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WO2005083019A1 - Composition de résine de revêtement - Google Patents

Composition de résine de revêtement Download PDF

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Publication number
WO2005083019A1
WO2005083019A1 PCT/JP2005/002912 JP2005002912W WO2005083019A1 WO 2005083019 A1 WO2005083019 A1 WO 2005083019A1 JP 2005002912 W JP2005002912 W JP 2005002912W WO 2005083019 A1 WO2005083019 A1 WO 2005083019A1
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WO
WIPO (PCT)
Prior art keywords
monomer
coating
group
alkyl group
fluorinated alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/002912
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English (en)
Japanese (ja)
Inventor
Hideya Suzuki
Kiyofumi Takano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dainippon Ink and Chemicals Co Ltd filed Critical Dainippon Ink and Chemicals Co Ltd
Priority to KR1020067011155A priority Critical patent/KR101099399B1/ko
Publication of WO2005083019A1 publication Critical patent/WO2005083019A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a coating resin composition having excellent thin film uniformity of a coating film.
  • a photolithography method is employed.
  • a resist film photosensitive resin composition
  • active energy rays such as ultraviolet rays, far ultraviolet rays, excimer laser light, and X-rays.
  • the resist agent is usually coated on a silicon wafer by a spin coating method or the like so as to have a thickness of about 11 2 / im.
  • the coating property of the resist agent is poor, the thickness of the obtained coating film is not uniform, or radial coating unevenness generally called striation is generated.
  • Such non-uniformity of the coating film may cause problems such as a decrease in linearity and reproducibility of fine patterns in fields requiring fine pattern accuracy, such as thin film transistors (TFT) arrays of LSIs and LCDs. Occurs.
  • TFT thin film transistors
  • Patent Document 2 a commercially available fluorine-based surfactant is used, and in a precise application as described above, an inhomogeneous portion (application unevenness) may still occur.
  • fluorosurfactants which are conventionally known and usually used as additives, are designed to maintain compatibility with a wide range of resins. It is considered that compatibility with the resin having an acidic group or an aromatic ring as used in Reference 2 is insufficient, and as a result, sufficient surface activity is not exhibited.
  • Resins having an acidic group or an aromatic ring include, in addition to the photosensitive colored resin composition described in Patent Document 2, a photosensitive resin composition such as a photoresist for a spacer for a liquid crystal cell, and a color resin. It is also used in filter overcoating agents and various hard coating agents. In these applications, it is necessary to form thin films by spin coating, slit & spin coating, slit coating, and the like. From these points, a resin composition for coating capable of obtaining a coating film having excellent uniformity in a thin film has been desired.
  • Patent Document 1 JP-A-10-309455 (pages 3-14)
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-222997 (page 13)
  • an object of the present invention is to provide a coating resin composition having excellent thin film uniformity of a coating film.
  • a fluorine-based surfactant comprising a fluorinated alkyl group-containing vinyl polymer having a fluorinated alkyl group, an aromatic ring, and an acidic group. And a binder resin having an aromatic ring and an acidic group.
  • a resin composition for coating a thin film having a submicron thickness of several tens of microns, particularly a few microns, is formed by a method such as spin coating, slit & spin coating, or slit coating.
  • the present inventors have found that coating unevenness does not occur when a thin film is formed, and the thin film is excellent in uniformity, and thus the present invention has been completed.
  • the present invention provides a fluorinated surfactant comprising a fluorinated alkyl group-containing vinyl polymer (A) having a fluorinated alkyl group (al), an aromatic ring (a2) and an acidic group (a3). And a binder resin (B) having an aromatic ring (bl) and an acidic group (b2).
  • A fluorinated alkyl group-containing vinyl polymer
  • A2 having a fluorinated alkyl group (al), an aromatic ring (a2) and an acidic group (a3)
  • a binder resin (B) having an aromatic ring (bl) and an acidic group (b2).
  • a coating resin composition having excellent thin film uniformity of a coating film.
  • the composition is used in fields requiring fine pattern accuracy, such as LSI and TFT arrays of LCDs, in the production of color filters used for color LCDs, etc., for overcoating of color filters, and for liquid crystal cells. It can be suitably used in a field where a thin film is required to be formed by a spin coat method, a slit & spin coat method, a slit coat method or the like such as a photoresist for a spacer.
  • a fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group), and one in which some hydrogen atoms in the alkyl group are fluorine atoms. It is a generic term for substituted (for example, HCF CF CF CF etc.), and may be any of linear or branched groups. It should be noted that those containing an oxygen atom in the fluorinated alkyl group (for example, CF-(OCF CF) etc.) are also included in the definition of the fluorinated alkyl group of the present invention.
  • the fluorinated alkyl group-containing vinyl polymer (A) used in the present invention comprises at least one fluorinated alkyl group (al), at least one aromatic ring (a2), and at least one acidic group (a3).
  • the molecular weight of the polymer (A) is determined based on the compatibility with the binder resin (B) described below, It is excellent in compatibility, prevents aggregation of fluorinated alkyl groups, and has excellent thin film uniformity of the resulting coating film, and suppresses foaming property and develops defoaming property in the composition.
  • the weight average molecular weight is usually 1,000 to 200,000, preferably 5,000 to 100,000, and more preferably 8,000 to 80,000.
  • fluorinated alkyl groups are hydrophobic and oleophobic. Therefore, in order for a compound having a fluorinated alkyl group to function as a surfactant, it is necessary to maintain compatibility with various media (solutions and resins) to which the compound is added. That is, it is necessary to introduce a lipophilic group (a lipophilic group and Z or a hydrophilic group) into the activator.
  • a lipophilic group a lipophilic group and Z or a hydrophilic group
  • the medium in which the fluorinated surfactant is used is not limited. Therefore, when designing an amphiphilic group, it is often less advantageous to select an amphiphilic group that maintains compatibility with a wider range of media. In addition, since the amount of the fluorinated surfactant added to the medium is small due to the high surfactant activity derived from the fluorinated alkyl group, the amphiphilic group is usually compatible with the resin component contained in the medium. Yes, it was not designed in consideration of. In addition, when selecting a surfactant for the type of the target medium, the compatibility with the solution (in this case, solubility) is confirmed, but the compatibility with the resin in the medium is usually focused on. Often not.
  • a surfactant which is compatible (dissolved) only in the solvent in the medium and hardly compatible with the resin may be selected.
  • a surfactant that is only compatible (dissolved) in a solvent cannot sufficiently exhibit a function as a surfactant. That is, even when the surfactant is compatible (dissolved) in the solution, the solvent or water is volatilized in the drying process after coating or in the coating, and the non-volatile content (resin concentration) is increased. When the amount of the coating increases, the coating appearance may be poor.
  • the surfactant has a large effect on the coating appearance (see
  • the term "thin film” in the present invention indicates a submicron to several tens of micron level.)
  • the present invention improves the compatibility between the resin and the fluorosurfactant in consideration of the functional groups constituting the resin when selecting the amphiphilic group in the fluorosurfactant, and as a result, It has improved homogeneity.
  • the fluorinated alkyl group (al) in the fluorinated alkyl group-containing polymer (A) is indispensable in order to develop a surface activity capable of preventing uneven coating.
  • the number of carbon atoms in the fluorinated alkyl group (al) is usually an integer of 120, preferably an integer of 3 12 because of a high effect of surface activity. And particularly preferably a linear perfluoroalkyl group.
  • the fluorine atom content in the polymer (A) is determined by burning and decomposing the polymer (A), extracting the decomposed product with water or alkaline water, and quantifying the fluorine ion concentration by ion chromatography.
  • the aromatic ring (a2) and the acidic group (a3) in the polymer (A) are required to increase the compatibility with the binder resin (B) described later.
  • the aromatic ring (a2) is not particularly limited, and examples thereof include a benzene ring and a naphthalene ring which may have a substituent such as an alkyl group, and two or more aromatic rings such as a biphenyl skeleton. May be connected.
  • the polymer (A) may contain two or more different aromatic rings (a2). Among these, a benzene ring is preferable because it is easy to achieve both compatibility between the polymer (A) and a binder resin (B) described later and surface activity.
  • FT-IR FT-IR spectroscopy
  • the copolymerization ratio of benzyl methacrylate and methyl methacrylate was changed, and azoisobutyronitrile (AIBN) was used as the initiator in methyl isobutyl ketone (MIBK) to obtain a copolymer having a weight average molecular weight of 30,000.
  • the polymer was synthesized by radical polymerization.
  • the content of the aromatic ring (a2) in the polymer (A) measured based on this calibration curve is preferably from 10 to 40% by weight, more preferably from 20 to 35% by weight.
  • Examples of the acidic group (a3) include a carboxy group, a hydroxyl group, a phosphoric acid group, and a sulfonic acid group. These groups are the fluorinated alkyl group (al) or the aromatic ring (a2
  • the position in the polymer (A) which may be present in the polymer (A) as a substituent of ()) is not limited. Further, the polymer (A) may have two or more different acidic groups (a3). Among these, from the viewpoint that compatibility between the polymer (A) and a binder resin (B) to be described later is easily compatible with surface activity, and that the storage stability of the obtained coating resin composition is excellent.
  • the compound be a carboxyl group or a hydroxyl group.
  • foaming is small, and from the viewpoint, a hydroxyl group is preferable.
  • the content of the acidic group (a3) in the polymer (A) is preferably 2 to 100 mgKOH / g, more preferably 7 to 70 mgK ⁇ H / g as the acid value, and the hydroxyl value is preferably 20 and 200 mgKOHZg, particularly preferably 30-130 mgKOH / g.
  • the method for producing the polymer (A) is not particularly limited, but it is easy to obtain industrial raw materials, easy to produce, easy to adjust the weight average molecular weight, and as described above. From the viewpoint of ease of introduction of a functional group (fluorinated alkyl group, aromatic ring, acidic group), fluorinated alkyl group-containing monomer (xl), aromatic ring-containing monomer (x2), and It is preferable to copolymerize the monomer (I), including the acidic group-containing monomer (x3).
  • a functional group fluorinated alkyl group, aromatic ring, acidic group
  • xl fluorinated alkyl group-containing monomer
  • x2 aromatic ring-containing monomer
  • xl a fluorinated alkyl group-containing vinyl monomer
  • x2 an aromatic ring-containing vinyl monomer
  • x3 an acidic group-containing vinyl monomer
  • the fluorinated alkyl group-containing monomer (xl), the aromatic ring-containing monomer (x2), and the acidic group-containing monomer in the monomer (I) The total of the isomer (x3) is 60% by weight or more, and the content of the fluorinated alkyl group-containing monomer (xl) in the monomer (I) is usually 3 to 50% by weight. %, Preferably 10 to 40% by weight, and the content of the aromatic ring-containing vinyl monomer (x2) is usually 40 to 90% by weight, preferably 50 to 80% by weight,
  • the content of the acidic group-containing vinyl monomer (x3) is usually 0.1 to 30% by weight, preferably 0.5 to 7% by weight.
  • the use ratio of the monomer (x4) which is a group of one or more other monomers described below, is good even when used together.
  • the content is preferably 40% by weight or less in the monomer (I), and particularly preferably 20% by weight or less.
  • the structure of the fluorinated alkyl group-containing monomer (xl) is not particularly limited, and various structures can be used. For example, the following general formula (xl-1) , (Xl-2).
  • CH 2 C CO-CX riir-Rf (xl-1)
  • R, R, and R are the same or different and are each a fluorinated alkyl group having 120 carbon atoms.
  • R is a hydrogen atom, a methyl group, a chlorine atom or a fluorine atom, and X 1 , X 2 , and X 3 are the same
  • m 1 m 3 is the same or different and is 0 or 1.
  • X 1 , X 2 , and X 3 (a divalent linking group) in the general formulas (xl-1) and (xl-2) are not particularly limited. No.
  • n is an integer of 110, and R is a hydrogen atom or an alkyl group having 116 carbon atoms.
  • Examples of the monomer (xl) include compounds represented by the following structural formulas (xl-1-l) — (xl-1-55) and (xl-2-1).
  • CH 2 CHCOOCH 2 (CF 2 ) 2 H xl-1-28
  • CH 2 CHCOOCH 2 (CF 2 ) 4 H
  • CH 2 CHCOOCH 2 (CF 2 ) 6 H
  • the monomer (xl) only one type may be used, or two or more types having different structures may be used. May be used as a mixture of the above compounds.
  • the number of carbon atoms in the fluorinated alkyl group in the monomer (xl) is preferably an integer of 3-12, particularly preferably an integer of 6-10. It is preferably a perfluoroalkyl group.
  • the aromatic ring-containing vinyl monomer (x2) has a structure having both a vinyl group and an aromatic ring such as a benzene ring or a naphthalene ring which may have a substituent in the same molecule. If it is a compound, it can be used without particular limitation.
  • (meth) acrylate refers to atalylate and / or methacrylate unless otherwise specified.
  • the monomer (x2) may be used singly or as a mixture of two or more compounds having different structures.
  • the acidic group-containing bull monomer (x3) has a structure having both a bull group and an acidic group such as a carboxyl group, a hydroxyl group, a phosphoric acid group, or a sulfonic acid group in the same molecule. If it is a compound, it can be used without particular limitation.
  • acrylic acid methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, 2- (meth) ataryloy mouth xishethyl succinic acid, 2- (meth) ataryloy mouth xyphthalic acid, 2- (meth) ataryloy Carboxyl group-containing vinyl monomers such as methoxyhexahydrophthalic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate
  • an acidic group-containing vinyl monomer in which the acidic group is a carboxyl group or a hydroxyl group, since the obtained resin composition for coating is excellent in storage stability. It is preferable to use a hydroxyl group-containing butyl monomer from the viewpoint of less foaming when the composition is prepared.
  • the monomer (I) another monomer (x4) can be used in combination, if necessary, as long as the effects of the present invention are not impaired.
  • the other monomer (x4) various monomers can be used as long as they can be copolymerized with the monomers (xl), (x2) and (x3).
  • alkyl (meth) acrylates having 18 carbon atoms in the alkyl group ie, methyl (meth) acrylate, methyl ethyl, propynole, butyl, octyl, 2-ethylhexyl, decyl, dodecinole, stearyl Esters and the like.
  • a monomer containing a bridge such as diester
  • dicyclopentanyloxylethyl (meth) atalylate isobornyloxylethyl (meth) atalylate, isobornyl (meth) atalylate, adamantyl (meth) acrylate
  • Acrylates dimethyl adamantyl (meth) atalylate, dicyclopentanyl (meth) atalylate, dicyclopentenyl (meth) atalylate, etc.
  • alkylbier ethers having 118-alkyl carbon atoms
  • acrylonitrile, butyl chloride, vinylidene chloride, N-butylpyrrolidone, butyl sulfonic acid, fatty acid butyl such as butyl acetate, a silane coupling group-containing monomer such as 3_ (meth) atalyloxypropyl trimethoxy silane examples include silicone chain-containing monomers such as polydimethylsiloxane chain-containing (meth) acrylates.
  • the method of copolymerizing the monomers (I) is not particularly limited, and various methods may be used. It is possible to For example, they can be produced by solution polymerization, bulk polymerization, emulsion polymerization, or the like, respectively, using a radical polymerization method, a cationic polymerization method, or an anion polymerization method. Particularly, a radical polymerization method is simple and industrially preferable.
  • Polymerization initiators that can be used in these cases are not particularly limited, and examples thereof include peroxides such as benzoyl peroxide and diacetyl peroxide, and benzenes such as AIBN and phenylazotriphenylmethane. Zo compounds and metal chelates such as Mn (acac). Polymerization
  • the amount of the initiator used is not particularly limited and may be appropriately selected depending on the desired weight average molecular weight of the copolymer and the like, but is usually 0.1 to 1% with respect to the monomer (I). 5 is the mole 0/0, it is preferable 0.3 is 3 mol 0/0.
  • a chain transfer agent such as lauryl mercaptan, 2_mercaptoethanol, ethyl thioglycolic acid, octyl thioglycolic acid may be used, or ⁇ -mercaptopropyltrimethoxysilane or the like may be used.
  • the coupling group-containing thiol conjugate can also be used as an additive such as a chain transfer agent.
  • the ability to obtain a random or block copolymer also by photopolymerization performed in the presence of a photosensitizer and a photoinitiator, or polymerization using radiation or heat as an energy source. S can.
  • the polymerization can be carried out in the presence or absence of a solvent, but the workability is preferred.
  • a solvent is preferred.
  • the solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, methyl acetate, and ethyl acetate.
  • polar solvents such as dimethylformamide, dimethylsulfoxide, etc., 1,1,1,1-trichloroethane, halogen solvents such as chloroform, ethers such as tetrahydrofuran, dioxane, benzene, toluene, etc.
  • Aromatic organic solvents such as xylene, and fluorinated acrylates such as perfluorooctane and perfluorotory n-butylamine can be used.
  • the method of introducing the reactants such as the monomer (1), the polymerization initiator, the solvent, etc. is not limited at all. ) May be added dropwise to the solvent to carry out the polymerization reaction.
  • a dripping solution is prepared by uniformly mixing the monomers (I) which may contain a solvent, and the solution is dropped into the reaction solvent.
  • a polymerization reaction is performed.
  • the copolymer obtained by the above method can be separated and purified by various methods such as various column treatments, washing with a solvent, and reprecipitation operation. Further, as the copolymer, only one kind may be used as the fluorine-based surfactant used in the present invention, and two or more kinds may be used at the same time.
  • the structure of the binder resin (B) used in the present invention is not particularly limited as long as it is at least one resin having at least one aromatic ring (bl) and at least one acidic group (b2). Not something. Further, as the binder resin (B), two or more resins having different structures may be used in combination.
  • Examples of the aromatic ring (bl) include a benzene ring and a naphthalene ring which may have a substituent, and a structure in which two or more aromatic rings such as a biphenyl skeleton are connected. There may be. Further, the binder resin (B) may contain two or more different aromatic rings (bl). Among them, benzene which may have a substituent is preferable because it has good compatibility with the fluorinated alkyl group-containing polymer (A) and a coating film having excellent thin film homogeneity can be obtained. It is preferably a ring.
  • substituents examples include an alkyl group having 11 to 10 carbon atoms, a hydroxyl group, an alkoxy group, a carboxyl group, a sulfonic acid group, and a fluorine atom.
  • the aromatic ring ( a2 ) in the fluorinated alkyl group-containing vinyl polymer (A) and the aromatic ring (bl) in the binder resin (B) are the same, including the presence or absence of a substituent. However, there is no restriction that they may be different from each other.
  • Examples of the acidic group (b2) include a carboxyl group, a hydroxyl group, a phosphoric acid group, and a sulfonic acid group. These groups may be present in the binder resin (B) as a substituent on the aromatic ring (bl), for example. Also, the binder resin (B) may have two or more different acidic groups (b2). Among them, good compatibility with the fluorinated alkyl group-containing polymer (A), excellent uniformity of the obtained coating film, and storage stability of the obtained coating resin composition. Acidic group (b2) is a carboxyl group or a hydroxyl group The hydroxyl group is preferred from the viewpoint of less foaming when the composition is preferably prepared.
  • the acidic group (a3) in the fluorinated alkyl group-containing vinyl polymer (A) and the acidic group (b2) in the binder resin (B) may be the same or different from each other, and are not limited. However, the same acidic group is preferable from the viewpoint of more excellent compatibility.
  • the binder resin (B) is a main component of the coating. According to the knowledge of the present inventors, the combination of the binder resin (B) and the fluorinated alkyl group-containing polymer (A) is known. Optimizing the combination is extremely important for obtaining thin film uniform coating properties.
  • the choice of the binder resin (B) is mainly determined by the application of the coating resin composition, the required properties (eg, mechanical properties, chemical resistance, optical properties, etch resistance), and the manufacturing process. You.
  • a phenol novolak resin is used as the binder resin (B).
  • a hydroxystyrene resin is used in the case of a photoresist using KrF line.
  • Various reactive compounds, such as photosensitizers, are used in combination.
  • an acrylic resin that is non-photosensitive as a binder resin (B) and soluble in an alkaline aqueous solution for example, benzyl (meth) acrylate and (meth) acrylic acid copolymer is used.
  • Copolymerization benzinole (meth) atalylate '(meth) atalylic acid / alkyl polyoxyethylene (meth) atalylate copolymer, etc.] and a polyfunctional atalylate as a photosensitive polymer component that is a reactive compound And the like, and further used in combination with a photopolymerization initiator.
  • An overcoating agent for a color filter, an antireflection coating agent for a polarizing plate surface, and the like do not involve a development step in their use.
  • a so-called photo-curable resin for example, an acrylic resin, an acrylic oligomer, an acrylic monomer, an epoxy resin, an acryl-modified epoxy resin, an epoxy-modified acrylic resin, a urethane-modified acrylic resin
  • the binder resin (B) is used as the binder resin (B).
  • a polyester-modified acrylic resin, etc. which is used in combination with a photopolymerization initiator to produce a coating agent, which is applied to the entire surface of the target base material, and which is light-cured and used.
  • acrylic copolymers having both an aromatic ring and a carboxyl group for example, benzyl (meth) atalylate and (meth) are particularly preferred from the viewpoint that the effects of the present invention can be easily realized.
  • Acrylic acid copolymers or multi-component copolymers of benzyl (meth) acrylate and (meth) acrylic acid with other monomers are preferred as the binder resin (B).
  • the acid value of the binder resin (B) is preferably 30 to 400 mgKOH / g, and the weight average molecular weight is preferably in the range of 1,000 to 300,000, preferably 5,000 to 200,000. That power S is particularly preferred.
  • the resin composition for coating of the present invention is not limited as long as it is a resin composition containing the above-mentioned fluorinated alkyl group-containing butyl polymer (A) and the binder resin (B). It is not done.
  • other components such as a photosensitive colored resin composition and the like can further contain a colorant (eg, a pigment or a dye), a dispersant, or the like. Since the fluorinated alkyl group-containing polymer (A) used in the present invention has an aromatic ring, it has good compatibility with commonly used organic colorants (pigments).
  • ком ⁇ онентs such as a cohesive agent, a thixotropic agent, a resin dissolution inhibitor, and a silane coupling agent may be added to the resin composition of the present invention.
  • examples of usable components when used as a negative photoresist include a combination of a butyl monomer capable of undergoing addition polymerization by light irradiation and a photopolymerization initiator.
  • Specific examples of the bier-based monomers include trimethylolpropane triatalylate, pentaerythritol tetraatalylate, dipentaerythritol pentaacrylate, dipentaerythritol hexatalylate, and the like.
  • examples of usable components when used as a positive photoresist include a quinonediazide compound which can be suitably used in combination with a novolak resin binder resin.
  • various solvents can be used without any limitation, for example, acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2_heptanone, methyl isobutyl Ketones, ketones such as butyrolataton, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butynoleanolone, tert-butynoleanolone, pentanole, heptano Ichinore, Ota Alcohols such as ethanol, nonanole, decanol, etc., ethers such as ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, dioxane, etc., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropynole Alcohol ethers such as athenole,
  • the obtained coating resin composition has an excellent balance between applicability and drying property.
  • the mixing ratio of the solvent can be appropriately adjusted according to application conditions such as a required film thickness when applying the coating resin composition. Force, but usually for coating 10 to 10,000 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight in total of the resin component of the fat composition and the above-mentioned various reactive compounds optionally used in combination with the rainer resin (B). It is 2,000 parts by weight.
  • pigments and dyes such as red, green, blue, and black can be used without particular limitation. Pigments are preferred in terms of heat resistance and light resistance.In general, the average particle size of the pigment is 0.005 3 xm, and in particular, a transparent coating film with good coatability of the resin composition for coating can be obtained. Therefore, it is preferably 0.01-1: 1 zm.
  • the dispersant is not particularly limited as long as the dispersant is effective in dispersing a colorant or the like.
  • a pigment intermediate, a dye intermediate, a polyamide-based compound, a polyurethane-based compound, an acrylic-based compound, a polyester-based compound, and the like can be given.
  • the content of the fluorinated alkyl group-containing polymer (A) in the coating resin composition of the present invention depends on the required film thickness when applying the resin composition to a substrate, application conditions, and the like. It is appropriately selected depending on the situation.
  • the fluorinated alkyl group-containing polymer (A) is 0.0005 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 1005 parts by weight, per 100 parts by weight of the resin composition. 0.05-1 part by weight.
  • the fluorine-containing alkyl group-containing vinyl polymer (A) having a low fluorine atom content When the fluorine-containing alkyl group-containing vinyl polymer (A) having a low fluorine atom content is used, the fluorinated anoalkyl group-containing vinyl polymer in the coating resin composition of the present invention is used. By increasing the content of the polymer (A), it is possible to sufficiently exert the effects of the present invention.
  • the method of mixing the fluorinated alkyl group-containing butyl polymer (A) is not limited.
  • a method in which the vinyl polymer (A) is added to a mixture in which the above-mentioned components are uniformly mixed in advance and mixed, or a colorant, which is usually used when preparing a photosensitive colored resin composition includes a binder resin.
  • B a method of dispersing with a dispersant, a solvent, or the like, a method of adding at the time of producing a so-called color paste, or the like, in which a vinyl polymer (A ) Is prepared by dissolving or dispersing the composition, and the like.
  • Various methods can be applied as a method of applying the coating resin composition of the present invention.
  • examples include spin coating, roll coating, dip coating, spray coating, blade coating, curtain coating, slit coating, slit & spin coating, etc. It can be suitably used for a thin film coating method such as a coating method and a slit coating method.
  • the method for forming the coating film is not particularly limited, and is selected according to the use of the coating resin composition and the like.
  • natural drying (lacquer), heat curing reaction, light curing reaction, etc. are appropriately selected and used as a method for obtaining a desired film. Is preferred.
  • the use of the coating resin composition of the present invention is not particularly limited.
  • photosensitive colored resin compositions for color filters for liquid crystal displays that require fine colored patterns, overcoating agents for color filters, spacer materials for liquid crystal cells, anti-reflective coating materials for optical films, and various hard coats When used as a material or the like, the effects of the present invention can be easily exhibited, and this is the most preferable use.
  • MIBK methyl isobutyl ketone
  • copolymer (A-1) The weight average molecular weight of the obtained copolymer was measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase and found to be 10,900 in terms of polystyrene.
  • a copolymer (A-5) was synthesized in the same manner as in Synthesis Example 1 except that 5) was used.
  • the weight average molecular weight of the obtained copolymer (A-5) was 10,700.
  • a copolymer (A-6) was synthesized in the same manner as in Synthesis Example 1 except that 6) was used. Obtained co The weight average molecular weight of the polymer (A-6) was 10,000.
  • the polymerization reaction was carried out by holding the mixture at the same temperature for 10 hours. Thereafter, the solvent was removed under reduced pressure at 80 ° C, and the remaining solid was dried to obtain a copolymer (A-9). .
  • the weight average molecular weight of the obtained copolymer (A-9) was 46,500.
  • Synthesis Example 11 Synthesis of fluorinated alkyl group-containing vinyl monomer described in Patent Document 1
  • monomers (I 1) were combined with 20 parts of a fluorinated alkyl group-containing vinyl monomer (X 1-1-1), 30 parts of isostearyl atalylate, and ethylene oxide having a molecular weight of about 400.
  • a copolymer (A) was prepared in the same manner as in Synthesis Example 1 except that a monomer ( ⁇ -ll) consisting of 42 parts of one-terminal acrylate and one part of methyl methacrylate was used as a copolymer of propylene oxide. -11) was synthesized. The weight average molecular weight of the obtained copolymer ( ⁇ -11) was 11,000.
  • the monomers (I-1) were converted to a fluorinated alkyl group-containing ethylenically unsaturated monomer (xl_l_l) 20 parts, isostearyl atalylate 30 parts, and one end of a molecular weight of about 500 was a methyl group.
  • a copolymer ( ⁇ - 12) was prepared in the same manner as in Synthesis Example 1 except that a monomer (42) containing one part of acrylate of one end of polyethylene oxide and 8 parts of methyl methacrylate was used. ) was synthesized. The weight average molecular weight of the obtained copolymer ( ⁇ -12) was 12,200.
  • Table 1 shows the fluorine atom content, the aromatic ring content, and the acid value / hydroxyl value of the fluorinated alkyl group-containing vinyl polymer synthesized as described above.
  • Example 11 and Comparative Example 1 except that Megafac R-30 (manufactured by Dainippon Ink and Chemicals, Inc., perfluoroalkyl group-containing fluorinated acrylic oligomer) was used as the fluorinated surfactant. The applicability was evaluated in the same manner as in 1-3.
  • MEGAFAK F-143 as a fluorinated surfactant [C FSON (R) CH CH 0 (CH CH O) H (R is an alkyl group, average of n is 15) manufactured by Dainippon Ink and Chemicals, Inc.]
  • Non-polymerized C F CH CH SCH CH COONH is used as the fluorinated surfactant
  • this coating method is spin coating, the rotation speed is relatively low, so that spin coating is performed. Scattering of the solvent in the pin coating 1 5 - 30% and less. [Rotating at high speeds (2000-3000 rpm) typically causes 85-95% of the solvent to scatter during spin coating. Therefore, in addition to the coating unevenness caused by the shearing force associated with rotation (coating unevenness that is a problem in spin coating), the presence or absence of solvent drying unevenness in the drying process, which is particularly problematic in slit coating, is also considered. Observable.
  • Methacrylic acid Z benzyl methacrylate as binder resin (B) 13Z87 (weight ratio) 25.0 parts of a copolymer (acid value: 84 mgKOH / g, weight average molecular weight: 22,000) in propylene glycol monomethyl ether acetate (nonvolatile content: 39.7% by weight), propylene glycol monomethyl ether acetate as a solvent 64.5 Of the copolymer (A-1) obtained in Synthesis Example 1-13 and a fluorosurfactant consisting of (A-13) and Megafac R_30, F_143, and CF CH CH SCH CH COONH to 0.
  • a coating resin composition having excellent thin film uniformity of a coating film is provided.
  • the composition can be suitably used in fields where fine pattern accuracy is required, fields where thin film formation is required, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Il est divulgué une composition de résine de revêtement caractérisé par le fait de contenir un surfactant de fluorure qui est composé d'un groupe contenant du polymère de vinyle (A) ayant un groupe d'alkyle fluoré (a1), un noyau aromatique (a2) et un groupe d'acide (a3), et un liant de résine (B) ayant un noyau aromatique(b1) et un groupe d'acides (b2).
PCT/JP2005/002912 2004-02-27 2005-02-23 Composition de résine de revêtement Ceased WO2005083019A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101271271B (zh) * 2007-03-21 2012-01-11 新应材股份有限公司 正型光阻剂
CN101154040B (zh) * 2006-09-25 2012-06-06 Az电子材料Ip(日本)株式会社 光致抗蚀剂组合物、其涂布方法及抗蚀剂图形的形成方法

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Publication number Priority date Publication date Assignee Title
CN103319959B (zh) * 2013-06-09 2015-11-18 广州市承信公路工程检验有限公司 桥梁缆索用聚乙烯防护底漆及其制作方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09302274A (ja) * 1996-05-08 1997-11-25 Dainippon Ink & Chem Inc 熱硬化性粉体塗料用樹脂組成物
JP2003222997A (ja) * 2001-11-22 2003-08-08 Fujifilm Arch Co Ltd 感光性着色樹脂組成物並びにその製造方法及びカラーフィルターの製造方法
JP2004002733A (ja) * 2002-03-28 2004-01-08 Dainippon Ink & Chem Inc コーティング用組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0559784B1 (fr) * 1990-11-27 1996-08-21 BAUSCH & LOMB INCORPORATED Macromonomeres tensioactifs
US5413885A (en) * 1993-12-22 1995-05-09 Rca Thompson Licensing Corp. Organic photoconductor for an electrophotographic screening process for a CRT

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09302274A (ja) * 1996-05-08 1997-11-25 Dainippon Ink & Chem Inc 熱硬化性粉体塗料用樹脂組成物
JP2003222997A (ja) * 2001-11-22 2003-08-08 Fujifilm Arch Co Ltd 感光性着色樹脂組成物並びにその製造方法及びカラーフィルターの製造方法
JP2004002733A (ja) * 2002-03-28 2004-01-08 Dainippon Ink & Chem Inc コーティング用組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154040B (zh) * 2006-09-25 2012-06-06 Az电子材料Ip(日本)株式会社 光致抗蚀剂组合物、其涂布方法及抗蚀剂图形的形成方法
CN101271271B (zh) * 2007-03-21 2012-01-11 新应材股份有限公司 正型光阻剂

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KR101099399B1 (ko) 2011-12-27
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CN100526404C (zh) 2009-08-12
TW200609308A (en) 2006-03-16
TWI346683B (en) 2011-08-11

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