WO2013058386A1 - 撥インク剤の製造方法、ネガ型感光性樹脂組成物、隔壁および光学素子 - Google Patents
撥インク剤の製造方法、ネガ型感光性樹脂組成物、隔壁および光学素子 Download PDFInfo
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- WO2013058386A1 WO2013058386A1 PCT/JP2012/077158 JP2012077158W WO2013058386A1 WO 2013058386 A1 WO2013058386 A1 WO 2013058386A1 JP 2012077158 W JP2012077158 W JP 2012077158W WO 2013058386 A1 WO2013058386 A1 WO 2013058386A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
Definitions
- the present invention relates to a method for producing an ink repellent, a negative photosensitive resin composition containing the ink repellent obtained by the method, a partition using the same, and an optical element having the partition.
- a partition used for a pixel portion of a color filter or an organic EL (Electro-Luminescence) element, which is an optical element, is known by a method in which a photosensitive resin composition is applied to a substrate and formed by photolithography.
- a cost reduction process using an inkjet method has been proposed as a method for manufacturing a color filter or an organic EL pixel portion.
- R red
- G green
- B blue
- inks are applied to the openings (dots) surrounded by the partition walls by an inkjet method. Spray and apply to form pixels.
- the partition wall is required to have a property of repelling ink containing water or an organic solvent which is an inkjet discharge liquid, so-called ink repellency.
- ink repellency since the ink layer formed on the pixel by the inkjet method is required to have high film thickness uniformity, the opening (dot) surrounded by the partition wall has good wettability with respect to the discharge liquid. It is required to have so-called ink affinity.
- the photosensitive resin composition may remain on the dots, and ink white spots may occur.
- ultraviolet / ozone irradiation treatment or the like is performed on the dots before ink injection, but there is also a problem that ink repellency of the partition walls is lowered at that time.
- Patent Document 1 includes an ink repellent agent composed of a hydrolyzed condensate of a fluorine-containing hydrolyzable silane compound that has a sufficiently small surface free energy and can retain ink repellency even after being subjected to ultraviolet / ozone irradiation treatment.
- a negative photosensitive resin composition is described.
- Patent Document 2 discloses a hydrolyzable silane having a secondary aromatic amino group that has good storage stability of a photosensitive resin composition and can improve the substrate adhesion of a cured film obtained using the composition.
- a photosensitive resin composition containing a compound is described.
- the negative photosensitive resin composition described in Patent Document 1 is stable when the silanol groups of the hydrolysis condensate constituting the ink repellent agent react with each other and are separated. In some cases, the properties were not sufficient.
- the hydrolyzable silane compound described in Patent Document 2 does not have a fluorine atom and does not function as an ink repellent agent.
- the present invention is excellent in storage stability in a negative photosensitive resin composition and excellent in ink repellency even when the partition wall produced from the composition is subjected to ultraviolet / ozone irradiation treatment.
- Method of ink repellent agent capable of imparting water, and negative photosensitive resin composition capable of producing partition walls that are excellent in storage stability and can maintain excellent ink repellency even after being subjected to ultraviolet / ozone irradiation treatment The purpose is to provide goods.
- Another object of the present invention is to provide a partition wall that has excellent ink repellency even after being subjected to ultraviolet / ozone irradiation treatment, and an optical element that has the partition wall and that suppresses the occurrence of white spots.
- the present invention provides a method for producing an ink repellent agent having the following configurations [1] to [13], a negative photosensitive resin composition, a partition, and an optical element.
- Ink repellent comprising a partially hydrolyzed condensate of a mixture containing a hydrolyzable silane compound represented by the following formula (c-1) and a hydrolyzable silane compound represented by the following formula (c-2)
- a method for producing the agent The manufacturing method of the ink repellent agent characterized by including the following process (I) and process (II).
- A represents a fluorine atom or a group represented by the following formula (1).
- each D is independently a hydrogen atom or a monovalent organic group having 1 to 12 carbon atoms in which the hydrogen atom bonded to the carbon atom may be substituted with an —NH 2 group.
- a group or a group represented by the following formula (2) is shown.
- R f a perfluoroalkylene group which may contain an etheric oxygen atom having 2 to 15 carbon atoms
- Q 1 , Q 3 a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms
- R H1 , R H2 a hydrocarbon group having 1 to 6 carbon atoms
- Q 2 and Q 4 are each independently a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms
- X 1 , X 2 , X 3 , X 4 each independently a hydrolyzable group
- q a number that is 0 or 1 and p + q is 1 or 2
- j 0 or 1.
- One of D and E in the formula (c-2) is a hydrogen atom, and the other is a C 6-12 carbon atom in which the hydrogen atom in the benzene ring may be substituted with an alkyl group
- R H3 a hydrocarbon group having 1 to 6 carbon atoms
- X 5 hydrolyzable group
- r 0, 1 or 2.
- R H3 and X 5 may be different from each other or the same.
- Y a group having an ethylenic double bond
- Q 5 a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms
- R H4 a hydrocarbon group having 1 to 6 carbon atoms
- X 6 hydrolyzable group
- g 1 or 2
- h Number that is 0 or 1 and g + h is 1 or 2.
- YQ 5 and X 6 may be different from each other or the same.
- the present invention when blended in a negative photosensitive resin composition, it has excellent storage stability in the composition, and excellent repellent properties even when the partition walls produced from the composition are subjected to ultraviolet / ozone irradiation treatment.
- Method for producing ink repellent agent capable of imparting ink properties, and negative photosensitive resin composition capable of producing partition walls that are excellent in storage stability and can maintain excellent ink repellency even after being subjected to ultraviolet / ozone irradiation treatment Can be provided.
- the present invention it is possible to provide a partition wall that has excellent ink repellency even after being subjected to ultraviolet / ozone irradiation treatment, and an optical element that has the partition wall and in which the occurrence of white spots or the like is suppressed.
- (meth) acryloyl ...” is a general term for “methacryloyl ...” and “acryloyl...”. The same applies to (meth) acrylate, (meth) acrylamide and (meth) acrylic resin.
- the group represented by Formula (1) in this specification is called group (1).
- the compound represented by formula (c-1) in this specification is referred to as compound (c-1).
- the “side chain” in the present specification is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting a main chain in a polymer in which a repeating unit constitutes the main chain.
- the “total solid content” in this specification refers to a partition-forming component among the components contained in the negative photosensitive resin composition, and the negative photosensitive resin composition is heated at 140 ° C. for 24 hours to remove the solvent. It is a removed residue. Specifically, all components other than the volatile component which volatilizes by heating etc.
- a film coated with the negative photosensitive resin composition is referred to as a “coating film”, a dried state is referred to as a “film”, and a film obtained by curing the film is referred to as a “cured film”. .
- the “surface” of the partition wall is used as a term indicating only the upper surface of the partition wall. Therefore, the “surface” of the partition does not include the side surface of the partition.
- the ink in the present specification is a general term for, for example, liquids having optically and electrically functions after being dried and cured, and is not limited to conventionally used coloring materials.
- pixels formed by injecting the ink are also used to indicate sections having optical and electrical functions, which are partitioned by partition walls.
- “Ink repellency” in the present specification refers to a property having moderately both water repellency and oil repellency in order to repel the ink, and can be evaluated by, for example, a method described later. Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification,% represents the mass%.
- the production method of the present invention comprises a hydrolyzable silane compound represented by the above formula (c-1) (hereinafter also referred to as hydrolyzable silane compound (c-1)) and the above formula (c-2). And a hydrolyzable silane compound (hereinafter, also referred to as a hydrolyzable silane compound (c-2)).
- c-1 hydrolyzable silane compound represented by the above formula (c-1)
- c-2 a hydrolyzable silane compound represented by the above formula (c-2)
- a hydrolyzable silane compound hereinafter, also referred to as a hydrolyzable silane compound (c-2)
- I) and process (II) are included.
- Step (II) A step of adding water and an acid catalyst to the mixture to cause hydrolysis and condensation of the mixture.
- the mixture contains a hydrolyzable silane compound (c-1) containing a fluorine atom and a hydrolyzable silane compound (c-2) having an amino group as essential components.
- the method for producing the ink repellent agent of the present invention using the mixture includes the following step. In the obtained ink repellent agent, a part or all of nitrogen atoms in the amino group derived from the hydrolyzable silane compound (c-2) is converted to an ammonium cation. As a production method, it has the effect of alleviating the tendency to aggregate due to the fluorine atom derived from the hydrolyzable silane compound (c-1) in the ink repellent agent.
- the ink repellent obtained by the production method of the present invention can maintain a stable state while having fluorine atoms, and when this is blended into a negative photosensitive resin composition, the entire composition It becomes possible to improve stability.
- the negative photosensitive resin composition the ammonium type cationic group is solvated. Thereby, it is considered that the ink repellent obtained by the production method of the present invention can exist more stably in the composition.
- the mixture used in the production method of the present invention may contain a hydrolyzable silane compound other than the hydrolyzable silane compound (c-1) and the hydrolyzable silane compound (c-2), if necessary.
- the mixture may contain a cyclic organopolysiloxane such as organodisiloxane or octamethylcyclotetrasiloxane that can be a monofunctional siloxane unit such as hexamethyldisiloxane.
- hydrolyzable silane compound contained in the mixture in addition to the hydrolyzable silane compound (c-1) and the hydrolyzable silane compound (c-2), a hydrolyzable silane compound (c-3) described later is used.
- a hydrolyzable silane compound (c-3) described later is used.
- organodisiloxane that can be a monofunctional siloxane unit include organodisiloxane (c-6) described later.
- step (I) and step (II) may be performed in that order, or may be performed simultaneously. It is more preferable to perform the step (II) after performing the step (I) because the condensation reaction of the silanol group using the amino group (base) in the compound (c-2) as a catalyst is suppressed. That is, in general, an amino group is considered to have a stronger ability of a condensation catalyst than an acid as a basic catalyst. Therefore, when an amino group is present, the condensation reaction of silanol groups generated by hydrolysis is promoted, the molecular weight of the ink repellent agent is increased more than necessary, and the storage stability of the negative photosensitive resin composition containing the ink repellent agent is increased. May be damaged. Therefore, it is preferred that after the nitrogen atom (amino group) is completely protonated in step (I), hydrolysis and condensation reaction of the mixture using an acid as a catalyst is performed in step (II).
- the production method of the present invention will be described as an example of producing an ink repellent agent by the reaction of the step (I) and the step (II) represented by the following formula (7).
- the method of manufacturing an ink repellent agent by reaction represented by the following Formula (7) is an illustration, Comprising:
- the manufacturing method of this invention is not limited to this.
- the product of the average composition formula represented by the formula (3-1) in the following formula (7) is a hydrolyzable silane compound in the hydrolysis condensate of the average composition formula represented by the formula (3) described later.
- R N of (c-2) derived from the condensation unit, a hydrolytic condensate is a group represented by the formula (5) all described below.
- the product obtained by the formula (7) is actually a partially hydrolyzed condensate in which a hydrolyzable group or silanol group remains.
- the obtained partially hydrolyzed condensate is used as an ink repellent agent.
- the chemical formula is based on the assumption that all of the hydrolyzable groups or silanol groups are siloxane bonds.
- the reaction represented by the formula (7) indicates a reaction when the ink repellent agent is manufactured in the order of step (I) and step (II).
- Formula (7) is an example in which only the hydrolyzable silane compound (c-5) is used as the hydrolyzable silane compound (c-5) and / or the organodisiloxane (c-6).
- HZ represents a monobasic acid, and other symbols are the same as those in Formula (3) described later, including preferred embodiments.
- the acid used for process (I) and process (II) has used monobasic acid, the acid used in the manufacturing method of this invention is not limited to this.
- Examples of the acid used in the step (I) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid, oxalic acid and maleic acid.
- inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid
- organic acids such as acetic acid, oxalic acid and maleic acid.
- the amount of the acid used in the step (I) is preferably 1.0 to 1.05 times by mole with respect to the nitrogen atom of the compound (c-2).
- examples of the acid used in the step (II) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid, oxalic acid and maleic acid.
- the acid used in step (II) is preferably the same acid as used in step (I). Therefore, it is preferable to use an inorganic acid, and hydrochloric acid and nitric acid are particularly preferable.
- the amount of acid used in the step (II) is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 1% by mass, based on water.
- the amount of water used in the step (II) is preferably 0.1 to 10 times mol, more preferably 0.5 to 5 times mol, and more preferably 1 to 2 times mol based on the total amount of hydrolyzable groups in the mixture. Is particularly preferred.
- the reaction temperature in step (I) and step (II) is preferably 0 to 100 ° C., particularly preferably 20 to 70 ° C.
- the reaction time in step (I) is preferably 0.5 to 2 hours.
- the reaction time in step (II) is preferably 0.3 to 7 hours. Specifically, the reaction is monitored by gas chromatography, and the reaction is continued for 0.5 to 5 hours after the compounds (c-1) to (c-5) as raw materials are below the detection limit. It is preferable to do.
- the time from the start of the reaction in the step (II) until the compounds (c-1) to (c-5) using the reaction as a raw material are below the detection limit is preferably 0.3 to 2 hours, and more preferably 0
- the reaction is preferably continued for 5 to 5 hours, and the total reaction time is preferably 0.3 to 7 hours.
- a solvent may be used in step (I) and step (II).
- the solvent include water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, ethylene glycol, glycerin, and propylene glycol; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Cellsolves such as 2-methoxyethanol and 2-ethoxyethanol; 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2 -Carbitols such as butoxyethoxy) ethanol; Esters such as methyl acetate, ethyl acetate, propylene glycol monomethyl ether acetate, 4-butyrolactone, butyl acetate, 3-methoxybutyl acetate; Examples include glycol
- a solvent may be used individually by 1 type, or may use 2 or more types together.
- the amount of the solvent used is 100 to 900 parts by mass with respect to 100 parts by mass of the mixture.
- the solvent used for manufacture of the said ink repellent agent may be mix
- the mixture used as a raw material component includes a hydrolyzable silane compound (c-1), a hydrolyzable silane compound (c-2), and an optional hydrolyzable silane compound contained as essential components.
- the decomposable silane compounds (c-3) to (c-5) and the organodisiloxane (c-6) will be described below.
- hydrolyzable silane compound (c-1) is an essential raw material component in the method for producing an ink repellent agent of the present invention, and is a compound represented by the following formula (c-1).
- AR f -Q 1 -SiX 1 3 (c-1) In the formula (c-1), A represents a fluorine atom or a group represented by the following formula (1). -Q 3 -SiX 3 3 (1) Symbols other than A in formula (c-1) and symbols in formula (1) are as follows.
- R f a perfluoroalkylene group which may contain an etheric oxygen atom having 2 to 15 carbon atoms
- Q 1 , Q 3 a divalent organic group containing no fluorine atom having 1 to 10 carbon atoms
- X 1 and X 3 are each independently a hydrolyzable group. However, when a plurality of X 1 and X 3 are present in the hydrolyzable silane compound, these may be different from each other or the same.
- the compound (c-1) is a fluorine-containing hydrolyzable silane compound having one or two trifunctional hydrolyzable silyl groups.
- R f is preferably a perfluoroalkylene group having 4 to 8 carbon atoms or a perfluoroalkylene group containing an etheric oxygen atom having 4 to 9 carbon atoms.
- a perfluoroalkylene group having 6 carbon atoms is particularly preferred.
- R f is a perfluoroalkylene group having 3 to 15 carbon atoms or a perfluoroalkyl group containing an etheric oxygen atom having 3 to 15 carbon atoms.
- An alkylene group is preferred, and a perfluoroalkylene group having 4 to 6 carbon atoms is particularly preferred.
- the partition formed using the negative photosensitive resin composition exhibits excellent ink repellency and ink repellency of UV / ozone resistance, and can be applied to a general-purpose solvent. It is preferable because of its excellent solubility.
- the structure of R f include a linear structure, a branched structure, a ring structure, or a structure having a partial ring, and a linear structure is preferable.
- R f include the following groups. - (CF 2) 4 -, - (CF 2) 6 -, - (CF 2) 8 -. -CF 2 CF 2 OCF 2 CF 2 OCF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 -, - CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 —.
- compound (c-1) has both Q 1 and Q 3 , these may be the same or different.
- Q 1 and Q 3 are specifically represented as — (CH 2 ) i1 — (i1 is 1 to 5) when Si is represented as the right bond and R f is bonded to the left bond.
- Q 1 and Q 3 are preferably groups represented by — (CH 2 ) i1 — (wherein i1 is the same as above).
- i1 is preferably an integer of 2 to 4, and — (CH 2 ) 2 — in which i1 is 2 is particularly preferable.
- the above Q 1 and Q 3 include — (CH 2 ) i1 —, —CH 2 O (CH 2 ) i2 —, —SO 2 NR A group represented by 1 — (CH 2 ) i3 —, — (C ⁇ O) —NR 1 — (CH 2 ) i4 — (i1 to i4 and R 1 are the same as described above) is preferable. Also in this case, — (CH 2 ) 2 — is particularly preferable.
- X 1 and X 3 represent a hydrolyzable group bonded to a silicon atom.
- X 1 and X 3 are each independently an alkoxy group, a halogen atom, an acyl group, an isocyanate group, an amino group, or a group in which a hydrogen atom of an amino group is substituted with an alkyl group.
- X 1 and X 3 are preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.
- compound (c-1) include the following compounds when A is a fluorine atom.
- F (CF 2 ) 4 CH 2 CH 2 Si (OCH 3 ) 3 F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 8 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2) 3 OCF (CF 3) CF 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3, F (CF 2) 2 O (CF 2) 2 O (CF 2) 2 CH 2 CH 2 Si (OCH 3) 3.
- specific examples of the compound (c-1) include the following compounds when A is the group (1).
- the compound (c-1) includes, among others, F (CF 2 ) 6 CH 2 CH 2 Si (OCH 3 ) 3 , F (CF 2 ) 3 OCF (CF 3 ) CF 2 O (CF 2 ) 2 CH 2 CH 2 Si (OCH 3 ) 3 or the like is particularly preferably used.
- compound (c-1) can be used alone or in combination of two or more.
- the content ratio of the compound (c-1) in the hydrolyzable silane compound mixture used in the method for producing the ink repellent agent of the present invention is such that the partial hydrolysis condensate obtained from the mixture by the production method of the present invention, That is, the ratio of the fluorine atom content in the ink repellent agent is within the above range.
- hydrolyzable silane compound (c-2) The hydrolyzable silane compound (c-2), together with the compound (c-1), is an essential raw material component in the method for producing the ink repellent agent of the present invention, and is a compound represented by the following formula (c-2) It is.
- D and E are each independently a hydrogen atom or a monovalent monovalent alkyl having 1 to 12 carbon atoms in which a hydrogen atom bonded to a carbon atom may be substituted with a —NH 2 group.
- An organic group or a group represented by the following formula (2) is shown. -Q 4 -SiX 4 (3-j) (R H2 ) j (2) Symbols other than D and E in formula (c-2) and symbols in formula (2) are as follows.
- R H1 , R H2 a hydrocarbon group having 1 to 6 carbon atoms
- Q 2 and Q 4 are each independently a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms
- X 2 and X 4 each independently a hydrolyzable group
- q a number that is 0 or 1
- p + q is 1 or 2
- j 0 or 1.
- EN (D) -Q 2 , X 2 , and X 4 are present in the hydrolyzable silane compound, these may be different from each other or the same.
- the compound (c-2) has p organic groups (EN (D) -Q 2 —) having an amino group (p is 1 or 2).
- the organic group having an amino group (E—N (D) -Q 2 —) is difunctional to the nitrogen atom as D and E via the linking group (Q 4 ).
- a trifunctional hydrolyzable silyl group (—SiX 4 (3-j) (R H2 ) j ) may be a group in which one or two are bonded.
- the ink repellent obtained by the production method of the present invention part or all of the nitrogen atoms in the amino group of the compound (c-2) are present as ammonium-type cations.
- the ammonium-type cation is bonded to the fluorine atom derived from the compound (c-1). It acts in a direction to relieve the tendency to easily aggregate.
- the ink repellent agent can maintain a stable state while having fluorine atoms, and when this is added to the negative photosensitive resin composition, the stability of the entire composition is improved. Is possible.
- the ink repellent agent obtained by the production method of the present invention it is particularly preferable that all of the nitrogen atoms in the amino group of the compound (c-2) are present as ammonium type cations.
- the amino group of the compound (c-2) is protonated with an acid as a method for causing the nitrogen atom in the compound (c-2) to exist as an ammonium cation. Applying the method.
- D and E are an atom bonded to a nitrogen atom or a monovalent group, and a hydrogen atom and a hydrogen atom bonded to a carbon atom are each independently substituted with an —NH 2 group.
- Examples of the monovalent organic group having 1 to 12 carbon atoms include a linear structure having 1 to 12 carbon atoms, a branched structure, a cyclo ring structure, or an alkyl group having a structure partially having a cyclo ring, and hydrogen in a benzene ring.
- some of the hydrogen atoms bonded to the carbon atoms may be substituted with —NH 2 groups.
- a part of —CH 2 — constituting the alkyl group may be substituted with —C ( ⁇ O) —.
- one is a hydrogen atom and the other to 1 or less carbon atoms which hydrogen atoms substituted by 2 groups -NH attached to a carbon atom 12 is preferably a monovalent organic group or a group represented by the above formula (2). More preferably, either one is a hydrogen atom and the other is a monovalent organic group having 1 to 12 carbon atoms in which a hydrogen atom bonded to a carbon atom may be substituted with a —NH 2 group. preferable. Further, either one is a hydrogen atom, the other hydrogen atom bonded to the carbon atom may be substituted with an —NH 2 group, and the hydrogen atom in the benzene ring may be substituted with an alkyl group.
- a phenyl group having 6 to 12 carbon atoms or a phenylalkyl group having 7 to 12 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group is particularly preferable.
- the compound (c-2) containing an amino group has a benzene ring
- the compound (c-2) is blended in a negative photosensitive resin composition, Since the interaction with the benzene ring in the alkali-soluble resin (A) is increased, the ink repellent agent is further stabilized, and the stability of the negative photosensitive resin composition is further improved.
- D and E in formula (c-2) are monovalent organic groups having 1 to 12 carbon atoms in which the hydrogen atom bonded to the carbon atom may be substituted with —NH 2 group
- Examples thereof include —C (O) NH 2 , —C (O) CH 3 , —C 6 H 5 , — (CH 2 ) 2 NH 2 , — (CH 2 ) 3 NH 2, and the like.
- Q 2 in the formula (c-2) is a linking group that bonds a hydrolyzable silyl group (—SiX 2 (4- pq ) (R H1 ) q ) and a nitrogen atom, and has 1 carbon atom. It is a divalent organic group not containing fluorine atoms of 6 to 6.
- R 2 is a hydrogen atom, methyl group or ethyl group, x2 is 1 or more, and an integer of 5 or less in total with the number of carbon atoms of R 2 )
- Q 2 is preferably an alkylene group having 2 or 3 carbon atoms.
- Q 4 in the formula (2) is a linking group that bonds a hydrolyzable silyl group (—SiX 4 (3-j) (R H2 ) j ) and a nitrogen atom, and is fluorine having 1 to 6 carbon atoms. It is a divalent organic group containing no atoms. Specific examples and preferred embodiments are the same as Q 2.
- X 2 in the formula (c-2) and X 4 in the formula (2) are hydrolyzable groups, and specific examples and preferred embodiments thereof are hydrolysis in the formula (c-1) and the formula (1). It is the same as X 1 and X 3 which are sex groups.
- p is 1 or 2
- q is 0 or 1
- p + q is a number that becomes 1 or 2. Therefore, the number (4-pq) of the hydrolyzable group X 2 is 2 or 3.
- p and q are preferably numbers such that the number of hydrolyzable groups X 2 is 3, that is, p is 1 and q is 0.
- the compound (c-2) preferably has a trifunctional hydrolyzable silyl group as the hydrolyzable silyl group.
- R H1 in formula (c-2) and R H2 in formula (2) represent a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, A methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.
- the compound (c-2) include an example in which both D and E are hydrogen atoms, one of D and E is a hydrogen atom, and the other hydrogen atom bonded to a carbon atom is —NH 2.
- Examples of the monovalent organic group having 1 to 12 carbon atoms which may be substituted on the group include the following compounds.
- Specific examples of the compound (c-2) include the following compounds when either one of D and E is a hydrogen atom and the other is represented by the above formula (2).
- compound (c-2) from the viewpoint of having a benzene ring, C 6 H 5 NH (CH 2 ) 3 Si (OCH 3 ) 3 (N-phenyl-3-aminopropyltrimethoxysilane), C 6 H 5 NH (CH 2 ) 3 Si (OC 2 H 5 ) 3 (N-phenyl-3-aminopropyltriethoxysilane) is particularly preferred.
- compound (c-2) can be used alone or in combination of two or more. .
- the content ratio of the compound (c-2) in the mixture used in the method for producing the ink repellent of the present invention is such that the amino group of the compound (c-2) is protonated to obtain the ink repellent If it is a ratio which stabilizes, it will not be restrict
- the compounding amount of such compound (c-2) is preferably 0.1 to 9 moles of compound (c-2), preferably 0.5 to 9 moles per mole of compound (c-1). It is particularly preferable to use it.
- the hydrolyzable silane compound (c-3) is arbitrarily used in the production method of the present invention in order to increase the film forming property of the ink repellent agent obtained and the solubility in a solvent. It is represented by R H3 r —SiX 5 (4-r) (c-3)
- X 5 representing a hydrolyzable group is the same as X 1 in the above formula (c-1), including preferred embodiments.
- R H3 is the same as R H1 in the above formula (c-2), including preferred embodiments.
- r is 0, 1 or 2.
- the compound (c-3) is preferably a tetrafunctional compound in which r is 0, or a trifunctional compound in which r is 1, and particularly preferably a tetrafunctional compound.
- the compound (c-3) one type may be used alone, or two or more types may be used in combination. When using 2 or more types together, a bifunctional compound can also be used together with a tetrafunctional compound and / or a trifunctional compound.
- the ink repellent agent is easily dissolved in a hydrocarbon solvent, and is relatively inexpensive when forming a coating film of a negative photosensitive resin composition on the surface of the substrate.
- a suitable solvent can be selected.
- oil repellency is exhibited by R f derived from the compound (c-1).
- the relative ratio of R f in the ink repellent agent is high.
- the compound (c-3) when r is 0, there is an advantage that the relative ratio of R f in the ink repellent agent is increased, the oil repellency is improved, and the film forming property is excellent.
- the compound (c-3) when r is 1 or 2, the presence of RH3 to some extent makes the ink repellent easy to dissolve in a hydrocarbon solvent, and the negative photosensitive resin is formed on the surface of the substrate.
- a relatively inexpensive solvent can be selected.
- the following examples are preferable. Further, as the compound (c-3), a partial hydrolysis-condensation product obtained by partial hydrolysis-condensation of a plurality of them in advance may be used as necessary. The same applies to other hydrolyzable silane compounds.
- Si (OCH 3 ) 4 Si (OCH 2 CH 3 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OCH 2 CH 3 ) 3 , CH 3 CH 2 Si (OCH 3 ) 3 , CH 3 CH 2 Si (OCH 2 CH 3 ) 3 , (CH 3 ) 2 Si (OCH 3 ) 2 , (CH 3 ) 2 Si (OCH 2 CH 3 ) 2 ,
- a compound obtained by hydrolytic condensation of Si (OCH 3 ) 4 for example, methyl silicate 51 (trade name) manufactured by Colcoat Co.
- Compounds obtained by hydrolytic condensation of Si (OCH 2 CH 3 ) 4 for example, ethyl silicate 40 and ethyl silicate 48 (both trade names) manufactured by Colcoat).
- hydrolyzable silane compound (c-3) when used as the hydrolyzable silane compound, which is a raw material in the method for producing the ink repellent agent of the present invention, one kind may be used alone or two or more kinds may be used alone. It is also possible to use together.
- the blending amount of the hydrolyzable silane compound (c-3) with respect to the total amount of the functional silane compound (c-1) and the hydrolyzable silane compound (c-2) is preferably 10 to 300 mol%, preferably 50 to 200 mol. % Is particularly preferred.
- hydrolyzable silane compound (c-4) The hydrolyzable silane compound (c-4) is represented by the following formula (c-4), which is arbitrarily used in the production method of the present invention for the purpose of improving the fixability of the obtained ink repellent agent to the upper surface of the partition wall. It is a hydrolyzable silane compound.
- X 6 representing a hydrolyzable group is the same as X 1 in formula (c-1), including preferred embodiments.
- R H4 is the same as R H1 in formula (c-2), including preferred embodiments.
- Y in the formula (c-4) is a group having an ethylenic double bond, and Q 5 is a divalent organic group containing no fluorine atom having 1 to 6 carbon atoms.
- g is 1 or 2
- h is 0 or 1
- g + h is a number that becomes 1 or 2.
- a plurality of YQ 5 and X 6 are present in the hydrolyzable silane compound, these may be different from each other or the same.
- the compound (c-4) has Y, when exposing the film of the negative photosensitive resin composition containing the ink repellent obtained by using the compound (c-4), on the upper surface of the film, It is possible to polymerize with the ink repellent agent through the group or with the ink repellent agent and other components having an ethylenic double bond contained in the composition. That is, it has the function of making the ink repellent agent easily stay on the upper surface of the partition wall after exposure. Even after development, post-baking, ink repellency treatment, and the like performed after exposure, the upper surface of the obtained partition wall can be imparted with ink repellency and the side surface can be maintained with ink repellency.
- Y in the formula (c-4) is preferably a (meth) acryloyloxy group, a vinylphenyl group or the like, and a (meth) acryloyloxy group is particularly preferable.
- Q 5 in the formula (c-4) is a linking group that binds a hydrolyzable silyl group (—SiX 6 (4- gh ) (R H4 ) h ) and Y.
- Examples thereof include an alkylene group having 2 to 6 carbon atoms and a phenylene group. Of these, — (CH 2 ) 3 — is preferable.
- the hydrolyzable silane compound (c-4) is used as the hydrolyzable silane compound that is a raw material in the method for producing the ink repellent agent of the present invention, one kind may be used alone, or two or more kinds may be used alone. It can also be used in combination.
- the ink repellent agent is produced using the compound (c-4) in addition to the compound (c-1) and the compound (c-2), the total of the compound (c-1) and the compound (c-2)
- the blending amount of the hydrolyzable silane compound (c-4) with respect to the amount is preferably 100 to 500 mol%, particularly preferably 50 to 400 mol%.
- the mixture used in the method for producing the ink repellent agent of the present invention contains the compound (c-3) and / or the compound (c-4) in addition to the compound (c-1) and the compound (c-2). Is preferred.
- the compound (c-3) or the compound (c-3) and the compound (c-4) are preferably included.
- the ink repellent agent is not firmly fixed to the upper surface of the partition wall as compared with the case of using the compound, and the ink repellent agent easily moves to the side surface of the partition wall after exposure.
- both the upper surface of the partition wall and the side surface of the partition wall can be made ink repellent, which is suitable for applications requiring such characteristics.
- the compound (c-4) can be appropriately used depending on the application.
- the compound (c-3) and the hydrolyzable silane compound (c-4) are used in the mixture in addition to the compound (c-1) and the compound (c-2), the compound (c-1) and the compound (c).
- the compounding amount of compound (c-3) with respect to the total amount of -2) is preferably 10 to 300 mol%, particularly preferably 50 to 200 mol%.
- the compounding amount of the compound (c-4) with respect to the total amount of the compound (c-1) and the compound (c-2) is preferably 20 to 200 mol%, particularly preferably 50 to 100 mol%.
- the total amount of compound (c-3) and compound (c-4) to the total amount of compound (c-1) and compound (c-2) is preferably 10 to 500 mol%, preferably 50 to 300 Mole% is particularly preferred.
- hydrolyzable silane compound (c-5) and organodisiloxane (c-6) Both the hydrolyzable silane compound (c-5) and the organodisiloxane (c-6) are improved in compatibility and reaction of the resulting ink repellent agent with the negative photosensitive resin composition in the production method of the present invention. It is a component that is arbitrarily used for the purpose of controlling sex.
- the hydrolyzable silane compound (c-5) is a monofunctional hydrolyzable silane compound represented by the following formula (c-5).
- X 7 in formula (c-5) is the same as X 1 in formula (c-1) including preferred embodiments, and R H5 includes R H1 in formula (c-2) and preferred embodiments. It is the same.
- W 1 represents AR f -Q 1 in the formula (c-1) (where A is a fluorine atom), R H5 or the formula (c-4 YQ 5 in the parentheses).
- two R H5 (3 R H5 when W 1 is R H5 ) may be the same as or different from each other.
- the hydrolyzable silane compound (c-5) by adjusting W 1 as appropriate, the compatibility between the ink repellent agent and the other components of the negative photosensitive resin composition is improved, and the silanol group is sealed.
- W 1 the compatibility between the ink repellent agent and the other components of the negative photosensitive resin composition is improved, and the silanol group is sealed.
- the organodisiloxane (c-6) is an organodisiloxane represented by the following formula (c-6).
- the compound (c-6) is a silane compound capable of generating a monofunctional siloxane unit.
- R H6 in formula (c-6) is the same as R H1 in formula (c-2), including preferred embodiments, and W 2 is the same as W 1 in formula (c-5) and preferred embodiments. It is the same including.
- W 2 may be the same as or different from each other.
- four R H6 (5 or 6 R H6 when W 2 is R H6 ) may be the same as or different from each other.
- compound (c-6) by adjusting W 2 appropriately, the same effect as that of the hydrolyzable silane compound (c-5) can be imparted to the ink repellent agent obtained by the production method of the present invention. it can.
- the W 1 and W 2 of the compound are AR.
- f 1 -Q 1 (where A is a fluorine atom) is preferred because the relative proportion of R f in the ink repellent agent is increased and excellent oil repellency can be exhibited.
- W 1 and W 2 are preferably R H5 and R H6 , respectively, because the solubility of the ink repellent agent in a hydrocarbon solvent is improved. It is preferable that W 1 and W 2 are YQ 5- , since the curability of the ink repellent agent is improved and the solubility in a hydrocarbon solvent is improved.
- Specific examples of the compound (c-6) include the following compounds. (CH 3 ) 3 SiOSi (CH 3 ) 3 .
- hydrolyzable silane compound (c-5) and / or the organodisiloxane (c-6) is used as the hydrolyzable silane compound which is a raw material in the method for producing the ink repellent agent of the present invention.
- these can be used alone or in combination of two or more.
- the mixture contains compound (c-5) and / or organodisiloxane (c-6) in addition to compound (c-1) and compound (c-2).
- the compounding amount of the compound (c-5) and / or the organodisiloxane (c-6) is preferably 5 to 300 mol% with respect to the total amount of the compound (c-1) and the compound (c-2). ⁇ 200 mol% is particularly preferred.
- the upper limit is preferably 150 mol%, and particularly preferably 100 mol%.
- the compound (c-4) and the compound (c-5) are used in addition to the compound (c-1) and the compound (c-2), the compound (c-1) and the compound (c-5)
- the compounding amount of compound (c-4) with respect to the total amount of -2) is preferably 1 to 500 mol%
- the compounding amount of compound (c-5) is preferably 1 to 300 mol%.
- the compounding amount of the compound (c-4) is 5 to 400 mol% with respect to the total amount of the compound (c-1) and the compound (c-2), and the compounding amount of the compound (c-5) is 5 ⁇ 200 mol%.
- the ink repellent agent obtained by the production method of the present invention includes a hydrolyzable silane compound (c-1), a hydrolyzable silane compound (c-2), and And a part or all of nitrogen atoms in the hydrolyzable silane compound (c-2) are present as ammonium-type cations.
- the hydrolysis condensation reaction in step (II) includes the generation of silanol groups by hydrolysis reaction of hydrolyzable groups and the siloxane bond by dehydration condensation reaction between silanol groups as described above.
- the ink repellent agent of the present invention is, as a preferred embodiment, a molecular design so that the silanol groups produced by the hydrolysis reaction remain in the partially hydrolyzed condensate thus obtained, and the number of silanol groups Is preferably 0.2 to 3.5 on average per silicon atom, more preferably 0.2 to 2.0 on average, and particularly preferably 0.5 to 1.5.
- the solubility of the ink repellent agent in the solvent and the compatibility with other components in the negative photosensitive resin composition are good, and workability is improved.
- it is below the upper limit of the above range evaporation of the ink repellent agent from the surface of the substrate can be prevented when the partition is formed using the negative photosensitive resin composition.
- the number of silanol groups in the partial hydrolysis-condensation product is calculated by the ratio of peak areas of Si groups having silanol groups and Si groups not having silanol groups, as measured by 29 Si-NMR.
- the ink repellent agent of the present invention has fluorine atoms derived from the hydrolyzable silane compound (c-1), so that the partition walls produced from the negative photosensitive resin composition containing the fluorine atom are subjected to ultraviolet / ozone irradiation treatment. Even after passing, excellent ink repellency can be imparted.
- the content of fluorine atoms in the partially hydrolyzed condensate (hereinafter also referred to as “fluorine atom content”) is preferably 10 to 55% by mass, more preferably 12 to 40% by mass, and particularly preferably 15 to 30% by mass. preferable.
- the partition obtained from the negative photosensitive resin composition containing the ink repellent agent can be provided with excellent ink repellency and ink repellent UV / ozone resistance.
- the ink repellent agent uses a hydrolyzable silane compound (c-5) and / or organodisiloxane (c-6) having a fluorine atom
- the ink repellent agent is a hydrolyzable silane.
- it contains a fluorine atom that combines the hydrolyzable silane compound (c-5) and / or the fluorine atom derived from the organodisiloxane (c-6).
- the ink repellent agent of the present invention further has a negative photosensitive resin composition because part or all of the nitrogen atoms in the amino group derived from the hydrolyzable silane compound (c-2) are present as an ammonium cation. When formulated, it can be stably present in the composition.
- the ink repellent agent in the present invention may be composed of a single compound, but is usually a mixture composed of a plurality of compounds having different degrees of polymerization. That is, the ink repellent agent is, for example, a compound in which A in the formula (c-1) is a fluorine atom as a hydrolyzable silane compound (c-1), and a formula (as a hydrolyzable silane compound (c-2)) D and E in c-2) are each independently a monovalent organic group having 1 to 12 carbon atoms in which a hydrogen atom or a hydrogen atom bonded to a carbon atom may be substituted with an —NH 2 group A certain compound is used as an essential component, and optionally hydrolyzable silane compound (c-3), hydrolyzable silane compound (c-4), hydrolyzable silane compound (c-5) and / or organodisiloxane (c In the case of producing using ⁇ 6), it becomes an agent having a structure of an average composition formula represented by the
- R F represents AR f -Q 1 (wherein A is a fluorine atom) in the above formula (c-1).
- R N represents NN (D) -Q 2 — in the above formula (c-2) (where D and E are each independently a hydrogen atom or a hydrogen atom bonded to a carbon atom to the —NH 2 group)
- D and E are each independently a hydrogen atom or a hydrogen atom bonded to a carbon atom to the —NH 2 group
- a nitrogen atom of the group is protonated to form an ammonium-type cation (5) The group shown by is shown.
- R V represents YQ 5 in the above formula (c-4).
- W represents W 1 in the above formula (c-5) or W 2 in the formula (c-6).
- R H represents R H5 in the above formula (c-5) or R H6 in the above formula (c-6).
- R H1 , R H3 , R H4 , p, q, r, g, and h are the same as in the above formulas (c-2) to (c-4), including preferred embodiments.
- m, n, k, s, and t represent mol% of each unit with respect to the total molar amount of the structural unit.
- m and n are numbers greater than 0, k, s, and t are numbers greater than 0, and m + n + k + s + t is 100.
- the units derived from the decomposable silane compound (c-4), the hydrolyzable silane compound (c-5) and / or the organodisiloxane (c-6) are presumed to be randomly arranged.
- m: n: k: s: t represents the compound (c-1) and the compound (c-2) in the mixture used for producing the ink repellent agent.
- the values of m and n are the average values of the entire ink repellent agent, and m: n is the co-condensation ratio of the hydrolyzable silane compound (c-2) to the hydrolyzable silane compound (c-1), respectively. It is preferable to be within the range.
- the ink repellent agent of the present invention is an agent in which part or all of the nitrogen atoms in the condensation unit portion derived from the hydrolyzable silane compound (c-2) are protonated to become ammonium-type cations. That is, the compound (3), R N of the unit derived from compound (c-2) is intended a group represented by the above formula (5) is always contained. In particular, where all of the nitrogen atoms derived from the hydrolyzable silane compound (c-2) becomes ammonium type cationic, i.e., in the compound (3), of units derived from the compound (c-2) R N Are all groups represented by the above formula (5).
- hydrolyzable silane compound (c-3), hydrolyzable silane compound (c-4), hydrolyzable silane compound (c-5) and / or organodisiloxane (c-6) optionally blended
- the co-condensation ratio in is also preferably within the above-described ratio range described for each of the above compounds as the mol% relative to m + n as the average value of the entire ink repellent agent.
- t in the above formula (3) is 0, and when m is 1 mol, n is 0.1 to 5 mol, k is 0.5 to 10 mol, and s is An average composition of 0.1 to 5 moles, or an average composition of 0.5 to 10 moles and k of 0.1 to 5 moles when t and s are 0 and m is 1 mole Is particularly preferred.
- the number average molecular weight (Mn) of the ink repellent agent of the present invention is preferably 500 or more, preferably less than 1,000,000, and particularly preferably less than 10,000.
- the number average molecular weight (Mn) is equal to or more than the lower limit, there is an advantage that evaporation from the substrate surface can be prevented when forming the partition using the negative photosensitive resin composition, and the number average molecular weight (Mn) Is less than the upper limit, the solubility in a solvent is improved, and there is an advantage that workability is improved.
- the number average molecular weight (Mn) of the ink repellent agent can be adjusted by selecting reaction conditions and the like in the method for producing the ink repellent agent described below.
- the ink repellent agent of the present invention is used as one component of a negative photosensitive resin composition used for producing a cured film having ink repellency.
- a negative photosensitive resin composition containing the ink repellent agent of this invention Specifically, the negative photosensitive resin composition of the following this invention etc. are mentioned.
- the ink repellent agent of the present invention is excellent in storage stability in a negative photosensitive resin composition and is cured with a cured film produced from the composition, for example, UV / ozone in partition walls. Even after the irradiation treatment, excellent ink repellency can be imparted.
- the negative photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a photopolymerization initiator (B), an ink repellent agent obtained by the production method of the present invention as an ink repellent agent (C), and a solvent ( D). Furthermore, a crosslinking agent (E) is contained as needed. Furthermore, a thermal crosslinking agent (F), a colorant (G), a polymer dispersant (H), a dispersion aid (I), a silane coupling agent (J), fine particles (K), a phosphoric acid compound (L) and Other additives may be contained.
- the alkali-soluble resin (A) in the present invention is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. Since the alkali-soluble resin (A) has an ethylenic double bond in the molecule, the exposed portion of the negative photosensitive resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B). The exposed part thus cured is not removed with an alkaline developer. Moreover, when the alkali-soluble resin (A) has an acidic group in the molecule, an unexposed portion of the uncured negative photosensitive resin composition can be selectively removed with an alkali developer. As a result, a partition wall can be formed.
- a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, These may be used individually by 1 type or may use 2 or more types together.
- limit especially as said ethylenic double bond The double bond which has addition polymerizability, such as a (meth) acryloyl group, an allyl group, a vinyl group, a vinyloxy group, a vinyloxyalkyl group, is mentioned, These are 1 You may use a seed
- the alkali-soluble resin (A) is not particularly limited, but is a resin (A1-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy group having an acidic group and an ethylenic double chain. And a resin (A1-2) having a bond introduced therein, and a monomer (A1-3) having a side chain having an acidic group and a side chain having an ethylenic double bond. These may be used alone or in combination of two or more.
- Resin (A1-1) can be synthesized, for example, by the following method (i) or (ii).
- a monomer having a reactive group other than an acidic group in the side chain for example, a monomer having a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain are copolymerized and reactive.
- a copolymer having a side chain having a group and a side chain having an acidic group is obtained.
- this copolymer is reacted with a compound having a functional group capable of bonding to the reactive group and an ethylenic double bond.
- a compound having a functional group capable of bonding to the acidic group and an ethylenic double bond is reacted with the acidic group after the reaction. React with the remaining amount.
- monomers having a hydroxyl group as a reactive group 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5 -Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl Meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.
- the monomer having an acidic group to be copolymerized is not particularly limited.
- examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate.
- Examples of the compound having an ethylenic double bond and a functional group capable of bonding to a hydroxyl group to be reacted with the obtained copolymer include an acid anhydride having an ethylenic double bond, an isocyanate group and an ethylenic double bond.
- Examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthal And acid anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride, and the like.
- Examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
- Examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.
- Examples of the monomer having an epoxy group as a reactive group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
- a monomer having an acidic group to be copolymerized with a monomer having an epoxy group as a reactive group the same monomers as described for the monomer having a hydroxyl group as a reactive group can be used, Copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acidic group can also be performed by a conventionally known method.
- Examples of the compound having an ethylenic double bond and a functional group capable of bonding to an epoxy group to be reacted with the obtained copolymer include compounds having a carboxy group and an ethylenic double bond.
- Specific examples of the compound include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
- a carboxy group may be introduced into the resin (A1-1) by reacting the generated hydroxyl group with an acid anhydride in which the dehydration condensation part of the carboxylic acid forms part of the cyclic structure.
- Examples of the monomer having a carboxy group as a reactive group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.
- these monomers are used also as a monomer which has the acidic group mentioned above.
- the monomer When using a monomer having a carboxy group as a reactive group, the monomer is polymerized as described above.
- the compound having an ethylenic double bond and a functional group capable of bonding to a carboxy group to be reacted with the obtained polymer include compounds having an epoxy group and an ethylenic double bond.
- the compound include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.
- the amount of the functional group capable of bonding to the carboxy group and the compound having an ethylenic double bond to be reacted with the polymer having a carboxy group is such that the carboxy group in the polymer becomes an acidic group after the reaction. The amount remaining in the chain.
- Resin (A1-2) is synthesized by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond, which will be described later, and then reacting with a polyvalent carboxylic acid or an anhydride thereof. Can do. Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting an epoxy resin with a compound having a carboxy group and an ethylenic double bond. Next, a carboxyl group can be introduce
- the epoxy resin is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having naphthalene skeleton, And an epoxy resin having a biphenyl skeleton represented by (A1-2a), an epoxy resin represented by the following formula (A1-2b), an epoxy resin having a biphenyl skeleton represented by the following formula (A1-2c), and the like. It is done.
- v is an integer of 1 to 50, preferably an integer of 2 to 10.
- the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, A halogen atom or a part of hydrogen atoms may be substituted with a phenyl group which may be substituted with a substituent.
- R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 or (It is an integer from 1 to 10.)
- the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which part of the hydrogen atoms may be substituted with a substituent.
- Z may be 0 or an integer of 1 to 10).
- the epoxy resin represented by the formulas (A1-2a) to (A1-2c) is reacted with a compound having a carboxy group and an ethylenic double bond and then reacted with a polyvalent carboxylic acid anhydride.
- the polycarboxylic acid anhydride is preferably a mixture of dicarboxylic acid anhydride and tetracarboxylic dianhydride.
- acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and salts thereof are preferred, and acrylic acid or methacrylic acid Acid is particularly preferred.
- the resin (A1-2) a commercially available product can be used.
- commercial products all are trade names, such as KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR- 1535H, ZAR-2001H, ZAR-2002, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (above, Nipponization) Medicinal Co., Ltd.), EX1010 (manufactured by Nagase ChemteX Corporation), Neopole 8430, 8473, 8475, 8478 (above, manufactured by Nippon Iupika Co., Ltd.).
- Examples of the monomer (A1-3) include 2,2,2-triacryloyloxymethylethylphthalic acid (NK ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the alkali-soluble resin (A) it is possible to obtain a high-resolution pattern by suppressing peeling of the cured film during development, the good linearity of the line, and the appearance after the post-baking process is maintained.
- the resin (A1-2) is preferably used from the viewpoint that a smooth cured film surface can be easily obtained.
- Examples of the resin (A1-2) include a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol A type epoxy resin, a resin in which an acidic group and an ethylenic double bond are introduced into a bisphenol F type epoxy resin, phenol Resin with acidic group and ethylenic double bond introduced into novolac epoxy resin, Resin with acidic group and ethylenic double bond introduced into cresol novolac epoxy resin, Acid group and ethylene into trisphenol methane type epoxy resin Particularly preferred are resins in which an acidic double bond is introduced, and resins in which an acidic group and an ethylenic double bond are introduced into the epoxy resins represented by the formulas (A1-2a) to (A1-2c).
- the number of ethylenic double bonds of the alkali-soluble resin (A) in one molecule is preferably 3 or more on average, and particularly preferably 6 or more.
- the exposed portion is excellent in curability, and a fine pattern can be formed with a smaller exposure amount.
- the mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 1.5 ⁇ 10 3 to 30 ⁇ 10 3 , particularly preferably 2 ⁇ 10 3 to 20 ⁇ 10 3 .
- the number average molecular weight (Mn) is preferably from 500 to 20 ⁇ 10 3 , particularly preferably from 1 ⁇ 10 3 to 10 ⁇ 10 3 .
- the acid value of the alkali-soluble resin (A) is preferably 10 to 300 mgKOH / g, particularly preferably 30 to 150 mgKOH / g. When the acid value is in the above range, the developability of the negative photosensitive resin composition is improved.
- the alkali-soluble resin (A) contained in the negative photosensitive resin composition may be used alone or in combination of two or more.
- the content of the alkali-soluble resin (A) in the total solid content in the negative photosensitive resin composition is preferably 5 to 80% by mass, particularly preferably 10 to 60% by mass. When the content ratio is in the above range, the developability of the negative photosensitive resin composition is good.
- the photopolymerization initiator (B) in the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, but a compound that generates a radical by light is preferable.
- Examples of the photopolymerization initiator (B) include ⁇ -diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.
- Acylloin ethers thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diisopropylthioxanthone, thioxanthone Thioxanthones such as 4-sulfonic acid; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Phenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4
- R 3 represents a hydrogen atom
- R 61 or OR 62 each of R 61 and R 62 independently represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom in a cycloalkane ring.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 30 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 5 represents an alkyl group having 1 to 20 carbon atoms, a hydrogen group in the benzene ring in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, or a hydrogen atom in the benzene ring in an alkyl group.
- An optionally substituted phenylalkyl group having 7 to 30 carbon atoms is shown.
- R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, a cyano group, a halogen atom, a nitro group, R 61 , OR 62 , an alkanoyl group having 2 to 20 carbon atoms, or a hydrogen atom in the benzene ring.
- a benzoyl group having 7 to 20 carbon atoms in which an atom may be substituted with an alkyl group a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, a carbon atom
- R 0 represents R 61 , OR 62 , a cyano group or a halogen atom.
- a is 0 or an integer of 1 to 3.
- R 3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a hydrogen atom in the benzene ring substituted with an alkyl group.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a 6 to 20 carbon atom in which a hydrogen atom in the benzene ring may be substituted with an alkyl group.
- R 5 represents an alkyl group having 1 to 12 carbon atoms.
- R 6 , R 7 , R 8 and R 9 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom in which a hydrogen atom in the cycloalkane ring may be substituted with an alkyl group.
- a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 6 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, an alkanoyl group having 2 to 20 carbon atoms, and a hydrogen atom in the benzene ring Is a benzoyl group having 7 to 20 carbon atoms which may be substituted with an alkyl group, a benzylcarbonyl group having 7 to 20 carbon atoms in which a hydrogen atom in the benzene ring may be substituted with an alkyl group, the number of carbon atoms
- the photopolymerization initiator (4) include compounds (4-1) in which, in the formula (4), R 3 to R 9 are each the following groups, and a indicating the number of R 0 is 0: To (4-10).
- a commercial item can be used for a photoinitiator (B).
- Examples of 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone include IRGACURE 907 (trade name, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholino
- Examples of phenyl) -butan-1-one include IRGACURE 369 (trade name, manufactured by BASF).
- Examples of oxime esters include IRGACURE OXE01 (corresponding to BASF, trade name: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), ADEKA.
- Examples of the photopolymerization initiator (4) include IRGACURE OXE02 (trade name: corresponding to the above compound (4-7) manufactured by BASF) as a commercial product.
- Examples of the photopolymerization initiator (4) include those described in International Publication No. 2008/078678. 1 to 71 can be used.
- photopolymerization initiators (B) exemplified above, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferable because they may exhibit a sensitizing effect when used together with other radical initiators. .
- photopolymerization initiator (B) 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime) (a compound corresponding to the above compound (4-7)) and 2,4-diethylthioxanthone are preferable. Furthermore, combinations of these with the above benzophenones such as 4,4′-bis (diethylamino) benzophenone are particularly preferred.
- the photopolymerization initiator (B) contained in the negative photosensitive resin composition may be one type or a mixture of two or more types.
- the ratio of the photopolymerization initiator (B) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 5 to 15% by mass. Is particularly preferred. Within the above range, the developability of the negative photosensitive resin composition is good.
- the negative photosensitive resin composition of the present invention contains the ink repellent agent obtained by the production method of the present invention as the ink repellent agent (C).
- the content ratio of the ink repellent agent (C) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass, and preferably 0.1 to 6% in the total solid content in the negative photosensitive resin composition. % By mass is more preferable, and 0.5 to 5% by mass is particularly preferable.
- solvent (D) Since the negative photosensitive resin composition of the present invention contains the solvent (D), the viscosity of the negative photosensitive resin composition is reduced, and the negative photosensitive resin composition is applied to the substrate surface. Cheap. Therefore, a uniform coating film of the negative photosensitive resin composition can be formed.
- the solvent (D) contained in the negative photosensitive resin composition of the present invention is the alkali-soluble resin (A), photopolymerization initiator (B), ink repellent agent (C) contained in the negative photosensitive resin composition.
- the crosslinking agent (E), and further optional components described later are uniformly dissolved or dispersed to uniformly and easily apply the negative photosensitive resin composition to the substrate on which the partition walls are formed. As long as it has a function to react and does not have reactivity with these components, it is not particularly limited.
- the solvent (D) for example, the same solvent as that which can be used at the time of synthesizing the ink repellent agent (C) exemplified above can be used.
- Other examples include chain hydrocarbons such as n-butane and n-hexane; cyclic saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene and xylene; benzyl alcohol and water. These may be used alone or in combination of two or more.
- a solvent having the required performance is appropriately selected and used as the solvent (D).
- the solvent (D) has a boiling point of 165 to 210 with respect to the total amount of the solvent.
- a solvent containing a solvent (D1) at a temperature of 10 to 100% by mass is preferably used.
- the boiling point of the solvent (D1) is 165 to 210 ° C, particularly preferably 170 to 200 ° C.
- the boiling point of the solvent (D1) is not less than the lower limit of the above range, the surface transition time of the ink repellent agent (C) can be sufficiently ensured, and the generation of aggregates can be prevented. Furthermore, it is possible to prevent the problem of unevenness of the film appearance and non-uniformity of the film thickness that occurs when drying is completed without taking a sufficient leveling period because the drying speed of the coating film is too high.
- the boiling point of the solvent (D1) is not more than the upper limit of the above range, there is no possibility of causing a decrease in productivity due to the occurrence of sticking or an increase in the time required for the drying step.
- the solvent it is possible to prevent influences such as a decrease in reliability due to peeling of a cured film at the time of development, outgas generation due to reheating after formation of the partition wall, and the like.
- the content of the solvent (D1) in the solvent (D) is preferably 10 to 100% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.
- the content is in the above range, in the coating and drying process of the negative photosensitive resin composition on the substrate surface, the film thickness is uniform and uniform, and a good film that does not generate aggregates on the film surface is obtained. can get.
- solvent (D1) examples include diethylene glycol ethyl methyl ether (EDM, boiling point 176 ° C.), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C.), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C.), propylene glycol diester.
- EDM diethylene glycol ethyl methyl ether
- EEE diethylene glycol diethyl ether
- IPDM diethylene glycol isopropyl methyl ether
- Acetate (boiling point: 190 ° C), propylene glycol n-butyl ether (boiling point: 170 ° C), 3-methoxybutyl acetate (boiling point: 171 ° C), 3-methoxy-3-methylbutyl acetate (boiling point: 188 ° C), dipropylene Examples include glycol dimethyl ether (boiling point: 175 ° C.), ethyl 3-ethoxypropionate (boiling point: 170 ° C.), 4-butyrolactone (boiling point: 204 ° C.), cyclohexanol acetate (boiling point: 173 ° C.), and the like. These may be used alone or in combination of two or more.
- a compound represented by the following formula (6) is particularly preferable. Since the compound (6) contains polar etheric oxygen, it has a high ability to dissolve the ink repellent agent (C) and can greatly contribute to the improvement of the storage stability of the negative photosensitive resin composition.
- R 11 represents an alkyl group having 1 to 10 carbon atoms
- R 12 represents an alkyl group having 2 to 10 carbon atoms
- y represents an integer of 1 to 10.
- R 11 is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 carbon atom.
- R 12 is preferably an alkyl group having 2 to 4 carbon atoms, particularly preferably an alkyl group having 2 carbon atoms.
- y is preferably 1 to 3, and 2 is particularly preferable.
- Examples of the compound (6) preferably used as the solvent (D1) are shown below together with their abbreviations and boiling points.
- Examples include diethylene glycol ethyl methyl ether (EDM, boiling point: 176 ° C.), diethylene glycol diethyl ether (EDE, boiling point: 189 ° C.), diethylene glycol isopropyl methyl ether (IPDM, boiling point: 179 ° C.), and the like. These may be used alone or in combination of two or more. Of these, diethylene glycol ethyl methyl ether is particularly preferable.
- the solvent (D2) is a compound having a hydroxyl group in the molecule and having a boiling point of less than 165 ° C., and preferably has a viscosity at 25 ° C. of 2 mP ⁇ s or less.
- the ink repellent agent (C) is a partially hydrolyzed condensate, silanol groups remain in the product. Therefore, by including the solvent (D2) having the same hydroxyl structure as the silanol group in the negative photosensitive resin composition, the dispersion state of the ink repellent agent (C) in the composition is further stabilized by solvation. As a result, the storage stability of the negative photosensitive resin composition can be further improved. On the other hand, since the solvent (D2) has a hydroxyl group, the viscosity is likely to increase due to hydrogen bonding between molecules as compared with a compound having the same molecular weight without a hydroxyl group.
- the viscosity will be generally below the above upper limit, the substrate surface will have good wetting and spreading at the time of coating, and a large amount of liquid will be required. Uniformity does not deteriorate and unevenness does not occur.
- the solvent (D2) specifically, propylene glycol monomethyl ether (PGME, boiling point: 120 ° C., viscosity: 1.71 mPa ⁇ s (25 ° C.)), water (boiling point: 100 ° C., viscosity: 0.89 mPa ⁇ s) s (25 ° C.)), 2-propanol (IPA, boiling point: 82 ° C., viscosity: 1.96 mPa ⁇ s (25 ° C.)), and the like.
- the ratio of the solvent (D2) to the total amount of the solvent (D) is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass.
- solvent (D3) other than the above-mentioned solvent (D1) and solvent (D2) as a solvent (D) as needed.
- solvent (D3) the solvent used in the synthesis of the alkali-soluble resin (A) or the ink repellent agent (C), or the like, together with the alkali-soluble resin (A) or the ink repellent agent (C), the negative photosensitive resin composition. Examples of the solvent used when blended with products.
- the said solvent (D1) and a solvent (D2) may be used as a solvent used for the synthesis
- the said solvent (D1) and a solvent (D2) may be used as a solvent used for the synthesis
- the said solvent (D1) and a solvent (D2) may be used as a solvent used for the synthesis
- combination of the said alkali-soluble resin (A) or an ink repellent agent (C) the said solvent (D1) and a solvent (D2) may be used.
- the negative photosensitive resin composition contains the solvent (D1) or the solvent (D2) derived from these compounding components, it is calculated by the total amount of the solvent (D1) and the solvent (D2) containing them. What is necessary is just to adjust so that content of the solvent (D1) and the solvent (D2) in a solvent (D) may become said range,
- solvent (D3) examples include propylene glycol 1-monomethyl ether 2-acetate (PGMEA, boiling point: 146 ° C.), diethylene glycol monoethyl ether acetate (EDGAC, boiling point: 217 ° C.), butyl acetate (boiling point: 126 ° C.) Cyclohexanone (boiling point: 156 ° C.), solvent naphtha (boiling point: 150 to 200 ° C.), and the like.
- Solvent naphtha is a mixed solvent of petroleum-based compounds, and the composition includes a compound classified as solvent (D1) as its boiling point indicates. In the present specification, the solvent having a boiling point exceeding the boiling point of the solvent (D1) is classified as the solvent (D3).
- the content of the solvent (D3) in the solvent (D) is an amount obtained by subtracting the amounts of the solvent (D1) and the solvent (D2) from the total amount of the solvent (D), specifically, the total amount of the solvent (D).
- the content is preferably 1 to 50% by mass, particularly preferably 5 to 40% by mass.
- an aspect configured by the solvent (D1), the solvent (D2), and / or the solvent (D3), which is configured only by the solvent (D1) can be given.
- solvent (D1): solvent (D2): solvent (D3) ) 50 to 90: 5 to 45: 5 to 45.
- the composition of the solvent (D) in the negative photosensitive resin composition of the present invention is not limited to this.
- the solvent (D) can be appropriately selected within a range that does not impair the effects of the present invention, depending on the required characteristics of the negative photosensitive resin composition.
- the content of the solvent (D) in the negative photosensitive resin composition varies depending on the composition and use of the negative photosensitive resin composition, but is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, 65 to 90% by mass is particularly preferable.
- the negative photosensitive resin composition of the present invention may contain a crosslinking agent (E) as an optional component that promotes radical curing.
- a crosslinking agent (E) a compound having two or more ethylenic double bonds in one molecule and having no acidic group is preferable.
- crosslinking agent (E) examples include diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ⁇ -caprolactone modified tris- (2-acryloxyethyl) isocyanurate, ⁇ 4-
- hept-5-ene-2,3-dicarboximide urethane acrylate and the like.
- urethane acrylate from the viewpoint of photoreactivity, it is preferable to have a large number of ethylenic double bonds.
- pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated isocyanuric acid triacrylate, and urethane acrylate are preferable.
- these may be used individually by 1 type, or may use 2 or more types together.
- crosslinking agent (E) Commercial products can be used as the crosslinking agent (E).
- Commercially available products include KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate), NK ester A-9530 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipenta Erythritol pentaacrylate and dipentaerythritol hexaacrylate)), NK ester A-9300 (trade name, Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate), NK ester A-9300-1CL (trade name, new) Nakamura Chemical Co., Ltd., ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate), BANI-M (trade name, manufactured by Maruzen Petro
- urethane acrylate examples include KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd., and specific product names include UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D- P20 etc. are mentioned.
- KAYARAD DPHA and NK ester A-9530 are preferable because they improve the sensitivity of the cured film obtained from the negative photosensitive resin composition.
- NK esters A-9300, BANI-M and BANI-X are preferred from the viewpoint of imparting hardness to the cured film and suppressing thermal sagging.
- NK ester A-9300-1CL is preferable from the viewpoint of imparting flexibility to the cured film.
- Urethane acrylate is preferable because an appropriate development time can be realized and developability is improved.
- the content of the crosslinking agent (E) in the total solid content in the negative photosensitive resin composition is preferably 10 to 60% by mass, particularly preferably 20 to 55% by mass. When it is in the above range, the storage stability of the negative photosensitive resin composition becomes good, and when the patterned substrate obtained using the negative photosensitive resin composition is formed, the ink-jet ink in the pixel becomes wet. Property is improved.
- the thermal crosslinking agent (F) in the present invention is a compound having two or more groups capable of reacting with a carboxy group and / or a hydroxyl group.
- the thermal crosslinking agent (F) reacts with the alkali-soluble resin (A) to increase the crosslinking density of the cured film and improve the heat resistance.
- thermal crosslinking agent (F) include at least one selected from the group consisting of amino resins, epoxy compounds, oxazoline compounds, polyisocyanate compounds, and polycarbodiimide compounds. These compounds may be used alone or in combination of two or more.
- the content of the thermal crosslinking agent (F) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 1 to 50% by mass, particularly preferably 5 to 30% by mass. The developability of the negative photosensitive resin composition obtained when it is in the above range becomes good.
- Colorant (G) When the negative photosensitive resin composition of the present invention is used for forming a black matrix, which is a grid-like black portion surrounding the three color pixels R, G, and B of a color filter of a liquid crystal display element, a colorant (G ) Is preferably included.
- the colorant (G) include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment black 1, 6, 7, 12, 20, 31 etc. are mentioned.
- the colorant (G) a mixture of organic pigments such as red pigments, blue pigments, green pigments, and inorganic pigments can also be used.
- the content of the colorant (G) in the total solid content in the negative photosensitive resin composition Is preferably 15 to 65% by mass, particularly preferably 20 to 50% by mass.
- the obtained negative photosensitive resin composition has good sensitivity, and the formed partition wall is excellent in light shielding properties.
- the negative photosensitive resin composition of the present invention contains a dispersible material such as the colorant (G), it preferably contains a polymer dispersant (H) in order to improve the dispersibility.
- the polymer dispersant (H) is not particularly limited, but is urethane, polyimide, alkyd, epoxy, polyester, melamine, phenol, acrylic, polyether, vinyl chloride, vinyl chloride acetic acid. Examples thereof include a vinyl copolymer system, a polyamide system, and a polycarbonate system, and a urethane system or a polyester system is preferable.
- the polymer dispersant (H) may have a structural unit derived from ethylene oxide and / or propylene oxide.
- the polymer dispersant (H) having a basic group is used in consideration of the affinity for the colorant (G). It is preferable. Although it does not specifically limit as a basic group, A primary, secondary, or tertiary amino group is mentioned.
- a commercially available product may be used as the polymer dispersant (H). Commercially available products include Disparon DA-7301 (trade name, manufactured by Enomoto Kasei Co., Ltd.), BYK161, BYK162, BYK163, BYK182 (all trade names, manufactured by BYK-Chemie), Solspurs 5000, Solspers 17000 (all trade names, Zeneca).
- the amount of the polymer dispersant (H) used is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, based on the colorant (G). When the amount used is not less than the lower limit of the above range, the dispersibility of the colorant (G) is improved.
- the negative photosensitive resin composition of the present invention may contain a phthalocyanine pigment derivative or a metal phthalocyanine sulfonamide compound as the dispersion aid (I).
- the dispersion aid (I) is considered to have a function of improving the dispersion stability by adsorbing to the dispersible material such as the colorant (G) and the polymer dispersant (H).
- the amount of the dispersion aid (I) used is preferably 1 to 10% by mass, particularly preferably 2 to 8% by mass, based on the colorant (G).
- the amount used is not less than the lower limit of the above range, the dispersion stability of the colorant (G) is improved, and when it is not more than the upper limit of the above range, the developability of the negative photosensitive resin composition becomes good. .
- silane coupling agent (J) When the negative photosensitive resin composition of the present invention uses a silane coupling agent (J), the substrate adhesion of the formed cured film is improved.
- the silane coupling agent (J) include tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-chloropropyl.
- trimethoxysilane 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, heptadecafluorooctylethyltrimethoxysilane, polyoxyalkylene chain-containing triethoxysilane, and the like. These may be used alone or in combination of two or more.
- the content of the silane coupling agent (J) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
- the content of the silane coupling agent (J) in the total solid content in the negative photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, particularly preferably 1 to 10% by mass.
- the negative photosensitive resin composition of the present invention may contain fine particles (K) as necessary. By mix
- the fine particles (K) are not particularly limited, and inorganic fine particles such as silica, zirconia, magnesium fluoride, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO); organic materials such as polyethylene and polymethyl methacrylate (PMMA) System fine particles.
- inorganic fine particles are preferable in consideration of heat resistance, and silica or zirconia is particularly preferable in consideration of availability and dispersion stability.
- the fine particles (K) can be obtained by considering the adsorption ability of the polymer dispersant (H). ) Is preferably negatively charged.
- the fine particles (K) do not absorb the light irradiated at the time of exposure, i-line (365 nm) which is the main emission wavelength of the ultra-high pressure mercury lamp, It is particularly preferred not to absorb h-line (405 nm) and g-line (436 nm).
- the particle diameter of the fine particles (K) is preferably 1 ⁇ m or less, particularly preferably 200 nm or less, since the surface smoothness of the partition wall is improved.
- the content of the fine particles (K) in the total solid content in the negative photosensitive resin composition is preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass. When the content ratio is not less than the lower limit of the above range, there is an effect of suppressing the decrease in ink repellency due to post-baking, and when it is not more than the upper limit of the above range, the storage stability of the negative photosensitive resin composition is good. Become.
- the negative photosensitive resin composition of the present invention may contain a phosphoric acid compound (L) as necessary. Adhesiveness with a board
- substrate can be improved because a negative photosensitive resin composition contains a phosphoric acid compound (L).
- the phosphoric acid compound (L) include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, tris (meth) acryloyloxyethyl phosphate, and the like.
- the content ratio of the phosphoric acid compound (L) in the total solid content in the negative photosensitive resin composition is preferably 0.1 to 10% by mass, particularly preferably 0.1 to 1% by mass. Adhesiveness with the base material of the cured film formed from the negative photosensitive resin composition obtained as it is the said range becomes favorable.
- the negative photosensitive resin composition of the present invention may further contain a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, a repellency inhibitor, an ultraviolet absorber, and the like as necessary. .
- Solvent (D) at least one selected from the group consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone and cyclohexanone Solvent, 50 to 99% by mass in the negative photosensitive resin composition.
- the alkali-soluble resin (A), the photopolymerization initiator (B), and the ink repellent agent (C) are the same as in the combination 1, and the solvent (D) is as follows.
- a solvent (D3) selected from acetate, butyl acetate, cyclohexanone, diethylene glycol
- Solvent (D) at least one selected from the group consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone and cyclohexanone 50 to 99% by mass of a negative photosensitive resin composition,
- Solvent (D) at least one selected from the group consisting of water, 2-propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, 4-butyrolactone and cyclohexanone 50 to 99% by mass of a negative photosensitive resin composition,
- an alkali-soluble resin A
- a photopolymerization initiator B
- an ink repellent agent C
- a solvent D
- a cross-linking agent E
- Thermal crosslinking agent F
- colorant G
- polymer dispersant H
- dispersion aid I
- silane coupling agent J
- fine particles K
- phosphoric acid compound L
- a method of mixing with other additives is preferred.
- the negative photosensitive resin composition of the present invention is used as a material such as photolithography in the same manner as an ordinary negative photosensitive resin composition, and the obtained cured film is an ordinary negative photosensitive resin composition. It can be used as a member of an optical element in which the cured film is used.
- the negative photosensitive resin composition of the present invention is used for forming a partition for an optical element having a plurality of pixels and a partition located between adjacent pixels on the surface of the substrate, an ultraviolet / ozone cleaning treatment, etc. Even after the ink repellency treatment, partition walls having sufficient ink repellency can be obtained, which is preferable.
- the negative photosensitive resin composition of the present invention contains the ink repellent agent obtained by the production method of the present invention as the ink repellent agent (C), so that the ink repellent agent aggregates and settles over a long period of time. Is a composition which is suppressed and has excellent storage stability.
- the partition of this invention is a partition formed in order to provide a division on the substrate surface, Comprising: It consists of a cured film of the said negative photosensitive resin composition of this invention.
- the partition of this invention is used suitably for the use of an optical element, and when a negative photosensitive resin composition contains a coloring agent (G), the partition obtained can be applied as a black matrix.
- the partition of the present invention is applied to an optical element having, for example, a plurality of pixels and a partition located between adjacent pixels on the substrate surface.
- Examples of the method for producing the partition for the optical element of the present invention using the negative photosensitive resin composition of the present invention include the following methods.
- the negative photosensitive resin composition of the present invention is applied to the substrate surface to form a coating film (coating film forming process), then the coating film is dried to form a film (drying process), and then the film Only the part to be a partition wall is exposed and photocured (exposure process), and then the coating film other than the photocured part is removed to form a partition wall comprising the photocured part of the coating film (development process)
- the partition walls for the optical element of the present invention can be manufactured by further thermally curing the formed partition walls and the like as necessary (post-baking step).
- you may put the process (post-exposure process) which further photocures the said formed partition etc. between a image development process and a post-baking process.
- the material of the substrate is not particularly limited, but various glass plates; polyester (polyethylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polysulfone, polyimide, poly (meth) acrylic resin, etc.
- Thermoplastic plastic sheet; Cured sheet of thermosetting resin such as epoxy resin and unsaturated polyester can be used.
- a heat resistant plastic such as a glass plate or polyimide is preferable from the viewpoint of heat resistance.
- a post exposure may be performed from the back surface (board
- FIG. 1 is a cross-sectional view schematically showing a production example of a partition for an optical element using the negative photosensitive resin composition of the present invention.
- FIG. 1 (I) is a view showing a cross section in a state where a coating film 2 made of the negative photosensitive resin composition of the present invention is formed on a substrate 1.
- FIG. 1 (II) schematically shows the exposure process.
- FIG. 1 (III) is a cross-sectional view showing the substrate 1 after the development process and the partition wall 6 formed on the substrate surface.
- the negative photosensitive resin composition of the present invention is applied onto a substrate 1 to form a coating film 2 made of the negative photosensitive resin composition.
- substrate 1 is wash
- the method for applying the negative photosensitive resin composition is not particularly limited as long as a coating film having a uniform film thickness is formed.
- Spin coating, spraying, slit coating, roll coating, spin coating The method used for normal coating-film formation, such as a method and a bar coating method, is mentioned.
- the film thickness of the coating film 2 is determined in consideration of the height of the partition wall finally obtained.
- the film thickness of the coating film 2 is preferably 100 to 200%, particularly preferably 100 to 130% of the height of the partition wall finally obtained.
- the thickness of the coating film 2 is preferably from 0.3 to 325 ⁇ m, particularly preferably from 1.3 to 65 ⁇ m.
- the coating film 2 formed on the substrate 1 in the coating film forming step is heated to obtain the film 2.
- the volatile components including the solvent contained in the negative photosensitive resin composition constituting the coating film are volatilized and removed, and a non-sticky film is obtained.
- the ink repellent agent (C) moves to the vicinity of the coating film surface.
- the heating method include a method in which the coating film 2 is heated together with the substrate 1 at a temperature of 50 to 120 ° C. for about 10 to 2,000 seconds using a heating device such as a hot plate or an oven.
- drying such as vacuum drying other than heating (drying) is performed. You may provide a process separately before a prebaking process. Further, in order to efficiently dry the coating film without causing unevenness in the appearance of the coating film, it is more preferable to use heating and vacuum drying in combination with drying by the above-described prebaking process.
- the conditions for vacuum drying vary depending on the type of each component, the blending ratio, and the like, but can be preferably performed at 500 to 10 Pa for a wide range of about 10 to 300 seconds.
- the film 2 is irradiated with light 5 through a mask 4 having a predetermined pattern.
- the light 5 is transmitted only through the predetermined pattern portion cut by the mask 4, reaches the film on the substrate 1, and only the portion is photocured. Therefore, when forming a partition, the said predetermined pattern is provided in the form suitable for the shape of a partition.
- the average partition wall width after the post-baking step is preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
- the average distance between adjacent partition walls is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less. It is preferable to use a mask in which a pattern is formed so as to be in this range.
- the exposed portion 3 of the film irradiated with light is composed of a cured film of a negative photosensitive resin composition, while the unexposed portion is an uncured negative photosensitive resin composition. In this state, the film 2 itself remains.
- the irradiation light 5 is visible light; ultraviolet light; far ultraviolet light; excimer laser such as KrF excimer laser, ArF excimer laser, F 2 excimer laser, Kr 2 excimer laser, KrAr excimer laser, Ar 2 excimer laser; X-ray; Examples include lines. Further, the irradiation light 5 is preferably an electromagnetic wave having a wavelength of 100 to 600 nm, more preferably a light ray having a distribution in the range of 300 to 500 nm, particularly i-line (365 nm), h-line (405 nm) and g-line (436 nm). preferable.
- Exposure is preferably 5 ⁇ 1,000mJ / cm 2, particularly preferably 50 ⁇ 400mJ / cm 2.
- the exposure amount is at least the lower limit of the above range, the negative photosensitive resin composition serving as a partition is sufficiently cured, and subsequent development does not easily cause dissolution or peeling from the substrate 1.
- a high resolution is obtained when it is not more than the upper limit of the above range.
- the exposure time depends on the exposure amount, the composition of the photosensitive composition, the thickness of the coating film, etc., but is preferably 1 to 60 seconds, and particularly preferably 5 to 20 seconds.
- an alkaline aqueous solution containing alkalis such as inorganic alkalis, amines, alcohol amines, and quaternary ammonium salts can be used.
- an organic solvent such as a surfactant or alcohol can be added to the developer in order to improve solubility and remove residues.
- Develop time (time for contacting with developer) is preferably 5 to 180 seconds.
- Examples of the developing method include a liquid piling method, a dipping method, and a shower method.
- water on the substrate 1 and the partition walls 6 can be removed by performing high-pressure water washing or running water washing and air-drying with compressed air or compressed nitrogen.
- the partition 6 on the substrate 1 is heated.
- the heating method include a method in which the partition wall 6 is heat-treated at 150 to 250 ° C. for 5 to 90 minutes with a heating device such as a hot plate or an oven together with the substrate 1.
- a heating device such as a hot plate or an oven together with the substrate 1.
- the heating temperature is particularly preferably 180 ° C. or higher.
- the heating temperature is too low, curing of the partition wall 6 is insufficient, so that sufficient chemical resistance cannot be obtained, and when the ink is injected into the dots 7 in the subsequent inkjet coating process, the solvent contained in the ink As a result, the partition wall 6 may swell or the ink may ooze. On the other hand, if the heating temperature is too high, thermal decomposition of the partition walls 6 may occur.
- the average partition wall width is preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
- the average distance between adjacent partition walls (dot width) is preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
- the average height of the partition walls is preferably 0.05 to 50 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
- the partition wall is formed on the substrate surface by the above manufacturing method, for example, the substrate surface exposed in the region surrounded by the substrate and the partition wall is subjected to ink affinity treatment (ink affinity treatment step), and then the region An optical element can be obtained by injecting ink into the ink jet method to form the pixel (ink injection step).
- ink affinity treatment examples include a cleaning process using an alkaline aqueous solution, an ultraviolet cleaning process, an ultraviolet / ozone cleaning process, an excimer cleaning process, a corona discharge process, and an oxygen plasma process.
- the cleaning process using an alkaline aqueous solution is a wet process for cleaning the substrate surface using an alkaline aqueous solution (potassium hydroxide, tetramethyl ammonium hydroxide aqueous solution or the like).
- the ultraviolet cleaning process is a dry process for cleaning the substrate surface using ultraviolet rays.
- the ultraviolet / ozone cleaning process is a dry process that cleans the substrate surface using a low-pressure mercury lamp that emits light having wavelengths of 185 nm and 254 nm.
- the excimer cleaning process is a dry process for cleaning the substrate surface using a xenon excimer lamp that emits light having a wavelength of 172 nm.
- the corona discharge treatment is a dry treatment that uses a high-frequency high voltage to generate corona discharge in the air and cleans the substrate surface.
- the oxygen plasma treatment is a dry treatment in which the surface of a substrate is cleaned using a highly reactive “plasma state” in which oxygen is excited mainly in a vacuum using a high-frequency power source or the like as a trigger.
- a dry treatment method such as an ultraviolet / ozone cleaning treatment is preferable because it is simple.
- UV / ozone can be generated using commercially available equipment.
- An ink-repellent treatment can be performed by placing a substrate on which a partition wall is formed inside an ultraviolet / ozone device and performing the treatment in air at room temperature for about 1 to 10 minutes within a range that does not impair the oil repellency of the partition wall. it can.
- about processing time what is necessary is just to adjust to the time used as the range which does not impair the oil repellency of a partition according to each ultraviolet-ray / ozone apparatus.
- the dots can be sufficiently made ink-philic, such as a color display device using the resulting optical element, etc. It is possible to prevent white spots.
- the partition obtained from the negative photosensitive resin composition of the present invention it is possible to make the ink affinity by the ultraviolet cleaning treatment or the like without reducing the ink repellency of the partition.
- the ink repellency (water / oil repellency) of the cured film formed from the negative photosensitive resin composition is contact of water and PGMEA (propylene glycol monomethyl ether acetate: an organic solvent often used as an ink solvent). It can be estimated in the corner.
- PGMEA propylene glycol monomethyl ether acetate: an organic solvent often used as an ink solvent. It can be estimated in the corner.
- the partition is required to have sufficient ink repellency even after the ink-philic treatment. It is done. Therefore, the water contact angle of the partition walls is preferably 90 ° or more, and particularly preferably 95 ° or more.
- the contact angle of PGMEA of the partition wall is preferably 30 degrees or more, particularly preferably 35 degrees or more.
- the dots are required to be ink-philic, and the water
- the contact angle is preferably 20 degrees or less, and particularly preferably 10 degrees or less.
- This step can be performed in the same manner as a normal method using an ink jet apparatus generally used in the ink jet method.
- the ink jet device used for forming such pixels is not particularly limited, but is a method in which charged ink is continuously ejected and controlled by a magnetic field, and ink is ejected intermittently using a piezoelectric element.
- Ink jet apparatuses using various methods such as a method of heating and a method of heating ink and ejecting intermittently using the foaming can be used.
- optical elements produced using the negative photosensitive resin composition of the present invention include color filters, organic EL elements, and organic TFT arrays.
- the shape of the pixel to be formed can be any known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type.
- the ink used for forming the pixel mainly includes a coloring component, a binder resin component, and a solvent.
- a coloring component it is preferable to use pigments and dyes excellent in heat resistance, light resistance and the like.
- the binder resin component a resin that is transparent and excellent in heat resistance is preferable, and examples thereof include an acrylic resin, a melamine resin, and a urethane resin.
- the water-based ink contains water and optionally a water-soluble organic solvent as a solvent, contains a water-soluble resin or a water-dispersible resin as a binder resin component, and contains various auxiliary agents as necessary.
- the oil-based ink contains an organic solvent as a solvent, a resin soluble in the organic solvent as a binder resin component, and various auxiliary agents as necessary. Moreover, after injecting ink by the inkjet method, it is preferable to perform drying, heat curing, ultraviolet curing, or the like, if necessary.
- a protective film layer is formed as necessary.
- the protective film layer is formed for the purpose of increasing the surface flatness and for blocking the eluate from the ink in the partition walls and the pixel portion from reaching the liquid crystal layer.
- a transparent electrode such as tin-doped indium oxide (ITO) is formed on a transparent substrate such as glass by sputtering or the like, and the transparent electrode is etched into a desired pattern as necessary.
- a barrier rib is formed using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-ink, a solution of a hole transport material and a light emitting material is sequentially applied to the dot using an inkjet method. And dried to form a hole transport layer and a light emitting layer. Thereafter, an electrode of aluminum or the like is formed by a vapor deposition method or the like, thereby obtaining a pixel of the organic EL element.
- An organic TFT array can be manufactured through the following steps (1) to (3).
- a partition wall is formed on a transparent substrate such as glass using the negative photosensitive resin composition of the present invention.
- the gate electrode is formed by applying a solution of a gate electrode material to the dots using an inkjet method.
- a gate insulating film is formed thereon.
- a barrier rib is formed using the negative photosensitive resin composition of the present invention, and after the dot is made into an ink-philic process, a solution of a source / drain electrode material is applied to the dot using an inkjet method. Then, source / drain electrodes are formed.
- a barrier rib is formed by using the negative photosensitive resin composition of the present invention so as to surround a region including the pair of source / drain electrodes, and the ink becomes an ink-insensitive dot.
- an organic semiconductor solution is applied to the dots using an inkjet method, and an organic semiconductor layer is formed between the source and drain electrodes.
- the partition using the negative photosensitive resin composition of the present invention may be used in only one step, or the negative of the present invention in two or more steps. You may utilize the partition using a type photosensitive resin composition.
- Examples 1 to 6 and Examples 8 to 13 are examples, and examples 7 and 14 are comparative examples.
- IR907 Trade name: IRGACURE 907, manufactured by BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone.
- EAB 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example 1 Synthesis of ink repellent agent (C1) and production of (C1) liquid
- the ink repellent agent (C1) was synthesized by the reaction represented by the following formula (71).
- the product obtained by the reaction represented by the formula (71) is actually a partial hydrolysis condensate in which a hydrolyzable group or silanol group remains, and in this example, the obtained partial hydrolysis condensate Was used as the ink repellent agent (C1).
- the average composition formula represented by formula (3-2) is represented by formula (71).
- the chemical formula is based on the assumption that all of the hydrolyzable groups or silanol groups are siloxane bonds.
- Step (II) the reaction was monitored by gas chromatography, and the reaction was further continued for 4 hours from the time when each compound as the raw material was below the detection limit, and stirring was performed for a total of 5 hours.
- Z represents an NO 3 or Cl.
- m, n, k, and s each represent mol% of a unit enclosed in parentheses (m + n + k + s is 100%).
- the obtained PGME solution containing the ink repellent agent (C1) at 10% by mass was used as the (C1) solution for the preparation of the following negative photosensitive resin composition.
- the fluorine atom content and number average molecular weight (Mn) of the ink repellent agent (C1) are shown in Table 1 together with the charged amount composition (mol%) of the ink repellent agent (C1).
- This charged amount composition is directly applied to the compound (c-11), the cationized compound (c-21), the compound (c-31) and the compound (c-41) in the average composition formula (C1). It can be said that it corresponds to mol%, m, n, k and s of the derived condensed unit.
- Example 2 Synthesis of ink repellent agent (C2) and production of (C2) liquid
- a 50 cm 3 three-necked flask equipped with a stirrer 0.5 g of compound (c-11), 0.41 g of compound (c-21), and 1.67 g of compound (c-31) were placed.
- a raw material mixture of the ink agent (C2) was obtained.
- 9.0 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).
- Step (II) the reaction was monitored by gas chromatography, and the reaction was further continued for 4 hours from the time when each compound as the raw material was below the detection limit, and stirring was performed for a total of 5 hours.
- the obtained PGME solution containing the ink repellent agent (C2) at 10% by mass was used as a (C2) solution for the production of the following negative photosensitive resin composition.
- the fluorine atom content and the number average molecular weight (Mn) of the ink repellent agent (C2) are shown in Table 1 together with the charged amount composition (mol%) of the ink repellent agent (C2).
- Example 3 Synthesis of ink repellent agent (C3) and production of (C3) liquid
- a 50 cm 3 three-necked flask equipped with a stirrer 0.5 g of the compound (c-11) and 1.14 g of the compound (c-21) were placed to obtain a raw material mixture of the ink repellent (C3).
- PGME 13.1 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).
- Step (II) the reaction was monitored by gas chromatography, and the reaction was further continued for 4 hours from the time when each compound as the raw material was below the detection limit, and stirring was performed for a total of 5 hours.
- the obtained PGME solution containing the ink repellent agent (C3) at 10% by mass was used as a (C3) solution for the production of the following negative photosensitive resin composition.
- Table 1 shows the fluorine atom content and the number average molecular weight (Mn) of the ink repellent agent (C3) together with the charged amount composition (mol%) of the ink repellent agent (C3).
- Example 4 Synthesis of ink repellent agent (C4) and production of (C4) liquid
- a 50 cm 3 three-necked flask equipped with a stirrer 0.5 g of compound (c-11), 0.34 g of compound (c-21), and 0.63 g of compound (c-41) were placed.
- a raw material mixture of the ink agent (C4) was obtained.
- 10.0 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).
- Step (II) the reaction was monitored by gas chromatography, and the reaction was further continued for 4 hours from the time when each compound as the raw material was below the detection limit, and stirring was performed for a total of 5 hours.
- the obtained PGME solution containing the ink repellent agent (C4) at 10% by mass was used as a (C4) solution for the production of the following negative photosensitive resin composition.
- Table 1 shows the fluorine atom content and the number average molecular weight (Mn) of the ink repellent agent (C4) together with the charged amount composition (mol%) of the ink repellent agent (C4).
- Example 5 Synthesis of ink repellent agent (C5) and production of (C5) liquid]
- 0.13 g of the 65 mass% aqueous nitric acid solution used in step (I) was changed to 0.14 g of the 35 mass% aqueous hydrochloric acid solution, and the 1.0 mass% nitric acid aqueous solution used in step (II) was changed.
- An ink repellent agent (C5) was obtained as a PGME solution (concentration of ink repellent agent (C5): 10% by mass) in the same manner except that 1.12 g was changed to 1.08 g of 1.0% by mass hydrochloric acid aqueous solution.
- Example 6 Synthesis of ink repellent agent (C6) and production of (C6) liquid
- An ink repellent agent (C6) was obtained as a PGMEA solution (concentration of ink repellent agent (C6): 10% by mass) in the same manner as in Example 1 except that the solvent was changed from PGME to PGMEA.
- the obtained PGMEA solution containing 10% by mass of the ink repellent agent (C6) was used as a (C6) solution for the production of the following negative photosensitive resin composition.
- Example 7 Synthesis of ink repellent agent (Cf1) and production of (Cf1) liquid
- a 50 cm 3 three-necked flask equipped with a stirrer 0.5 g of compound (c-11), 1.1 g of compound (c-31), and 0.63 g of compound (c-41) were placed.
- a raw material mixture of the ink agent (Cf1) was obtained.
- 8.5 g of PGME was added to the raw material mixture to prepare a solution (raw material solution).
- Step (II) 1.17 g of 1.0 mass% nitric acid aqueous solution was dropped into the obtained raw material solution while stirring at room temperature. After the completion of dropping, the mixture was further stirred for 5 hours, and the hydrophobization reaction was performed to convert the ink repellent agent (Cf1) in which n is 0 in the average composition formula (C1) to a PGME solution (ink repellent agent (Cf1) concentration: 10 Mass%) (step (II)).
- Step (II) the reaction was monitored by gas chromatography, and the reaction was further continued for 4 hours from the time when each compound as the raw material was below the detection limit, and stirring was performed for a total of 5 hours.
- the obtained PGME solution containing 10% by mass of the ink repellent agent (Cf1) was used as a (Cf1) liquid for the production of the following negative photosensitive resin composition (Comparative Example).
- Table 1 shows the fluorine atom content and the number average molecular weight (Mn) of the ink repellent agent (Cf1) together with the charged amount composition (mol%) of the ink repellent agent (Cf1).
- Example 8 Production of negative photosensitive resin composition and production of cured film]
- Manufacture of negative photosensitive resin composition 0.26 g of liquid (C1) obtained in Example 1 above (containing 0.026 g of ink repellent agent (C1) as a solid content, the rest being a solvent PGME), 4.0 g of CCR-1235 (solid content is 2.4 g, the rest is the solvent EDGAC (diethylene glycol monoethyl ether acetate): 1.07 g, solvent naphtha: 0.53 g), IR907 0.29 g, EAB 0.19 g, A9530 2.5 g, PGME 5 .4 g, 1 g of 2-propanol, and 1 g of water were put into a 50 cm 3 stirring container and stirred for 30 minutes to produce a negative photosensitive resin composition 1.
- EDGAC diethylene glycol monoethyl ether acetate
- UV / ozone cleaning A 10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds and then subjected to ultraviolet / ozone cleaning for 5 minutes.
- UV / ozone cleaning PL2001N-58 (manufactured by Sen Engineering) was used as an UV / ozone generator.
- this apparatus was used as the ultraviolet / ozone generator.
- the negative photosensitive resin composition 1 was applied to the surface of the glass substrate after the cleaning using a spinner and then dried on a hot plate at 100 ° C. for 2 minutes to form a film having a thickness of 1.3 ⁇ m. .
- a gap of 50 ⁇ m is formed on the surface of the obtained film from the film side through a photomask having a hole pattern (2.5 cm ⁇ 5 cm) (a photomask in which light is irradiated to a region other than the pattern portion). Then, ultraviolet rays from a high-pressure mercury lamp were irradiated at 25 mW / cm 2 for 10 seconds to obtain a cured film.
- the film thickness of the obtained cured film was 1.1 ⁇ m.
- the exposed glass substrate was developed by immersing in a 0.4% by mass tetramethylammonium hydroxide aqueous solution for 40 seconds, and the unexposed film was washed away with water and then dried. Subsequently, the glass substrate 1 in which the cured film (partition) of the negative photosensitive resin composition 1 is formed in a region excluding the opening pattern portion by heating it at 230 ° C. for 20 minutes on a hot plate. Got.
- the ultraviolet-ray / ozone irradiation process was performed for 1 minute to the whole surface by which the coating-film cured
- the PGMEA contact angle on the surface of the cured coating film and the water contact angle of the unexposed part were measured.
- ⁇ Film thickness> Measurement was performed using a laser microscope (manufactured by Keyence Corporation, apparatus name: VK-8500).
- Negative photosensitive resin compositions 2 to 7 were produced in the same manner as in Example 8 except that the liquid (C1) which was the ink repellent solution was changed to the liquids shown in Table 2, respectively.
- PGMEA was used as the additive solvent instead of PGMEA in accordance with the solvent of the (C6) solution.
- glass substrates 2 to 7 were obtained in which cured films (partitions) of the negative photosensitive resin compositions 2 to 7 were formed in the region excluding the opening pattern portion.
- the negative photosensitive resin compositions 2 to 7 obtained above have storage stability, and the glass substrates 2 to 7 on which a cured film (partition) is formed have a film thickness, an exposed part and an unexposed part. Evaluation of property and ink affinity was carried out in the same manner as in Example 8. The results are shown in Table 2.
- the storage stability was good, and the cured film was excellent even after being subjected to ultraviolet / ozone irradiation treatment. It had ink properties.
- the negative photosensitive resin composition of Example 14 used an ink repellent obtained by a method not according to the production method of the present invention, the storage stability was insufficient.
- the negative photosensitive resin composition of the present invention can produce barrier ribs with good ink repellency, such as being able to maintain ink repellency even after UV / ozone irradiation, and has good storage stability.
- it can be suitably used for the formation of partition walls for color filter production, organic EL element production, and organic TFT array production using an inkjet recording technique.
Abstract
Description
例えば、カラーフィルタの製造においては、隔壁をフォトリソグラフィにより形成した後に、隔壁で囲まれた開口部(ドット)にR(レッド)、G(グリーン)、およびB(ブルー)のインクをインクジェット法により噴射し、塗布して、画素を形成する。
一方、インクジェット法で画素に形成されるインク層には、高い膜厚均一性を有することが要求されているため、隔壁で囲まれた開口部(ドット)は吐出液に対して良好な濡れ性、いわゆる親インク性を有することが要求される。
特許文献2には、感光性樹脂組成物の貯蔵安定性が良好で、該組成物を用いて得られる硬化膜の基材密着性を向上できる、2級芳香族アミノ基を有する加水分解性シラン化合物を含む感光性樹脂組成物が記載されている。
特許文献2に記載の加水分解性シラン化合物は、フッ素原子を有しておらず、撥インク剤として機能するものではない。
また、本発明は、紫外線/オゾン照射処理を経ても撥インク性に優れた隔壁、および該隔壁を有し、白抜け現象等の発生が抑制された光学素子を提供することを目的とする。
[1]下式(c-1)で表される加水分解性シラン化合物と下式(c-2)で表される加水分解性シラン化合物とを含む混合物の部分加水分解縮合物からなる撥インク剤の製造方法であって、
以下の工程(I)および工程(II)を含むことを特徴とする撥インク剤の製造方法。
工程(I):前記混合物に酸を含ませて、加水分解性シラン化合物(c-2)における窒素原子をプロトン化する工程、
工程(II):前記混合物に水と酸触媒とを含ませて、該混合物を加水分解および縮合反応させる工程。
式(c-1)において、Aはフッ素原子または下式(1)で表される基を示す。
-Q3-SiX3 3 …(1)
式(c-2)において、D、は、それぞれ独立して、水素原子、炭素原子に結合する水素原子が-NH2基に置換されていてもよい炭素原子数1~12の1価の有機基または下式(2)で表される基を示す。
-Q4-SiX4 (3-j)(RH2)j …(2)
式(c-1)、(c-2)中のA、D、E以外の記号、および式(1)および(2)中の記号は、以下の通りである。
Rf:炭素原子数2~15のエーテル性酸素原子を含んでいてもよいペルフルオロアルキレン基、
Q1、Q3:炭素原子数1~10のフッ素原子を含まない2価の有機基、
RH1、RH2:炭素原子数1~6の炭化水素基、
Q2、Q4:それぞれ独立して、炭素原子数1~6のフッ素原子を含まない2価の有機基、
X1、X2、X3、X4:それぞれ独立して、加水分解性基、
p:1または2、
q:0または1であり、p+qが1または2となる数、
j:0または1。
ただし、X1~X4が式(c-1)および/または式(c-2)内に複数個存在する場合、またはE-N(D)-Q2が式(c-2)内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
[2]前記混合物中の加水分解性シラン化合物(c-1)および(c-2)の含有割合は、加水分解性シラン化合物(c-1)の1モルに対して、加水分解性シラン化合物(c-2)が0.1~9モルである上記[1]の撥インク剤の製造方法。
[3]前記部分加水分解縮合物のフッ素原子の含有割合が10~55質量%である、上記[1]または[2]の撥インク剤の製造方法。
[4]前記部分加水分解縮合物がシラノール基を含有し、ケイ素原子1個当たりのシラノール基が0.2~3.5個である、上記[1]~[3]のいずれかの撥インク剤の製造方法。
[5]前記式(c-2)におけるDおよびEのいずれか一方が水素原子であって、他方がベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~12のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~12のフェニルアルキル基である、上記[1]~[4]のいずれかの撥インク剤の製造方法。
[6]前記式(c-2)で表される加水分解性シラン化合物が、N-フェニル-3-アミノプロピルトリメトキシシランまたはN-フェニル-3-アミノプロピルトリエトキシシランである、上記[1]~[5]のいずれかの撥インク剤の製造方法。
[7]前記混合物が、さらに下式(c-3)で表される加水分解性シラン化合物を含む、上記[1]~[6]のいずれかの撥インク剤の製造方法。
RH3 r-SiX5 (4-r) …(c-3)
式(c-3)中の記号は、以下の通りである。
RH3:炭素原子数1~6の炭化水素基、
X5:加水分解性基、
r:0、1または2である。
ただし、RH3およびX5が、前記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
[8]前記混合物がさらに下式(c-4)で表される加水分解性シラン化合物を含む、上記[1]~[7]のいずれかの撥インク剤の製造方法。
式(c-4)中の記号は、以下の通りである。
Y:エチレン性二重結合を有する基、
Q5:炭素原子数1~6のフッ素原子を含まない2価の有機基、
RH4:炭素原子数1~6の炭化水素基、
X6:加水分解性基、
g:1または2、
h:0または1であり、g+hが1または2となる数。
ただし、Y-Q5およびX6が、前記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
[9]上記[1]~[8]のいずれかの製造方法で得られた撥インク剤、アルカリ可溶性樹脂(A)、光重合開始剤(B)および溶媒(D)を含むネガ型感光性樹脂組成物。
[10]前記撥インク剤の含有割合が、ネガ型感光性樹脂組成物における全固形分中、0.01~10質量%である上記[9]のネガ型感光性樹脂組成物。
[11]さらに、架橋剤(E)を含み、該架橋剤(E)が1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物である、上記[9]または[10]のネガ型感光性樹脂組成物。
[12]基板表面を画素形成用の複数の区画に仕切る形に形成された隔壁であって、上記[9]~[11]のいずれかのネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。
[13]基板表面に複数の画素と隣接する画素間に位置する隔壁とを有する光学素子であって、前記隔壁が上記[12]の隔壁で形成されていることを特徴とする光学素子。
また、本発明によれば、紫外線/オゾン照射処理を経ても撥インク性に優れた隔壁、および該隔壁を有し白抜け現象等の発生が抑制された光学素子の提供が可能である。
本明細書における式(c-1)で表される化合物を、化合物(c-1)という。他の化合物についても同様である。
本明細書における「側鎖」とは、繰り返し単位が主鎖を構成する重合体において、主鎖を構成する炭素原子に結合する、水素原子またはハロゲン原子以外の基である。
本明細書における「全固形分」とは、ネガ型感光性樹脂組成物が含有する成分のうち、隔壁形成成分をいい、ネガ型感光性樹脂組成物を140℃で24時間加熱して溶媒を除去した、残存物である。具体的には、溶媒(D)等の隔壁形成過程における加熱等により揮発する揮発性成分以外の全成分を示す。なお、全固形分の量は仕込み量からも計算できる。
本明細書においては、ネガ型感光性樹脂組成物を塗布した膜を「塗膜」、それを乾燥させた状態を「膜」、さらに、それを硬化させて得られる膜を「硬化膜」という。
本明細書におけるインクとは、乾燥硬化した後に、例えば光学的、電気的に機能を有する液体を総称するものであり、従来から用いられている着色材料に限定されるものではない。また、上記インクを注入して形成される「画素」についても同様に、隔壁で仕切られた、光学的、電気的な機能を有する区分を表すものとして用いられる。
本明細書における「撥インク性」とは、上記インクをはじくために、撥水性と撥油性の両方を適度に有する性質をいい、例えば、後述の方法で評価できる。
以下、本発明の実施の形態を説明する。なお、本明細書において特に説明のない場合、%は質量%を表す。
本発明の製造方法は、上式(c-1)で表される加水分解性シラン化合物(以下、加水分解性シラン化合物(c-1)ともいう。)と上式(c-2)で表される加水分解性シラン化合物(以下、加水分解性シラン化合物(c-2)ともいう。)とを含む混合物の部分加水分解縮合物からなる撥インク剤の製造方法であって、以下の工程(I)および工程(II)を含むことを特徴とする。
工程(I):前記混合物に酸を含ませて加水分解性シラン化合物(c-2)における窒素原子をプロトン化する工程、
工程(II):前記混合物に水と酸触媒とを含ませて該混合物を加水分解および縮合反応させる工程。
ネガ型感光性樹脂組成物中においては、アンモニウム型カチオン基は溶媒和される。これにより、本発明の製造方法で得られた撥インク剤は、該組成物中でより安定に存在することが可能となると考えられる。
下式(7)中の式(3-1)で表される平均組成式の生成物は、後述の式(3)で表される平均組成式の加水分解縮合物において、加水分解性シラン化合物(c-2)に由来する縮合単位のRNが、全て後述の式(5)で表される基である加水分解縮合物である。
ここで、式(7)で得られる生成物は、実際は加水分解性基またはシラノール基が残存した部分加水分解縮合物であり、本発明においては、得られた部分加水分解縮合物を撥インク剤として使用する。ただし、この生成物(部分加水分解縮合物)を化学式で表すことは困難であり、式(7)中、式(3-1)で表される平均組成式は、式(7)に表される反応によって製造された部分加水分解縮合物において、加水分解性基またはシラノール基の全てがシロキサン結合となったと仮定した場合の化学式である。
ここで、式(7)においては、工程(I)および工程(II)に用いる酸は、いずれも一塩基酸を用いているが、本発明の製造方法において用いる酸はこれに限定されない。
具体的には、反応をガスクロマトグラフィーでモニターし、原料としての化合物(c-1)~(c-5)が検出限界以下になった時点から、さらに、0.5~5時間反応を継続することが好ましい。すなわち、工程(II)の反応開始から、反応を原料としての化合物(c-1)~(c-5)が検出限界以下になるまでの時間は、0.3~2時間が好ましく、さらに0.5~5時間反応を継続することが好ましく、全反応時間としては、0.3~7時間が好ましい。
該溶媒としては、水;メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、イソブタノール、2-メチル-2-プロパノール、エチレングリコール、グリセリン、プロピレングリコール等のアルコール類;アセトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類;2-メトキシエタノール、2-エトキシエタノール等のセルソルブ類;2-(2-メトキシエトキシ)エタノール、2-(2-エトキシエトキシ)エタノール、2-(2-ブトキシエトキシ)エタノール等のカルビトール類;メチルアセテート、エチルアセテート、プロピレングリコールモノメチルエーテルアセテート、4-ブチロラクトン、ブチルアセテート、3-メトキシブチルアセテート等のエステル類;プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル等のグリコールのモノアルキルエーテル類;ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジプロピレングリコールジメチルエーテル等のグリコールのジアルキルエーテル類;が挙げられる。その他には、ベンジルアルコール、N,N-ジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、N-メチルピロリドン等が挙げられる。溶媒は1種を単独で用いても2種以上を併用してもよい。
なお、上記撥インク剤の製造に用いた溶媒は、溶質である撥インク剤とともに溶液の形で、ネガ型感光性樹脂組成物に配合されてもよい。
加水分解性シラン化合物(c-1)は、本発明の撥インク剤の製造方法における必須の原料成分であり、下式(c-1)で表される化合物である。
A-Rf-Q1-SiX1 3 …(c-1)
式(c-1)において、Aはフッ素原子または下式(1)で表される基を示す。
-Q3-SiX3 3 …(1)
式(c-1)中のA以外の記号、および式(1)中の記号は、以下の通りである。
Rf:炭素原子数2~15のエーテル性酸素原子を含んでいてもよいペルフルオロアルキレン基、
Q1、Q3:炭素原子数1~10のフッ素原子を含まない2価の有機基、
X1、X3:それぞれ独立して、加水分解性基。
ただし、X1、X3が、上記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
Rfが上記範囲であると、ネガ型感光性樹脂組成物を用いて形成される隔壁が、優れた撥インク性および撥インク性の耐紫外線/オゾン性を示し、また、汎用の溶媒への溶解性が優れているため好ましい。
Rfの構造は、直鎖構造、分岐構造、環構造、または部分的に環を有する構造が挙げられるが、直鎖構造が好ましい。
-(CF2)4-、-(CF2)6-、-(CF2)8-。
-CF2CF2OCF2CF2OCF2-、-CF2CF2OCF2CF2OCF2CF2-、-CF2CF2OCF2CF2OCF2CF2OCF2CF2OCF2-、-CF2CF2OCF2CF2OCF2CF2OCF2CF2OCF2CF2-。
-CF2CF2CF2OCF2-、-CF2CF2CF2OCF2CF2-、-CF2CF2CF2OCF(CF3)-、-CF2CF2CF2OCF(CF3)CF2-、-CF2CF2CF2OCF(CF3)CF2OCF2CF2-、-CF2CF2CF2OCF(CF3)CF2OCF(CF3)-、-CF2CF2CF2OCF(CF3)CF2OCF(CF3)CF2-、-CF2OCF(CF3)CF2OCF(CF3)-、-CF2CF2OCF(CF3)CF2OCF(CF3)-。
Q1およびQ3は、右側の結合手にSiが、左側の結合手にRfがそれぞれ結合するとして表示した場合に、具体的には、-(CH2)i1-(i1は1~5の整数。)、-CH2O(CH2)i2-(i2は1~4の整数。)、-SO2NR1-(CH2)i3-(R1は水素原子、メチル基またはエチル基、i3は1以上であり、R1の炭素原子数との合計で4以下の整数。)、-(C=O)-NR1-(CH2)i4-(R1は上記と同様であり、i4は1以上であり、R1の炭素原子数との合計で4以下の整数。)で表される基が好ましい。Q1およびQ3としては、i1が2または3である-(CH2)i1-がより好ましく、-(CH2)2-が特に好ましい。
また、Rfがエーテル性酸素原子を含むペルフルオロアルキレン基である場合、上記Q1およびQ3としては、-(CH2)i1-、-CH2O(CH2)i2-、-SO2NR1-(CH2)i3-、-(C=O)-NR1-(CH2)i4-で表される基(i1~i4およびR1は上記と同様)が好ましい。この場合においても、-(CH2)2-が特に好ましい。
F(CF2)4CH2CH2Si(OCH3)3、F(CF2)6CH2CH2Si(OCH3)3、F(CF2)8CH2CH2Si(OCH3)3、F(CF2)3OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3、F(CF2)2O(CF2)2O(CF2)2CH2CH2Si(OCH3)3。
(CH3O)3SiCH2CH2(CF2)4CH2CH2Si(OCH3)3、
(CH3O)3SiCH2CH2(CF2)6CH2CH2Si(OCH3)3、
(CH3O)3SiCH2CH2(CF2)2OCF2(CF3)CFO(CF2)2OCF(CF3)CF2O(CF2)2CH2CH2Si(OCH3)3。
なお、本発明の撥インク剤の製造方法における原料である加水分解性シラン化合物として、化合物(c-1)は、1種を単独で用いることも2種以上を併用することも可能である。
加水分解性シラン化合物(c-2)は、上記化合物(c-1)とともに、本発明の撥インク剤の製造方法における必須の原料成分であり、下式(c-2)で表される化合物である。
-Q4-SiX4 (3-j)(RH2)j …(2)
式(c-2)中のD、E以外の記号、並びに式(2)中の記号は、以下の通りである。
RH1、RH2:炭素原子数1~6の炭化水素基、
Q2、Q4:それぞれ独立して、炭素原子数1~6のフッ素原子を含まない2価の有機基、
X2、X4:それぞれ独立して、加水分解性基、
p:1または2、
q:0または1であり、p+qが1または2となる数、
j:0または1。
ただし、E-N(D)-Q2、X2、X4が、上記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
また、化合物(c-2)において、アミノ基を有する有機基(E-N(D)-Q2-)は、窒素原子に、D、Eとして、連結基(Q4)を介して2官能性または3官能性の加水分解性シリル基(-SiX4 (3-j)(RH2)j)が、1個または2個結合した基であってもよい。
本発明の製造方法で得られる撥インク剤においては、化合物(c-2)における窒素原子をアンモニウム型カチオンとして存在させる方法として、化合物(c-2)が有するアミノ基を、酸によりプロトン化する方法を適用している。
炭素原子数1~12の1価の有機基としては、炭素数1~12の直鎖構造、分岐構造、シクロ環構造、または部分的にシクロ環を有する構造のアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~12のフェニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~24のフェニルアルキル基、等が挙げられる。これらの炭化水素基において、炭素原子に結合する水素原子の一部は-NH2基に置換されていてもよい。さらに、アルキル基を構成する-CH2-の一部は-C(=O)-に置換されていてもよい。
本発明の撥インク剤の製造方法において、アミノ基を含む化合物(c-2)がベンゼン環を有する場合は、該化合物(c-2)をネガ型感光性樹脂組成物に配合した際に、アルカリ可溶性樹脂(A)中のベンゼン環との相互作用が高まるため、撥インク剤がさらに安定化され、ネガ型感光性樹脂組成物の安定性がより向上する。
式(c-2)中、pは1または2、qは0または1であり、p+qが1または2となる数である。よって、加水分解性基X2の数(4-p-q)は、2または3である。pおよびqは、造膜性の観点から、加水分解性基X2の数が3となる数、すなわちpが1で、qが0であることが好ましい。また、式(2)中、jは0または1であるが、上記と同様に造膜性の観点から、加水分解性基X4の数が3となる数、すなわちjが0であることが好ましい。このように、化合物(c-2)は、加水分解性シリル基として3官能性の加水分解性シリル基を有することが好ましい。
H2N(CH2)2NH(CH2)3SiCH3(OCH3)2、
H2N(CH2)2NH(CH2)3Si(OCH3)3、
H2N(CH2)2NH(CH2)3Si(OC2H5)3、
H2N(CH2)3Si(OCH3)3、
H2N(CH2)3Si(OC2H5)3、
H2NC(O)NH(CH2)3Si(OC2H5)3、
CH3C(O)NH(CH2)3Si(OCH3)3、
C6H5NH(CH2)3Si(OCH3)3、
C6H5NH(CH2)3Si(OC2H5)3。
HN((CH2)3Si(OC2H5)3)2、HN((CH2)3Si(OCH3)3)2、
(CH3O)3Si(CH2)3-NH-(CH2)2-NH-(CH2)3Si(OCH3)3、((C2H5O)3Si-(CH2)3-NH)2C=O、((CH3O)3Si-(CH2)3-NH)2C=O、HN((CH2)3SiCH3(OC2H5)2)2。
なお、本発明の撥インク剤の製造方法における原料である、加水分解性シラン化合物として、化合物(c-2)は、1種を単独で用いることも2種以上を併用することも可能である。
加水分解性シラン化合物(c-3)は、本発明の製造方法において、得られる撥インク剤の造膜性や溶媒への溶解性を高めるために任意に用いられ、下式(c-3)で表される。
RH3 r-SiX5 (4-r) …(c-3)
なお、式(c-3)において、加水分解性基を示すX5は、上式(c-1)中のX1と好ましい態様を含めて同様である。また、RH3は上式(c-2)中のRH1と好ましい態様を含めて同様である。式(c-3)中、rは0、1または2である。RH3およびX5が、上記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
化合物(c-3)を用いることより、撥インク剤は炭化水素系の溶媒に溶解しやすくなり、基材の表面にネガ型感光性樹脂組成物の塗膜を形成する際に、比較的安価な溶媒を選択できる。
Si(OCH3)4、Si(OCH2CH3)4、CH3Si(OCH3)3、
CH3Si(OCH2CH3)3、CH3CH2Si(OCH3)3、
CH3CH2Si(OCH2CH3)3、(CH3)2Si(OCH3)2、
(CH3)2Si(OCH2CH3)2、
Si(OCH3)4を加水分解縮合した化合物(例えば、コルコート社製のメチルシリケート51(商品名))、
Si(OCH2CH3)4を加水分解縮合した化合物(例えば、コルコート社製のエチルシリケート40、エチルシリケート48(いずれも商品名))。
加水分解性シラン化合物(c-4)は、本発明の製造方法において、得られる撥インク剤の隔壁上面への定着性を高める目的で任意に用いられる、下式(c-4)で表される加水分解性シラン化合物である。
式(c-4)において、加水分解性基を示すX6は、上記式(c-1)中のX1と好ましい態様を含めて同様である。また、RH4は上記式(c-2)中のRH1と好ましい態様を含めて同様である。
式(c-4)中のYは、エチレン性二重結合を有する基であり、Q5は、炭素原子数1~6のフッ素原子を含まない2価の有機基である。gは1または2であり、hは0または1であり、g+hが1または2となる数である。ただし、Y-Q5およびX6が、上記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。
式(c-4)中のQ5は、加水分解性シリル基(-SiX6 (4-g-h)(RH4)h)とYとを結合する連結基であり、具体的には、炭素原子数2~6のアルキレン基、フェニレン基等が挙げられる。なかでも、-(CH2)3-が好ましい。
式(c-4)中、gが1、hが0または1であることが好ましい。
CH2=C(CH3)COO(CH2)3Si(OCH3)3、
CH2=C(CH3)COO(CH2)3Si(OC2H5)3、
CH2=CHCOO(CH2)3Si(OCH3)3、
CH2=CHCOO(CH2)3Si(OC2H5)3、
[CH2=C(CH3)COO(CH2)3]CH3Si(OCH3)2、
[CH2=C(CH3)COO(CH2)3]CH3Si(OC2H5)2。
撥インク剤を、化合物(c-1)および化合物(c-2)に加えて、化合物(c-4)を用いて製造する場合、化合物(c-1)および化合物(c-2)の合計量に対する加水分解性シラン化合物(c-4)の配合量は、100~500モル%が好ましく、50~400モル%が特に好ましい。
加水分解性シラン化合物(c-5)およびオルガノジシロキサン(c-6)はともに、本発明の製造方法において、得られる撥インク剤のネガ型感光性樹脂組成物への相溶性の向上や反応性の制御等を目的として任意に用いられる成分である。
加水分解性シラン化合物(c-5)は、下式(c-5)で表される1官能性の加水分解性シラン化合物である。
式(c-5)中、W1は、上式(c-1)に中のA-Rf-Q1(ただし、Aはフッ素原子である。)、RH5または上式(c-4)中のY-Q5を示す。なお、式(c-5)中、2個のRH5(W1がRH5の場合は3個のRH5)は互いに同一であっても異なっていてもよい。
加水分解性シラン化合物(c-5)において、W1を適宜調整することより、撥インク剤とネガ型感光性樹脂組成物の他の構成成分との相溶性の向上、シラノール基を封止することによる撥インク剤自体の反応性の抑制、硬化膜の撥インク性の調整、膜の硬化性向上など、ネガ型感光性樹脂組成物の特性についてより細かく調整することができる。
化合物(c-6)において、W2を適宜調整することより、上記加水分解性シラン化合物(c-5)と同様の効果を、本発明の製造方法で得られる撥インク剤に付与することができる。
F(CF2)6CH2CH2(CH3)2SiOCH3、(CH3)3SiOCH3、[CH2=C(CH3)COO(CH2)3](CH3)2SiOCH3。
化合物(c-6)の具体例としては、以下の化合物が挙げられる。
(CH3)3SiOSi(CH3)3。
本発明の製造方法で得られる撥インク剤(以下、「本発明の撥インク剤」ともいう。)は、加水分解性シラン化合物(c-1)と加水分解性シラン化合物(c-2)とを含む混合物の部分加水分解縮合物からなり、加水分解性シラン化合物(c-2)における窒素原子の一部または全部が、アンモニウム型カチオンとして存在することを特徴とする。
なお、部分加水分解縮合物中のシラノール基数は、29Si-NMRにより測定されるシラノール基を有するSi基と、シラノール基を有しないSi基とのピーク面積の比により算出される。
RNは、上式(c-2)におけるE-N(D)-Q2-(ただし、DおよびEが、それぞれ独立に、水素原子または炭素原子に結合する水素原子が-NH2基に置換されていてもよい炭素原子数1~12の1価の有機基である。)で示される基、または該基の窒素原子が、プロトン化されてアンモニウム型カチオンとなった下式(5)で示される基を示す。
Wは、上式(c-5)におけるW1、または式(c-6)におけるW2を示す。
RHは、上式(c-5)におけるRH5、または上式(c-6)におけるRH6を示す。
RH1、RH3、RH4、p、q、r、g、hについては、上式(c-2)~上式(c-4)におけるのと、好ましい態様を含めて同様である。
m、n、k、s、tは、構成単位の合計モル量に対する各単位のモル%を示す。m、nはそれぞれ0を超える数であり、k、s、tは0以上の数であり、m+n+k+s+tは、100である。
撥インク剤の数平均分子量(Mn)は、以下に説明する撥インク剤の製造方法において反応条件等を選択することにより調節できる。
本発明の撥インク剤は、ネガ型感光性樹脂組成物に配合した際に、該組成物中での貯蔵安定性に優れ、該組成物から製造される硬化膜、例えば、隔壁において紫外線/オゾン照射処理を経ても優れた撥インク性を付与することが可能である。
本発明のネガ型感光性樹脂組成物は、アルカリ可溶性樹脂(A)、光重合開始剤(B)、撥インク剤(C)として本発明の製造方法で得られた撥インク剤、および溶媒(D)を含有する。さらに、必要に応じて、架橋剤(E)を含有する。さらに、熱架橋剤(F)、着色剤(G)、高分子分散剤(H)、分散助剤(I)、シランカップリング剤(J)、微粒子(K)、リン酸化合物(L)およびその他の添加剤を含有してもよい。
本発明におけるアルカリ可溶性樹脂(A)は、1分子中に酸性基とエチレン性二重結合とを有する感光性樹脂である。アルカリ可溶性樹脂(A)が分子中にエチレン性二重結合を有することで、ネガ型感光性樹脂組成物の露光部は、光重合開始剤(B)から発生したラジカルにより重合して硬化する。このように硬化した露光部分は、アルカリ現像液にて除去されない。また、アルカリ可溶性樹脂(A)が分子中に酸性基を有することで、アルカリ現像液にて、硬化していないネガ型感光性樹脂組成物の未露光部を選択的に除去することができる。その結果、隔壁を形成することができる。
前記エチレン性二重結合としては、特に制限されないが、(メタ)アクリロイル基、アリル基、ビニル基、ビニルオキシ基、ビニルオキシアルキル基等の付加重合性を有する二重結合が挙げられ、これらは1種を単独で用いても2種以上を併用してもよい。なお、エチレン性二重結合基が有する水素原子の一部または全てが、アルキル基、好ましくはメチル基で置換されていてもよい。
(i)側鎖に酸性基以外の反応性基、例えば、水酸基、エポキシ基等の反応性基を有する単量体と、側鎖に酸性基を有する単量体とを共重合させ、反応性基を有する側鎖と、酸性基を有する側鎖を有する共重合体を得る。次いで、この共重合体と、上記反応性基に対して結合し得る官能基およびエチレン性二重結合を有する化合物を反応させる。または、側鎖に酸性基、例えばカルボキシ基等を有する単量体を共重合させた後、酸性基に対して結合し得る官能基およびエチレン性二重結合を有する化合物を、反応後に酸性基が残る量で反応させる。
なお、(i)または(ii)は溶媒中で実施することが好ましい。
これらのうちでも、本発明においては(i)の方法が好ましく用いられる。以下、(i)の方法について具体的に説明する。
エチレン性二重結合を有する酸無水物としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸、メチル-5-ノルボルネン-2,3-ジカルボン酸無水物、3,4,5,6-テトラヒドロフタル酸無水物、cis-1,2,3,6-テトラヒドロフタル酸無水物、2-ブテン-1-イルサクシニックアンハイドライド等が挙げられる。
イソシアナート基とエチレン性二重結合とを有する化合物としては、2-(メタ)アクリロイルオキシエチルイソシアネート、1,1-ビス((メタ)アクリロイルオキシメチル)エチルイソシアネート等が挙げられる。
塩化アシル基とエチレン性二重結合とを有する化合物としては、(メタ)アクリロイルクロライド等が挙げられる。
反応性基としてエポキシ基を有する単量体と共重合させる酸性基を有する単量体としては、上記水酸基を反応性基として有する単量体で説明したものと同様の単量体が使用でき、エポキシ基を反応性基として有する単量体と酸性基を有する単量体の共重合についても、従来公知の方法で行うことができる。
具体的には、エポキシ樹脂と、カルボキシ基とエチレン性二重結合を有する化合物とを反応させることにより、エポキシ樹脂にエチレン性二重結合が導入される。次に、エチレン性二重結合が導入されたエポキシ樹脂に、多価カルボン酸またはその無水物を反応させることにより、カルボキシ基を導入することができる。
(式(A1-2a)中、vは、1~50の整数であり、2~10の整数が好ましい。またベンゼン環の水素原子は、それぞれ独立に、炭素原子数1~12のアルキル基、ハロゲン原子、または一部の水素原子が置換基で置換されていてもよいフェニル基で置換されていてもよい。)
(式(A1-2c)中、ベンゼン環の水素原子は、それぞれ独立に、炭素原子数1~12のアルキル基、ハロゲン原子、または一部の水素原子が置換基で置換されていてもよいフェニル基で置換されていてもよい。zは、0または1~10の整数である。)
樹脂(A1-2)としては、ビスフェノールA型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、ビスフェノールF型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、フェノールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、クレゾールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、トリスフェノールメタン型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、式(A1-2a)~(A1-2c)で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂が特に好ましい。
アルカリ可溶性樹脂(A)の酸価は、10~300mgKOH/gが好ましく、30~150mgKOH/gが特に好ましい。酸価が上記範囲であると、ネガ型感光性樹脂組成物の現像性が良好になる。
ネガ型感光性樹脂組成物における全固形分中のアルカリ可溶性樹脂(A)の含有割合は、5~80質量%が好ましく、10~60質量%が特に好ましい。含有割合が上記範囲であると、ネガ型感光性樹脂組成物の現像性が良好である。
本発明における光重合開始剤(B)は、光重合開始剤としての機能を有する化合物であれば特に制限されないが、光によりラジカルを発生する化合物が好ましい。
R4は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~30のフェニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~30のフェニルアルキル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基、またはシアノ基を示す。
R6、R7、R8およびR9は、それぞれ独立に、水素原子、シアノ基、ハロゲン原子、ニトロ基、R61、OR62、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンジルカルボニル基、炭素原子数2~12のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基、または炭素原子数1~20のアミド基を示す。
R0は、R61、OR62、シアノ基またはハロゲン原子を示す。
aは0または1~3の整数である。
R3は、水素原子、炭素原子数1~12のアルキル基、炭素原子数3~8のシクロアルキル基、炭素原子数2~5のアルケニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェノキシ基を示す。
R4は、水素原子、炭素原子数1~20のアルキル基、炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、炭素原子数2~12のアルコキシカルボニル基、またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基を示す。
R6、R7、R8およびR9は、それぞれ独立に、水素原子、炭素原子数1~12のアルキル基、シクロアルカン環中の水素原子がアルキル基に置換されていてもよい炭素原子数3~8のシクロアルキル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~20のフェニル基、炭素原子数2~20のアルカノイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンゾイル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のベンジルカルボニル基、炭素原子数2~12のアルコキシカルボニル基、ベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~20のフェノキシカルボニル基、炭素原子数1~20のアミド基、またはニトロ基を示す。
R0の個数を示すaは0である。
R3:フェニル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(4-1)、
R3:メチル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(4-2)、
R3:メチル基、R4:ブチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(4-3)、
R3:メチル基、R4:ヘプチル基、R5:エチル基、R6、R8、R9:水素原子、R7:ベンゾイル基である化合物(4-4)、
R3:フェニル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチルベンゾイル基である化合物(4-5)、
R3:メチル基、R4:オクチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチルベンゾイル基である化合物(4-6)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチルベンゾイル基である化合物(4-7)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチル-4-テトラヒドロピラニルメトキシベンゾイル基である化合物(4-8)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチル-5-テトラヒドロフラニルメトキシベンゾイル基である化合物(4-9)、
R3:メチル基、R4:メチル基、R5:エチル基、R6、R8、R9:水素原子、R7:2-メチル-5-テトラヒドロピラニルメトキシベンゾイル基である化合物(4-10)
光重合開始剤(4)としては、市販品として、IRGACURE OXE02(BASF社製、商品名:上記化合物(4-7)に相当する。)等が挙げられる。
光重合開始剤(4)としては、また、国際公開第2008/078678号に記載のNo.1~71が使用できる。
光重合開始剤(B)としては、2-メチル-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1-オン、1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)、エタノン1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシム)(上記化合物(4-7)に相当する化合物。)、2,4-ジエチルチオキサントンが好ましい。さらに、これらと上記ベンゾフェノン類、例えば、4,4’-ビス(ジエチルアミノ)ベンゾフェノンとの組み合わせが特に好ましい。
ネガ型感光性樹脂組成物における全固形分中の光重合開始剤(B)の割合は、0.1~50質量%が好ましく、0.5~30質量%がより好ましく、5~15質量%が特に好ましい。上記範囲であると、ネガ型感光性樹脂組成物の現像性が良好である。
本発明のネガ型感光性樹脂組成物は、撥インク剤(C)として上記本発明の製造方法で得られた撥インク剤を含有する。
本発明のネガ型感光性樹脂組成物は、溶媒(D)を含有することで、ネガ型感光性樹脂組成物の粘度が低減し、ネガ型感光性樹脂組成物の基板表面への塗布がしやすい。よって、均一なネガ型感光性樹脂組成物の塗膜が形成できる。
R11O(C2H4O)yR12 (6)
式(6)中、R11は炭素原子数が1~10のアルキル基、R12は炭素原子数が2~10のアルキル基を示し、yは1~10の整数を示す。
R12としては炭素原子数が2~4のアルキル基が好ましく、2のアルキル基が特に好ましい。また、yは1~3が好ましく、2が特に好ましい。
ジエチレングリコールエチルメチルエーテル(EDM、沸点:176℃)、ジエチレングリコールジエチルエーテル(EDE、沸点:189℃)、ジエチレングリコールイソプロピルメチルエーテル(IPDM、沸点:179℃)等が挙げられる。これらは1種を用いても、2種以上を併用してもよい。なかでも、ジエチレングリコールエチルメチルエーテルが特に好ましい。
一方、溶媒(D2)は水酸基を有するため、分子間の水素結合により、水酸基を持たない同程度の分子量の化合物と比較して粘度が上昇しやすい。溶媒(D2)の沸点が上記上限値未満であると、その粘度は概ね上記上限値以下となり、塗工時に基板表面の濡れ広がりが良好となって、多くの液量を必要としたり、面内均一性が悪化したり、ムラが生じたりすることがない。
溶媒(D)の全量に対する溶媒(D2)の割合は、1~50質量%が好ましく、5~40質量%が特に好ましい。
本明細書においては、このように混合溶媒であって、沸点の範囲が溶媒(D1)の沸点の範囲を超えている溶媒については、溶媒(D3)に分類した。
本発明のネガ型感光性樹脂組成物は、ラジカル硬化を促進する任意成分として、架橋剤(E)を含んでもよい。架橋剤(E)としては、1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物が好ましい。ネガ型感光性樹脂組成物が架橋剤(E)を含むことにより、露光時におけるネガ型感光性樹脂組成物の硬化性が向上し、低い露光量でも隔壁を形成することができる。
本発明における熱架橋剤(F)は、カルボキシ基および/または水酸基と反応し得る基を2個以上有する化合物である。熱架橋剤(F)は、アルカリ可溶性樹脂(A)がカルボキシ基および/または水酸基を有する場合、アルカリ可溶性樹脂(A)と反応し、硬化膜の架橋密度を増大させ耐熱性を向上させるという作用を有する
本発明のネガ型感光性樹脂組成物を液晶表示素子のカラーフィルタのR、G、Bの三色の画素を囲む格子状の黒色部分であるブラックマトリックス形成のために用いる場合、着色剤(G)を含むことが好ましい。
着色剤(G)としては、例えば、カーボンブラック、アニリンブラック、アントラキノン系黒色顔料、ペリレン系黒色顔料、具体的には、C.I.ピグメントブラック1、6、7、12、20、31等が挙げられる。着色剤(G)としては、赤色顔料、青色顔料、緑色顔料等の有機顔料や無機顔料の混合物を用いることもできる。
本発明のネガ型感光性樹脂組成物が、上記着色剤(G)等の分散性材料を含有する場合、その分散性を向上させるために、高分子分散剤(H)を含有することが好ましい。
高分子分散剤(H)としては、特に限定されず、ウレタン系、ポリイミド系、アルキッド系、エポキシ系、ポリエステル系、メラミン系、フェノール系、アクリル系、ポリエーテル系、塩化ビニル系、塩化ビニル酢酸ビニル系共重合体系、ポリアミド系、ポリカーボネート系等が挙げられ、ウレタン系、またはポリエステル系が好ましい。また、高分子分散剤(H)は、エチレンオキサイドおよび/またはプロピレンオキサイド由来の構成単位を有していてもよい。
高分子分散剤(H)としては市販品を用いてもよい。市販品としては、ディスパロンDA-7301(商品名、楠本化成社製)、BYK161、BYK162、BYK163、BYK182(以上全て商品名、BYK-Chemie社製)、ソルスパーズ5000、ソルスパーズ17000(以上全て商品名、ゼネカ社製)等が挙げられる。
高分子分散剤(H)の使用量は、着色剤(G)に対して、5~30質量%であることが好ましく、10~25質量%が特に好ましい。使用量が上記範囲の下限値以上であると、着色剤(G)の分散性が向上し、上記範囲の上限値以下であると、ネガ型感光性樹脂組成物の現像性が良好になる。
本発明のネガ型感光性樹脂組成物は、分散助剤(I)として、フタロシアニン系顔料誘導体や金属フタロシアニンスルホンアミド化合物を含有してもよい。分散助剤(I)は、着色剤(G)等の分散性材料と高分子分散剤(H)に吸着して、分散安定性を向上させる機能を有すると考えられる。
本発明のネガ型感光性樹脂組成物は、シランカップリング剤(J)を使用すると、形成される硬化膜の基材密着性が向上する。
シランカップリング剤(J)の具体例としては、テトラエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、メチルトリメトキシシラン、ビニルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、へプタデカフルオロオクチルエチルトリメトキシシラン、ポリオキシアルキレン鎖含有トリエトキシシラン等が挙げられる。これらは単独で用いてもよいし、2種以上を併用してもよい。
本発明のネガ型感光性樹脂組成物は、必要に応じて、微粒子(K)を含んでいてもよい。微粒子(K)を配合することにより、ネガ型感光性樹脂組成物から得られる隔壁の熱垂れを防止することが可能となる。
また、ネガ型感光性樹脂組成物が、着色剤(G)および高分子分散剤(H)を含有する場合には、該高分子分散剤(H)の吸着能を考慮すれば、微粒子(K)は、負に帯電していることが好ましい。
さらに、ネガ型感光性樹脂組成物の露光感度を考慮すると、微粒子(K)は、露光時に照射される光を吸収しないことが好ましく、超高圧水銀灯の主発光波長であるi線(365nm)、h線(405nm)およびg線(436nm)を吸収しないことが特に好ましい。
ネガ型感光性樹脂組成物における全固形分中の微粒子(K)の含有割合は、5~35質量%が好ましく、10~30質量%が特に好ましい。含有割合が上記範囲の下限値以上であると、ポストベークによる撥インク性の低下抑制効果があり、上記範囲の上限値以下であると、ネガ型感光性樹脂組成物の貯蔵安定性が良好になる。
本発明のネガ型感光性樹脂組成物は、必要に応じて、リン酸化合物(L)を含んでいてもよい。ネガ型感光性樹脂組成物がリン酸化合物(L)を含むことで、基板との密着性を向上させることができる。
リン酸化合物(L)しては、モノ(メタ)アクリロイルオキシエチルフォスフェート、ジ(メタ)アクリロイルオキシエチルフォスフェート、トリス(メタ)アクリロイルオキシエチルフォスフェート等が挙げられる。
本発明のネガ型感光性樹脂組成物においては、さらに必要に応じて硬化促進剤、増粘剤、可塑剤、消泡剤、レベリング剤、ハジキ防止剤、紫外線吸収剤等を含有することができる。
本発明のネガ型感光性樹脂組成物は、用途や要求特性に合わせて、組成と配合比を適宜選択することが好ましい。
本発明のネガ型感光性樹脂組成物における各種配合成分の好ましい組成を以下に示す。
アルカリ可溶性樹脂(A):ビスフェノールA型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、ビスフェノールF型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、フェノールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、クレゾールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、トリスフェノールメタン型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、および上記式(A1-2a)~(A1-2c)で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂からなる群から選ばれる少なくとも1つの樹脂であって、ネガ型感光性樹脂組成物における全固形分中に5~80質量%、
撥インク剤(C):加水分解性シラン化合物(c-1)および(c-2)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)および(c-3)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)、(c-3)および(c-4)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)および(c-4)の部分加水分解縮合物、および加水分解性シラン化合物(c-1)、(c-2)、(c-3)、(c-4)および(c-5)の部分加水分解縮合物からなる群から選ばれる少なくとも1つの部分加水分解縮合物であって、加水分解性シラン化合物(c-2)由来の窒素原子の一部または全部が、該部分加水分解縮合物においてアンモニウム型カチオンとして存在する撥インク剤を、ネガ型感光性樹脂組成物における全固形分中に0.01~10質量%、
アルカリ可溶性樹脂(A)、光重合開始剤(B)および撥インク剤(C)は組み合わせ1と同様であり、溶媒(D)が以下である。
溶媒(D):該溶媒(D)の全量に対して、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、3-メトキシブチルアセテート、ジプロピレングリコールジメチルエーテル、3-エトキシプロピオン酸エチル、4-ブチロラクトンおよびシクロヘキサノールアセテートから選ばれる溶媒(D1)を50~90質量%、水、2-プロパノールおよびプロピレングリコールモノメチルエーテルから選ばれる溶媒(D2)を5~45質量%、プロピレングリコール1-モノメチルエーテル2-アセテート、ブチルアセテート、シクロヘキサノン、ジエチレングリコールモノエチルエーテルアセテートおよびソルベントナフサから選ばれる溶媒(D3)を5~45質量%、それぞれ含有し、溶媒(D)はネガ型感光性樹脂組成物中に50~99質量%である。
アルカリ可溶性樹脂(A):ビスフェノールA型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、ビスフェノールF型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、フェノールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、クレゾールノボラック型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、トリスフェノールメタン型エポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂、および上記式(A1-2a)~(A1-2c)で表されるエポキシ樹脂に酸性基とエチレン性二重結合とを導入した樹脂からなる群から選ばれる少なくとも1つの樹脂であって、ネガ型感光性樹脂組成物における全固形分中に5~80質量%、
撥インク剤(C):加水分解性シラン化合物(c-1)および(c-2)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)および(c-3)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)、(c-3)および(c-4)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)および(c-4)の部分加水分解縮合物、および加水分解性シラン化合物(c-1)、(c-2)、(c-3)、(c-4)および(c-5)の部分加水分解縮合物からなる群から選ばれる少なくとも1つの部分加水分解縮合物であって、加水分解性シラン化合物(c-2)由来の窒素原子の一部または全部が、該部分加水分解縮合物においてアンモニウム型カチオンとして存在する撥インク剤を、ネガ型感光性樹脂組成物における全固形分中に0.01~10質量%、
アルカリ可溶性樹脂(A):上記式(A1-2a)で表されるビフェニル骨格を有するエポキシ樹脂、上記式(A1-2b)で表されるエポキシ樹脂、および上記式(A1-2c)で表されるビフェニル骨格を有するエポキシ樹脂からなる群から選ばれる少なくとも1つの樹脂に、酸性基とエチレン性二重結合とを導入した樹脂であって、ネガ型感光性樹脂組成物における全固形分中に5~80質量%、
撥インク剤(C):加水分解性シラン化合物(c-1)および(c-2)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)および(c-3)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)、(c-3)および(c-4)の部分加水分解縮合物、加水分解性シラン化合物(c-1)、(c-2)および(c-4)の部分加水分解縮合物、および加水分解性シラン化合物(c-1)、(c-2)、(c-3)、(c-4)および(c-5)の部分加水分解縮合物からなる群から選ばれる少なくとも1つの部分加水分解縮合物であって、加水分解性シラン化合物(c-2)由来の窒素原子の一部または全部が、該部分加水分解縮合物においてアンモニウム型カチオンとして存在する撥インク剤を、ネガ型感光性樹脂組成物における全固形分中に0.01~10質量%、
着色剤(G):カーボンブラック、赤色顔料、青色顔料、緑色顔料等の有機顔料の混合物から選ばれる少なくとも1つの着色剤であって、ネガ型感光性樹脂組成物における全固形分中に15~65質量%。
ネガ型感光性樹脂組成物を製造する方法としては、アルカリ可溶性樹脂(A)、光重合開始剤(B)、撥インク剤(C)、溶媒(D)、必要に応じて、架橋剤(E)、熱架橋剤(F)、着色剤(G)、高分子分散剤(H)、分散助剤(I)、シランカップリング剤(J)、微粒子(K)、リン酸化合物(L)およびその他の添加剤とを混合する方法が好ましい。
特に、本発明のネガ型感光性樹脂組成物を、基板表面に、複数の画素と隣接する画素間に位置する隔壁とを有する光学素子用の隔壁の形成に用いると、紫外線/オゾン洗浄処理等の親インク化処理後も、充分に撥インク性を有する隔壁を得ることができ、好ましい。
また、本発明のネガ型感光性樹脂組成物は、撥インク剤(C)として、上記本発明の製造方法により得られた撥インク剤を含有することにより、長期にわたって撥インク剤の凝集・沈降が抑制され、貯蔵安定性に優れる組成物である。
本発明の隔壁は、基板表面に区画を設けるために形成される隔壁であって、上記本発明のネガ型感光性樹脂組成物の硬化膜からなる。
本発明の隔壁は、光学素子の用途に好適に用いられ、ネガ型感光性樹脂組成物が着色剤(G)を含有する場合には、得られる隔壁はブラックマトリックスとしての適用が可能である。
本発明の隔壁は、例えば、基板表面に、複数の画素と隣接する画素間に位置する隔壁とを有する光学素子用として適用される。
また、現像工程とポストベーク工程の間に、上記形成された隔壁等をさらに光硬化させる工程(ポスト露光工程)を入れてもよい。
基板のネガ型感光性樹脂組成物の塗布面は、塗布前に予めアルコール洗浄、紫外線/オゾン洗浄等で洗浄することが好ましい。
図1(I)は、基板1上に本発明のネガ型感光性樹脂組成物からなる塗膜2が形成された状態の断面を示す図である。図1(II)は露光工程を模式的に示す図である。図1(III)は、現像工程後の基板1と基板表面に形成された隔壁6を示す断面図である。
以下、図1を用いて本発明のネガ型感光性樹脂組成物を用いた、光学素子用隔壁の製造方法を具体的に説明する。
図1(I)に断面を示すように、基板1上に上記本発明のネガ型感光性樹脂組成物を塗布してネガ型感光性樹脂組成物からなる塗膜2を形成する。なお、基板1上にネガ型感光性樹脂組成物の塗膜2を形成させる前に、基板1のネガ型感光性樹脂組成物の塗布面をアルコール洗浄、紫外線/オゾン洗浄等で洗浄することが好ましい。
塗膜2の膜厚は、最終的に得られる隔壁の高さを勘案して決められる。塗膜2の膜厚は、最終的に得られる隔壁の高さの100~200%が好ましく、100~130%が特に好ましい。塗膜2の膜厚は0.3~325μmが好ましく、1.3~65μmが特に好ましい。
上記塗膜形成工程で基板1上に形成された塗膜2を加熱し、膜2を得る。加熱によって、塗膜を構成するネガ型感光性樹脂組成物に含まれる溶媒を含む揮発成分が揮発し、除去され、粘着性のない膜が得られる。また、撥インク剤(C)が塗膜表面近傍に移行する。加熱の方法としては、基板1とともに塗膜2をホットプレート、オーブン等の加熱装置により、50~120℃で10~2,000秒間程度の加熱処理をする方法が挙げられる。
図1(II)に示すように、膜2に所定パターンのマスク4を介して光5を照射する。上記マスク4に切られた所定パターン部分のみを光5が透過し、基板1上の膜に到達して、その部分のみが光硬化する。したがって、隔壁の形成を行う場合、上記所定パターンは、隔壁の形状に適合する形に設けられる。
例えば、ポストベーク工程後における隔壁の幅の平均は、100μm以下であるのが好ましく、20μm以下が特に好ましい。また、隣接する隔壁間の距離の平均は、300μm以下であるのが好ましく、100μm以下が特に好ましい。該範囲となるようにパターンを形成したマスクを用いることが好ましい。
露光量は、5~1,000mJ/cm2が好ましく、50~400mJ/cm2が特に好ましい。露光量が上記範囲の下限値以上であると、隔壁となるネガ型感光性樹脂組成物の硬化が充分であり、その後の現像で、溶解や基板1からの剥離が生じにくくなる。上記範囲の上限値以下であると、高い解像度が得られる。露光時間としては、露光量、感光組成物の組成、塗膜の厚さ等にもよるが、1~60秒間が好ましく、5~20秒間が特に好ましい。
現像液を用いて現像を行い、図1(II)に示される基板1上の未露光部分2を除去する。これにより、図1(III)に断面図が示されるような、基板1と上記基板表面にネガ型感光性樹脂組成物の硬化膜により形成された隔壁6とから構成された基板が得られる。また、隔壁6と基板1で囲まれた部分は、インク注入等により画素が形成されるドット7と呼ばれる部分である。得られた基板10は、後述のポストベーク工程を経て、インクジェット方式での光学素子の作製に用いることが可能な基板となる。
また現像液には、溶解性の向上や残渣除去のために、界面活性剤やアルコール等の有機溶媒を添加することができる。
基板1上の隔壁6を加熱する。加熱の方法としては、基板1とともに隔壁6をホットプレート、オーブン等の加熱装置により、150~250℃で、5~90分間加熱処理をする方法が挙げられる。加熱処理により、基板1上のネガ型感光性樹脂組成物の硬化膜からなる隔壁6がさらに硬化し、隔壁6と基板1で囲まれるドット7の形状もより固定化される。なお、上記加熱温度は180℃以上であることが特に好ましい。加熱温度が低すぎると隔壁6の硬化が不充分であるために、充分な耐薬品性が得られず、その後のインクジェット塗布工程でドット7にインクを注入した場合に、そのインクに含まれる溶媒により隔壁6が膨潤したり、インクが滲んでしまうおそれがある。一方、加熱温度が高すぎると、隔壁6の熱分解が起こるおそれがある。
上記製造方法によって基板表面に隔壁を形成した後、例えば、上記基板と上記隔壁で囲まれた領域内に露出した基板表面に親インク化処理をし(親インク化処理工程)、次いで、上記領域にインクジェット法によりインクを注入して上記画素を形成する(インク注入工程)ことで光学素子が得られる。
(親インク化処理工程)
親インク化処理の方法としては、アルカリ水溶液による洗浄処理、紫外線洗浄処理、紫外線/オゾン洗浄処理、エキシマ洗浄処理、コロナ放電処理、酸素プラズマ処理等の方法が挙げられる。
アルカリ水溶液による洗浄処理は、アルカリ水溶液(水酸化カリウム、テトラメチル水酸化アンモニウム水溶液等)を用いて、基板表面を洗浄する湿式処理である。
紫外線洗浄処理は、紫外線を用いて、基板表面を洗浄する乾式処理である。
紫外線/オゾン洗浄処理は、185nmと254nmの波長の光を発光する低圧水銀ランプを用いて、基板表面を洗浄する乾式処理である。
エキシマ洗浄処理は、172nmの波長の光を発光するキセノンエキシマランプを用いて、基板表面を洗浄する乾式処理である。
コロナ放電処理は、高周波高電圧を利用し、空気中にコロナ放電を発生させ、基板表面を洗浄する乾式処理である。
酸素プラズマ処理は、主に真空中で高周波電源等をトリガーとして酸素を励起させ、反応性の高い「プラズマ状態」にしたものを用いて、基板表面を洗浄する乾式処理である。
上記本発明のネガ型感光性樹脂組成物を用いて形成された隔壁を有する基板を用いて光学素子を製造する場合、隔壁は上記親インク化処理後も充分な撥インク性を有することが求められる。そこで、隔壁の水の接触角は90度以上が好ましく、95度以上が特に好ましい。また、同様に隔壁のPGMEAの接触角は30度以上が好ましく、35度以上が特に好ましい。一方、上記本発明のネガ型感光性樹脂組成物を用いて形成された隔壁を有する基板を用いて光学素子を製造する場合、ドットについては、親インク性であることが求められ、その水の接触角は20度以下が好ましく、10度以下が特に好ましい。
親インク化処理工程後のドットに、インクジェット法によりインクを注入して画素を形成する工程である。この工程は、インクジェット法に一般的に用いられるインクジェット装置を用いて、通常の方法と同様に行うことができる。このような画素の形成に用いられるインクジェット装置としては、特に限定されるものではないが、帯電したインクを連続的に噴射し、磁場によって制御する方法、圧電素子を用いて間欠的にインクを噴射する方法、インクを加熱し、その発泡を利用して間欠的に噴射する方法等の各種の方法を用いたインクジェット装置を用いることができる。
隔壁の形成、ドットの親インク化処理、およびインクジェット法によるインク注入は上述の通りである。カラーフィルタにおいて、形成される画素の形状は、ストライプ型、モザイク型、トライアングル型、4画素配置型等の公知のいずれの配列とすることも可能である。
水性のインクは、溶媒として、水および必要に応じて水溶性有機溶媒を含み、バインダー樹脂成分として、水溶性樹脂または水分散性樹脂を含み、必要に応じて各種助剤を含む。
また、油性のインクは、溶媒として、有機溶媒を含み、バインダー樹脂成分として、有機溶媒に可溶な樹脂を含み、必要に応じて各種助剤を含む。
また、インクジェット法によりインクを注入した後、必要により、乾燥、加熱硬化、紫外線硬化等を行うことが好ましい。
さらに必要に応じて、カラーフィルタを用いて製造される液晶パネルの高品位化のために、フォトスペーサーを隔壁で構成されるブラックマトリックス上に形成することが好ましい。
隔壁を形成する前に、ガラス等の透明基材にスズドープ酸化インジウム(ITO)等の透明電極をスパッタ法等によって製膜し、必要に応じて所望のパターンに透明電極をエッチングする。次に、本発明のネガ型感光性樹脂組成物を用いて隔壁を形成し、ドットの親インク化処理後、インクジェット法を用いて、ドットに正孔輸送材料、発光材料の溶液を順次塗布し、乾燥して、正孔輸送層、および発光層を形成する。その後アルミニウム等の電極を蒸着法等によって形成することによって、有機EL素子の画素が得られる。
以下の(1)~(3)の工程を経て、有機TFTアレイを製造することができる。
(1)ガラス等の透明基材に、本発明のネガ型感光性樹脂組成物を用いて隔壁を形成する。ドットの親インク化処理後、インクジェット法を用いて、ドットにゲート電極材料の溶液を塗布し、ゲート電極を形成する。
(2)ゲート電極を形成させた後、その上にゲート絶縁膜を形成させる。ゲート絶縁膜上に、本発明のネガ型感光性樹脂組成物を用いて隔壁を形成し、ドットの親インク化処理後、インクジェット法を用いて、ドットにソース・ドレイン電極材料の溶液を塗布し、ソース・ドレイン電極を形成する。
(3)ソース・ドレイン電極を形成させた後、一対のソース・ドレイン電極を含む領域を囲むように、本発明のネガ型感光性樹脂組成物を用いて隔壁を形成し、ドットの親インク化処理後、インクジェット法を用いて、ドットに有機半導体の溶液を塗布し、有機半導体層をソース・ドレイン電極間に形成させる。
なお、(1)~(3)は、それぞれ1工程のみにおいて、本発明のネガ型感光性樹脂組成物を用いた隔壁を利用してもよいし、2つ以上の工程において、本発明のネガ型感光性樹脂組成物を用いた隔壁を利用してもよい。
[数平均分子量(Mn)]
分子量測定用の標準試料として市販されている重合度の異なる数種の単分散ポリスチレン重合体のゲルパーミエーションクロマトグラフィー(GPC)を、市販のGPC測定装置(東ソー社製、装置名:HLC-8320GPC)を用いて測定し、ポリスチレンの分子量と保持時間(リテンションタイム)との関係をもとに検量線を作成した。
試料をテトラヒドロフランで1.0質量%に希釈し、0.5μmのフィルターを通過させた後、該試料についてのGPCを、前記GPC測定装置を用いて測定した。
前記検量線を用いて、試料のGPCスペクトルをコンピュータ解析することにより、該試料の数平均分子量(Mn)を求めた。
静滴法により、JIS R3257「基板ガラス表面のぬれ性試験方法」に準拠して、基材上の測定表面の3ヶ所に水滴を載せ、各水滴について測定した。液滴は2μL/滴であり、測定は20℃で行った。接触角は、3測定値の平均値(n=3)で示す。
静滴法により、JIS R3257「基板ガラス表面のぬれ性試験方法」に準拠して、基材上の測定表面の3ヶ所にPGMEA滴を載せ、各PGMEA滴について測定した。液滴は2μL/滴であり、測定は20℃で行った。接触角は、3測定値の平均値(n=3)で示す。
(撥インク剤(C)の原料としての加水分解性シラン化合物)
加水分解性シラン化合物(c-1)に相当する、化合物(c-11):CF3(CF2)5CH2CH2Si(OCH3)3(TSL8257:商品名;モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製)
加水分解性シラン化合物(c-2)に相当する、化合物(c-21):C6H5NH(CH2)3Si(OCH3)3(KBM-573:商品名;信越化学工業社製)
加水分解性シラン化合物(c-3)に相当する、化合物(c-31):Si(OC2H5)4(コルコート社製)
加水分解性シラン化合物(c-4)に相当する、化合物(c-41):CH2=CHCOO(CH2)3Si(OCH3)3(東京化成工業社製)
(アルカリ可溶性樹脂(A))
CCR-1235:商品名;KAYARAD CCR-1235、日本化薬社製、クレゾールノボラック型エポキシ樹脂にカルボキシ基とエチレン性二重結合を導入した樹脂、酸価:60mgKOH/g、固形分:60質量%。
(光重合開始剤(B))
IR907:商品名;IRGACURE 907、BASF社製、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン。
EAB:4,4’-ビス(ジエチルアミノ)ベンゾフェノン(東京化成工業社製)。
PGME:プロピレングリコールモノメチルエーテル。
PGMEA:プロピレングリコールモノメチルエーテルアセテート。
(架橋剤(E))
A9530:商品名;NKエステル A-9530、新中村化学工業社製、ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートの混合品。
以下に示す式(71)で表される反応で、撥インク剤(C1)を合成した。
なお、式(71)で表される反応で得られる生成物は、実際は加水分解性基またはシラノール基が残存した部分加水分解縮合物であり、本例においては、得られた部分加水分解縮合物を撥インク剤(C1)として使用した。ただし、この生成物(部分加水分解縮合物)を化学式で表すことは困難であり、式(71)中、式(3-2)で表される平均組成式は、式(71)に表される反応によって製造された部分加水分解縮合物において、加水分解性基またはシラノール基の全てがシロキサン結合となったと仮定した場合の化学式である。
5分後、さらに、1.0質量%硝酸水溶液を1.12g滴下した。滴下終了後、さらに、室温で、5時間撹拌して、下式(71)で表される反応により、平均組成式(C1)で表される撥インク剤(C1)をPGME溶液(撥インク剤(C1)濃度:10質量%)として得た(工程(II))。なお、工程(II)は、反応をガスクロマトグラフィーでモニターし、原料としての各化合物が検出限界以下になった時点から、さらに、4時間反応を継続して合計5時間の撹拌とした。
撥インク剤(C1)のフッ素原子含有率および数平均分子量(Mn)を、撥インク剤(C1)の仕込み量組成(モル%)とともに表1に示す。なお、この仕込み量組成が、そのまま平均組成式(C1)における、それぞれ化合物(c-11)、カチオン化された化合物(c-21)、化合物(c-31)および化合物(c-41)に由来する縮合単位のモル%、m、n、kおよびsに相当するといえる。以下、撥インク剤(C2)~(C4)および(Cf1)についても同様である。
撹拌機を備えた50cm3の三口フラスコに、化合物(c-11)の0.5g、化合物(c-21)の0.41g、および化合物(c-31)の1.67gを入れて、撥インク剤(C2)の原料混合物を得た。次いで、該原料混合物にPGMEの9.0gを入れて、溶液(原料溶液)とした。
5分後、さらに、1.0質量%硝酸水溶液を1.44g滴下した。滴下終了後、さらに、5時間撹拌して、加水分解縮合反応により、平均組成式(C1)においてsが0である撥インク剤(C2)をPGME溶液(撥インク剤(C2)濃度:10質量%)として得た(工程(II))。なお、工程(II)は、反応をガスクロマトグラフィーでモニターし、原料としての各化合物が検出限界以下になった時点から、さらに、4時間反応を継続して合計5時間の撹拌とした。
撹拌機を備えた50cm3の三口フラスコに、化合物(c-11)の0.5g、および化合物(c-21)の1.14gを入れて、撥インク剤(C3)の原料混合物を得た。次いで、該原料混合物にPGMEの13.1gを入れて、溶液(原料溶液)とした。
5分後、さらに、1.0質量%硝酸水溶液を0.6g滴下した。滴下終了後、さらに、5時間撹拌して、加水分解縮合反応により、平均組成式(C1)においてkおよびsが0である撥インク剤(C3)をPGME溶液(撥インク剤(C3)濃度:10質量%)として得た(工程(II))。なお、工程(II)は、反応をガスクロマトグラフィーでモニターし、原料としての各化合物が検出限界以下になった時点から、さらに、4時間反応を継続して合計5時間の撹拌とした。
撹拌機を備えた50cm3の三口フラスコに、化合物(c-11)の0.5g、化合物(c-21)の0.34g、および化合物(c-41)の0.63gを入れて、撥インク剤(C4)の原料混合物を得た。次いで、該原料混合物にPGMEの10.0gを入れて、溶液(原料溶液)とした。
5分後、さらに、1.0質量%硝酸水溶液を0.54g滴下した。滴下終了後、さらに、5時間撹拌して、加水分解縮合反応により、平均組成式(C1)においてkが0である撥インク剤(C4)をPGME溶液(撥インク剤(C4)濃度:10質量%)として得た(工程(II))。なお、工程(II)は、反応をガスクロマトグラフィーでモニターし、原料としての各化合物が検出限界以下になった時点から、さらに、4時間反応を継続して合計5時間の撹拌とした。
上記例1において工程(I)で用いた65質量%硝酸水溶液の0.13gを、35質量%塩酸水溶液の0.14gに変更し、工程(II)で用いた1.0質量%硝酸水溶液の1.12gを1.0質量%塩酸水溶液の1.08gに変更した以外は同様にして、撥インク剤(C5)をPGME溶液(撥インク剤(C5)濃度:10質量%)として得た。
上記例1において溶媒を、PGMEからPGMEAに変更した以外は同様にして、撥インク剤(C6)をPGMEA溶液(撥インク剤(C6)濃度:10質量%)として得た。得られた、撥インク剤(C6)を10質量%で含有するPGMEA溶液を、(C6)液として、以下のネガ型感光性樹脂組成物の製造に用いた。
撹拌機を備えた50cm3の三口フラスコに、化合物(c-11)の0.5g、化合物(c-31)の1.1g、および化合物(c-41)の0.63gを入れて、撥インク剤(Cf1)の原料混合物を得た。次いで、該原料混合物にPGMEの8.5gを入れて、溶液(原料溶液)とした。
(ネガ型感光性樹脂組成物の製造)
上記例1で得られた(C1)液の0.26g(撥インク剤(C1)を固形分として0.026g含有し、残りは溶媒のPGME)、CCR-1235の4.0g(固形分は2.4g、残りは溶媒のEDGAC(ジエチレングリコールモノエチルエーテルアセテート):1.07g、ソルベントナフサ:0.53g)、IR907の0.29g、EABの0.19g、A9530の2.5g、PGMEの5.4g、2-プロパノールの1g、および水の1gを50cm3の撹拌用容器に入れ、30分間撹拌して、ネガ型感光性樹脂組成物1を製造した。
10cm四方のガラス基板を、エタノールで30秒間超音波洗浄し、次いで、5分間の紫外線/オゾン洗浄を行った。紫外線/オゾン洗浄には、紫外線/オゾン発生装置としてPL2001N-58(センエジニアリング社製)を使用した。なお、以下の全ての紫外線/オゾン処理についても、紫外線/オゾン発生装置としては本装置を使用した。
上記で得られたネガ型感光性樹脂組成物1、および硬化膜(隔壁)が形成されたガラス基板1について以下の評価を行った。結果を表2に示す。
<露光部分および未露光部分の撥インク性・親インク性評価>
上記工程により得られたガラス基板1の塗膜硬化物表面(露光部分:隔壁)のPGMEA接触角と、ガラス基板表面(現像により塗膜が除去された未露光部分。以下、単に「未露光部分」という。:ドット)の水接触角を上記の方法で測定した。それぞれ、46度、51度であった。
その後、得られた塗膜硬化物が形成されたガラス基板1の塗膜硬化物が形成された側の表面全体に、紫外線/オゾン照射処理を1分間行った。照射1分後、塗膜硬化物表面のPGMEA接触角、および未露光部分の水接触角を測定した。
<硬化膜の膜厚>
レーザー顕微鏡(キーエンス社製、装置名:VK-8500)を用いて測定した。
<ネガ型感光性樹脂組成物の貯蔵安定性>
ネガ型感光性樹脂組成物をガラス製スクリュー瓶にて、23℃(室温)で一か月保存した。一か月保存後、液の外観を観察して、以下の基準により貯蔵安定性を評価した。
○(良好):液の白濁、沈澱物なし、
×(不良):液の白濁、沈澱物あり。
(ネガ型感光性樹脂組成物の製造)
上記例8において、撥インク剤の溶液である(C1)液を、表2に示す液にそれぞれ変更した以外は、同様の方法で、ネガ型感光性樹脂組成物2~7を製造した。なお、例12においては、(C6)液の溶媒に合わせて、添加溶媒としてPGMEの替わりにPGMEAを用いた。
(硬化膜の製造)
次に、例8と同様の方法で、開孔パターン部を除く領域にネガ型感光性樹脂組成物2~7の硬化膜(隔壁)が形成されたガラス基板2~7を得た。
上記で得られたネガ型感光性樹脂組成物2~7について貯蔵安定性を、また、硬化膜(隔壁)が形成されたガラス基板2~7について膜厚、露光部分および未露光部分の撥インク性・親インク性の評価を、例8と同様の方法で行った。結果を表2に示す。
なお、2011年10月21日に出願された日本特許出願2011-232277号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (13)
- 下式(c-1)で表される加水分解性シラン化合物と下式(c-2)で表される加水分解性シラン化合物とを含む混合物の部分加水分解縮合物からなる撥インク剤の製造方法であって、
以下の工程(I)および工程(II)を含むことを特徴とする撥インク剤の製造方法。
工程(I):前記混合物に酸を含ませて、加水分解性シラン化合物(c-2)における窒素原子をプロトン化する工程、
工程(II):前記混合物に水と酸触媒とを含ませて、該混合物を加水分解および縮合反応させる工程。
式(c-1)において、Aはフッ素原子または下式(1)で表される基を示す。
-Q3-SiX3 3 …(1)
式(c-2)において、D、Eは、それぞれ独立して、水素原子、炭素原子に結合する水素原子が-NH2基に置換されていてもよい炭素原子数1~12の1価の有機基または下式(2)で表される基を示す。
-Q4-SiX4 (3-j)(RH2)j …(2)
式(c-1)、(c-2)中のA、D、E以外の記号、および式(1)および(2)中の記号は、以下の通りである。
Rf:炭素原子数2~15のエーテル性酸素原子を含んでいてもよいペルフルオロアルキレン基、
Q1、Q3:炭素原子数1~10のフッ素原子を含まない2価の有機基
RH1、RH2:炭素原子数1~6の炭化水素基、
Q2、Q4:それぞれ独立して、炭素原子数1~6のフッ素原子を含まない2価の有機基、
X1、X2、X3、X4:それぞれ独立して、加水分解性基、
p:1または2、
q:0または1であり、p+qが1または2となる数、
j:0または1。
ただし、X1~X4が式(c-1)および/または式(c-2)内に複数個存在する場合、またはE-N(D)-Q2が式(c-2)内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。 - 前記混合物中の加水分解性シラン化合物(c-1)および(c-2)の含有割合が、加水分解性シラン化合物(c-1)の1モルに対して、加水分解性シラン化合物(c-2)が0.1~9モルである請求項1に記載の撥インク剤の製造方法。
- 前記部分加水分解縮合物のフッ素原子の含有割合が10~55質量%である、請求項1または2に記載の撥インク剤の製造方法。
- 前記部分加水分解縮合物がシラノール基を含有し、ケイ素原子1個当たりのシラノール基が0.2~3.5個である、請求項1~3のいずれか一項に記載の撥インク剤の製造方法。
- 前記式(c-2)におけるDおよびEのいずれか一方が水素原子であって、他方がベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数6~12のフェニル基またはベンゼン環中の水素原子がアルキル基に置換されていてもよい炭素原子数7~12のフェニルアルキル基である、請求項1~4のいずれか一項に記載の撥インク剤の製造方法。
- 前記式(c-2)で表される加水分解性シラン化合物が、N-フェニル-3-アミノプロピルトリメトキシシランまたはN-フェニル-3-アミノプロピルトリエトキシシランである、請求項1~5のいずれか一項に記載の撥インク剤の製造方法。
- 前記混合物が、さらに下式(c-3)で表される加水分解性シラン化合物を含む、請求項1~6のいずれか一項に記載の撥インク剤の製造方法。
RH3 r-SiX5 (4-r) …(c-3)
式(c-3)中の記号は、以下の通りである。
RH3:炭素原子数1~6の炭化水素基、
X5:加水分解性基、
r:0、1または2である。
ただし、RH3およびX5が、前記加水分解性シラン化合物内に複数個存在する場合は、これらは互いに異なっていても、同一であってもよい。 - 請求項1~8のいずれか一項に記載の製造方法で得られた撥インク剤、アルカリ可溶性樹脂(A)、光重合開始剤(B)および溶媒(D)を含むネガ型感光性樹脂組成物。
- 前記撥インク剤の含有割合が、ネガ型感光性樹脂組成物における全固形分中、0.01~10質量%である請求項9に記載のネガ型感光性樹脂組成物。
- さらに、架橋剤(E)を含み、該架橋剤(E)が1分子中に2つ以上のエチレン性二重結合を有し、酸性基を有しない化合物である、請求項9または10に記載のネガ型感光性樹脂組成物。
- 基板表面を画素形成用の複数の区画に仕切る形に形成された隔壁であって、請求項9~11のいずれか一項に記載のネガ型感光性樹脂組成物の硬化膜からなることを特徴とする隔壁。
- 基板表面に複数の画素と隣接する画素間に位置する隔壁とを有する光学素子であって、前記隔壁が、請求項12に記載の隔壁で形成されていることを特徴とする光学素子。
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