink falling properties for highly polar inks. 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.

  When the content of fluorine atoms in the monomer composition and the ratio of the copolymer (A) in the total solid content of the photosensitive resin composition are within the above ranges, the cured film exhibits sufficient ink repellency. In addition, the substrate adhesion is excellent. That is, when the copolymer (A) moves to the vicinity of the coating film surface during pre-baking, the concentration of the copolymer (A) on the surface of the cured coating film relatively increases, and the copolymer (A Since the concentration of A) is relatively reduced, sufficient ink repellency and ink fall-off properties can be imparted to the surface of the cured coating film, while a decrease in the substrate adhesion of the cured coating film can be prevented.

  When the monomer composition further comprises a monomer (a3) having a carboxyl group and an ethylenic double bond and / or a monomer (a4) having a hydroxyl group and an ethylenic double bond, a copolymer (A ) Is cross-linked with the cross-linking agent (C) and immobilized near the surface of the cured coating film. Therefore, the ink repellency and ink falling property of the cured film are excellent in sustainability.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the coating-film hardened | cured material excellent in ink repellency, ink falling property, base-material adhesiveness, and coating-film external appearance 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 includes a monomer (a1) having a group represented by the following formula 1 and an ethylenic double bond, and a single group having a group represented by the following formula 2 and an ethylenic double bond. A copolymer (A) having a structure obtained by polymerizing a monomer composition containing the monomer (a2);
-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.)
As the monomer (a1) having a group represented by the above formula 1 and an ethylenic double bond,
CH ₂ = CR ⁴ COOR ⁵ [1],
CH ₂ = CR ⁴ COOR ⁶ NR ⁴ SO ₂ [1],
CH ₂ = CR ⁴ COOR ⁶ NR ⁴ CO [1],
_{^{CH 2 = CR 4 COOCH 2 CH}} (OH) R 5 [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, ^{R 5} is a divalent organic group single bond or a 1 to 6 carbon atoms, ^{R 6} is a divalent organic group having 1 to 6 carbon atoms, [1] is the The group represented by Formula 1 is shown.

Specific examples of R ⁵ and R ⁶ 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 Can be mentioned.

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. Further, the etheric oxygen atom may exist between the carbon-carbon bonds of the alkyl group or may exist 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). As a result, the copolymer (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 copolymer (A) exhibits good ink repellency, particularly organic repellency. Moreover, the compatibility of the monomer represented by the above formula 1, the monomer (a1) having an ethylenic double bond, and other monomers having an ethylenic double bond 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 monomer represented by the above formula 1 and the monomer (a1) having an ethylenic double bond may be used alone or in combination of two or more.

As the monomer (a2) having a group represented by the above formula 2 and an ethylenic double bond,
CH ₂ = CHCOOR ⁷ [2]
_{CH 2 = C (CH 3)} COOR 7 [2]
Etc. However, R ⁷ 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 ⁷ include a single bond, —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 or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, since the copolymer (A) exhibits excellent ink falling properties. A methyl group or a phenyl group is more preferable, and R ¹ and R ² of all siloxane units are particularly preferably a methyl group. 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 group represented by the above formula 2 and the monomer (a2) having an ethylenic double bond may be used alone or in combination of two or more.

  The monomer composition preferably contains a monomer (a3) having a carboxyl group and an ethylenic double bond and / or a monomer (a4) having a hydroxyl group and an ethylenic double bond. When the copolymer (A) contains a carboxyl group and / or a hydroxyl group, the copolymer (A) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group (C). It is cross-linked to be immobilized on the surface of the cured coating film, and the ink repellency and ink tumbling durability are improved.

  Examples of the monomer (a3) having a carboxyl group and an ethylenic double bond include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. It is done.

  As the monomer (a4) having a hydroxyl group and an ethylenic double bond, 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 (meta) ) Acrylate, glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydride Ximethyl (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 composition includes a monomer (a1) having a group represented by the formula 1 and an ethylenic double bond, and a monomer having a group represented by the formula 2 and an ethylenic double bond. (A2) monomers other than the monomer (a3) having a carboxyl group and an ethylenic double bond and the monomer (a4) having a hydroxyl group and an ethylenic double bond (other monomers (a5) ) May be included.

  Other monomers (a5) 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 copolymer (A) can be synthesized, for example, by a method in which the monomer composition 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 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 content rate of the fluorine atom in a monomer composition is 1-30 mass%, and the ratio in the total solid of the photosensitive resin composition of a copolymer (A) is 1.5-30 mass%. Within this range, the copolymer (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, when it is in the range, the compatibility of the copolymer (A) with other components of the photosensitive resin composition is good, and the copolymer (A ) There is no aggregation between each other. 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 composition is preferably 3% by mass, and the upper limit is preferably 25% by mass. The lower limit of the proportion of the copolymer (A) in the total solid content of the photosensitive resin composition is preferably 2.5% by mass, more preferably 3% by mass, and the upper limit is preferably 20% by mass, more preferably 10% by mass. preferable. In particular, when the ratio of the copolymer (A) in the total solid content of the photosensitive resin composition is 2.5% by mass or more, the ink repellency / ink fall-off property after irradiation of the coating film cured product with short wavelength ultraviolet rays is excellent. I understood it.

  It is preferable that the content rate of the silicon atom in a monomer composition is 0.1-10 mass%, More preferably, it is 0.5-5 mass%. When the content is 0.1% by mass or more, the ink repellency after irradiation of the coating film cured product with short wavelength ultraviolet rays is good. When it is 10% by mass or less, the photosensitive resin composition has good compatibility with other components, and the resulting cured product has a good coating film appearance.

  When the monomer composition contains the monomer (a3) having a carboxyl group and an ethylenic double bond, the acid value of the copolymer (A) is preferably 1 to 100 mgKOH / g, and 5 to 50 mgKOH / g. Is more preferable. When the acid value is within this range, the durability of the ink repellency and the ink tumbling property of the cured coating film based on the crosslinking reaction of the copolymer (A) and the crosslinking agent (C) 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 composition includes a monomer (a4) having a hydroxyl group and an ethylenic double bond, the hydroxyl value of the copolymer (A) is preferably 50 to 300 mgKOH / g, and 100 to 200 mgKOH / g. More preferred. When the hydroxyl value is within this range, the durability of the ink repellency and the ink tumbling property of the cured coating film based on the crosslinking reaction of the copolymer (A) and the crosslinking agent (C) becomes good. The hydroxyl value is the mass (unit: mg) of potassium hydroxide required to acetylate 1 g of the resin, and the unit is described as mgKOH / g in this specification.

  The proportion of other monomers in the monomer composition is preferably 70% by mass or less, and more preferably 50% by mass or less. Within this range, the developability of the photosensitive resin composition will be good.

  The number average molecular weight of the copolymer (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 alkali-soluble resin (B) has a carboxyl group and / or a phenolic hydroxyl group. Crosslinking with the crosslinking agent (C), which is a compound that is soluble in an alkaline solution by having a carboxyl group and / or a phenolic hydroxyl group, and has two or more groups that can react with the carboxyl group and / or the phenolic hydroxyl group Then, a cured film can be formed. The alkali-soluble resin (B) can be used without any limitation as long as it is a resin that is soluble in an alkaline solution constituting a developer used in photolithography of the photosensitive resin composition. Resin (B1) and phenol resin (B2) obtained by polymerizing a monomer having a group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as essential. . These resins are preferably substantially free of fluorine atoms.

  The resin (B1) obtained by polymerizing a monomer having a carboxyl group and an ethylenic double bond and / or a monomer having a phenolic hydroxyl group and an ethylenic double bond as an essential component is the copolymer (A ), The monomer (a3) having a carboxyl group and an ethylenic double bond and / or the monomer (a4) having a phenolic hydroxyl group and an ethylenic double bond, if necessary, other single quantities It can be obtained by copolymerizing with the body (a5). In the resin (B1), the proportion of the monomer units based on the other monomer (a5) is preferably 70% by mass or less, and more preferably 50% by mass or less. Within this range, the alkali solubility and developability of the photosensitive resin composition are good.

  As the phenol resin (B2), at least one phenol selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol and hydroquinone and alkyl-substituted or halogen-substituted aromatic compounds is used as formaldehyde, acetaldehyde, benzaldehyde. For example, phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde co-condensation resin and the like can be mentioned.

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

  The number average molecular weight of the alkali-soluble resin (B) is preferably 200 to 20000, more preferably 2000 to 15000. Within this range, the alkali solubility and developability of the photosensitive resin composition will be good.

  10-90 mass% is preferable, and, as for the ratio in the total solid of the photosensitive resin composition of alkali-soluble resin (B), 30-80 mass% is more preferable. Within this range, the developability of the photosensitive resin composition of the present invention is good.

  The crosslinking agent (C) is a compound having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group. By having two or more groups capable of reacting with a carboxyl group and / or a phenolic hydroxyl group, it can be crosslinked with an alkali-soluble resin (B) having a carboxyl group and / or a phenolic hydroxyl group to form a cured coating film. Moreover, when a copolymer (A) has a carboxyl group and / or a hydroxyl group, it can also bridge | crosslink with a copolymer (A) and can form a coating-film hardened | cured material. The cross-linking agent (C) is preferably a compound that does not substantially contain a fluorine atom.

  The crosslinking agent (C) is preferably at least one selected from the group consisting of amino resins, epoxy compounds, and oxazoline compounds. These 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.

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

  The photoacid generator (D) is a compound that generates an acid by light. Examples of the photoacid generator (D) 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 and the like.

  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 (D) in the total solid content of the photosensitive resin composition is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass. Within this range, the developability of the photosensitive resin composition will be good.

  In the photosensitive resin composition, a silane coupling agent (E) can be used 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 (E) 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 (F) can be used. Specific examples of the diluent (F) include the solvents exemplified as the solvent for synthesizing the copolymer (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 coating film having no fluidity 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 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 is preferable to expose in the range of the exposure amount of 5 to 1000 mJ / cm ² .

  Next, if necessary, the acid is diffused, PEB treatment for accelerating the crosslinking reaction is performed, development is performed with a developer, and unexposed portions are removed.

  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 30 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. Further, 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, parts and% are based on mass unless otherwise specified. The number average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.

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, AA: acrylic acid, 2-HEMA: 2-hydroxyethyl methacrylate, MMA: methyl methacrylate, CHMA: cyclohexyl methacrylate,
IBMA: isobornyl methacrylate,
DSH: n-dodecyl mercaptan, V-70: 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, trade name V-70),
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 resin (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 copolymer (A-1)>
Into a 1 L internal reaction vessel equipped with a stirrer, acetone (557 g), C4FMA (108.0 g), X-8201 (24.0 g), MAA (12.0 g), MMA (48.0 g), IBMA ( 48.0 g), a chain transfer agent DSH (6.9 g) and a polymerization initiator V-70 (3.6 g) were charged and polymerized at 40 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a copolymer (A A solution of -1) was obtained. Water was added to the obtained copolymer (A-1) acetone solution for reprecipitation purification, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain 238 g of copolymer (A-1). . The number average molecular weight of the copolymer (A-1) was 7000, and the acid value of the copolymer (A-1) was 33 mgKOH / g.

[Synthesis Examples 2 to 7]
<Synthesis of copolymer (A-2 to 4) and copolymer (R-1 to 3)>
In the synthesis of the copolymer (A-1), the copolymer (A-2), the copolymer (A-3), the copolymer were synthesized by the same polymerization reaction except that the blending of raw materials was changed as shown in Table 1. A polymer (R-1), a copolymer (R-2), and a copolymer (R-3) were obtained.

  Table 1 shows the fluorine atom content in the monomer composition, the silicon atom content in the monomer composition, the acid value (mgKOH / g), and the hydroxyl value (mgKOH / g).

[Synthesis Example 8]
<Synthesis of alkali-soluble resin (B)>
To a 1 L internal reaction tank equipped with a stirrer, acetone (555 g), AA (36.0 g), 2-HEMA (108.0 g), IBMA (72.0 g), chain transfer agent DSH (9.7 g) And polymerization initiator V-70 (5.1 g) were charged and polymerized at 40 ° C. for 18 hours with stirring in a nitrogen atmosphere to obtain a solution of an alkali-soluble resin (B-1). Water was added to the obtained acetone solution of the alkali-soluble resin (B-1) for reprecipitation purification, then reprecipitation purification with petroleum ether, and vacuum drying to obtain 235 g of the alkali-soluble resin (B-1). . The number average molecular weight of the alkali-soluble resin (B-1) was 5000, and the acid value of the alkali-soluble resin (B-1) was 119 mgKOH / g.

[Examples 1 to 9]
<Evaluation of photosensitive resin composition>
Copolymer (A), copolymer (R), alkali-soluble resin (B), photoacid crosslinking agent (C), acid generator (D), silane coupling in the proportions (parts by mass) shown in Table 2. A photosensitive resin composition was obtained by blending the agent (E) and the diluent (F).

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, 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, developability, coating film appearance, substrate adhesion, ink repellency, ink falling property, ink repellency after short wavelength ultraviolet irradiation, ink falling property after short wavelength ultraviolet irradiation were measured by the following methods, evaluated. The evaluation results are shown in Table 2.

[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 coated plate was scratched with a cutter so that the number of squares was 25 at intervals of 2 mm. 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]
Using a low-pressure mercury lamp as a light source, evaluation was made based on the contact angle between water and xylene after irradiating a short-wave ultraviolet ray for 3 minutes to the cured film formed on the glass substrate.

[Ink tumbling after short wavelength UV irradiation]
Using a low-pressure mercury lamp as a light source, evaluation was made based on the contact angle between water and xylene after irradiating a short-wave ultraviolet ray for 3 minutes to the cured film formed on the glass substrate.

  In Example 5, the proportion of the copolymer (A) in the total solid content of the photosensitive resin composition is too low, and the ink repellency and the ink falling property of the cured film are inferior. In Example 6, the proportion of the copolymer (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 7, the content of fluorine atoms in the monomer composition is too low, and the ink repellency and ink tumbling properties of the cured coating film are poor. In Example 8, the fluorine atom content in the monomer composition is too high, and the coating film appearance and substrate adhesion are poor. In Example 9, the monomer composition does not contain the monomer represented by the above formula 2 and the monomer (a2) having an ethylenic double bond. Poor ink repellency and ink tumbling properties.

The photosensitive resin composition of the present invention can be applied to applications that require ink repelling properties. For example, it is suitably used for forming partition walls for color filters for liquid crystal displays or organic EL displays, and for forming partition walls for forming wiring patterns in semiconductor devices or electric circuits.

Claims (5)

Monomer having a group represented by the following formula 1 and a monomer (a1) having an ethylenic double bond and a monomer having a group represented by the following formula 2 and an ethylenic double bond (a2) A copolymer (A) having a structure obtained by polymerizing the composition, an alkali-soluble resin (B) having a carboxyl group and / or a phenolic hydroxyl group, and a group capable of reacting with the carboxyl group and / or the phenolic hydroxyl group; A photosensitive resin composition for light having a wavelength of 100 to 600 nm, comprising a crosslinking agent (C), which is a compound having two or more compounds, and a photoacid generator (D),
-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 fluorine atom content in the monomer composition is 1 to 30% by mass, and the proportion of the copolymer (A) in the total solid content of the photosensitive resin composition is 1.5 to 30% by mass. A photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein a ratio of the copolymer (A) in the total solid content of the photosensitive resin composition is 2.5 to 30% by mass.   The photosensitive resin composition according to claim 1 or 2, wherein a content of silicon atoms in the monomer composition is 0.1 to 10% by mass.   The monomer composition further comprises a monomer (a3) having a carboxyl group and an ethylenic double bond and / or a monomer (a4) having a hydroxyl group and an ethylenic double bond. The photosensitive resin composition in any one. A cured coating film obtained from the photosensitive resin composition according to claim 1.