WO2007132892A1

WO2007132892A1 - Positive photosensitive resin composition containing siloxane compound

Info

Publication number: WO2007132892A1
Application number: PCT/JP2007/060042
Authority: WO
Inventors: Tadashi Hatanaka
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2006-05-16
Filing date: 2007-05-16
Publication date: 2007-11-22
Also published as: KR20090008326A; CN101443705A; TWI411884B; TW200804984A; JP5071686B2; CN101443705B; KR101309252B1; JPWO2007132892A1

Abstract

[PROBLEMS] To provide: a photosensitive resin composition from which an image coating film having high pattern surface water repellency, etc. even after a treatment with a plasma or the like and having insulating properties can be easily formed with high accuracy at a high throughput rate; and a cured film which is obtained from such positive photosensitive resin composition and is suitable for use as a film material for various displays. [MEANS FOR SOLVING PROBLEMS] The positive photosensitive resin composition comprises: ingredient (A) which is an alkali-soluble resin having a functional group enabling the resin to undergo a heat-crosslinking reaction and further having a functional group for a heat-curing reaction and for film curing, and having a number-average molecular weight of 2,000-30,000; ingredient (B) which is a siloxane compound having a number-average molecular weight of 100-2,000; ingredient (C) which is a compound having two or more vinyl ether groups per molecule; ingredient (D) which is a compound having two or more blocked isocyanate groups per molecule; ingredient (E) which is a photo-acid generator; and a solvent (F).

Description

Specification

Positive photosensitive resin composition containing a siloxane compound

Technical field

[0001] The present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, a positive photosensitive resin composition having high water repellency on the pattern surface and capable of producing pores whose size can be controlled in the film, a cured film thereof, and various materials using the cured film It is about. Furthermore, the present invention uses a positive photosensitive resin composition capable of forming an image having high water repellency and high oil repellency on the surface even after treatment with UV-ozone, a cured film thereof, and the cured film. Also related to various materials. The positive photosensitive resin composition of the present invention is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light shielding material corresponding to an inkjet method, or a partition material. Background art

In general, display elements such as a thin film transistor (TFT) type liquid crystal display element and an organic EL (electroluminescent) element are provided with an electrode protective film, a flat film, an insulating film and the like on which a pattern is formed. As a material for forming these films, among the photosensitive resin compositions, the photosensitive resin composition is characterized in that it has a small number of steps for obtaining the required image and has sufficient flatness. Products have been widely used in the past.

[0003] In addition, in the process of manufacturing a display display element, a full-color display substrate manufacturing technique using an inkjet has been actively studied in recent years. For example, for the production of a power color filter in a liquid crystal display element, a section (hereinafter referred to as a bank) that prescribes a pixel pattern that has been preliminarily defined in comparison with the conventional printing method, electrodeposition method, dyeing method or pigment dispersion method. ) Is formed with a photosensitive resin layer that blocks light, and a color filter that drops ink droplets into an opening surrounded by the bank and a manufacturing method thereof (for example, Patent Document 1, Patent Document 2, and Patent Document) 3) is proposed. In addition, a method for manufacturing an organic EL display element in advance is also proposed (for example, see Patent Document 4) in which a bank is prepared in advance and an ink serving as a light emitting layer is dropped in the same manner. . [0004] However, when ink droplets surrounded by banks by the inkjet method are dropped, in order to prevent the ink droplets from overflowing to the adjacent pixels beyond the bank, the substrate is made to have ink affinity (hydrophilicity) The bank surface needs to have water repellency.

[0005] In order to achieve the above object, it is possible to impart hydrophilicity to the substrate and water repellency to the bank by continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment. It has been proposed that this can be done (for example, see Patent Document 5), but the process is complicated. Proposals have also been made in which fluorosurfactants and fluoropolymers are combined with photosensitive organic thin films (see, for example, Patent Document 6). It was difficult to say that it was practical because there were many points to consider.

[0006] In addition to water repellency, these films described above have excellent process resistance such as low dielectric constant, heat resistance, and solvent resistance, good adhesion to the substrate, and use. Various characteristics such as a wide process margin that can form an image under various process conditions according to the purpose, high sensitivity and transparency, and low film unevenness after development are required. Is done. Therefore, from the viewpoint of such required characteristics, conventionally, a resin containing a naphthoquinone diazide compound has been widely used as the photosensitive resin composition.

[0007] By the way, sensitivity is one of the particularly important characteristics of the required characteristics of such a photosensitive resin material. The improvement in sensitivity makes it possible to significantly reduce the production time in industrial production of display elements and so on. In the current situation where the demand for liquid crystal displays is increasing significantly, the sensitivity Is one of the most important properties required for this type of photosensitive resin material.

[0008] Thus, several developments have been made so far for the purpose of increasing the sensitivity of photosensitive resin materials. For example, a radiation-sensitive resin composition containing an alkali-soluble resin, at least one of a specific polyhydroxyl compound and a derivative thereof has been proposed (see, for example, Patent Document 7).

On the other hand, a chemically amplified resist has been developed as a photosensitive material with high sensitivity and high resolution. Conventional chemically amplified resists that have been developed as resists for semiconductors can be applied to light sources (KrF, ArF) having wavelengths shorter than those of i-line, and can form finer images. In the presence of a resist stripper at high temperatures Bonding part of protective group and thermal bridge part of ether bond are easily decomposed! It was almost impossible to use it as a permanent film with extremely low heat resistance and chemical resistance (see, for example, Patent Document 8). In addition, in order to enable thermosetting, an attempt to introduce a cross-linking system of epoxides and aminoplasts into a chemically amplified resist also causes the photoacid generator (PAG) force in the resist to be generated by exposure. Due to the influence, cross-linking of the exposed part proceeds and new problems such as disappearance of dissolution contrast with the unexposed part occur, so it was difficult to introduce such a cross-linking system into a chemically amplified resist. .

Patent Document 1: Japanese Patent Laid-Open No. 10-206627

Patent Document 2: Japanese Patent Laid-Open No. 11-326625

Patent Document 3: Japanese Patent Laid-Open No. 2000-187111

Patent Document 4: Japanese Patent Laid-Open No. 11 54270

Patent Document 5: Japanese Unexamined Patent Publication No. 2000-353594

Patent Document 6: Japanese Patent Laid-Open No. 10-197715

Patent Document 7: Japanese Patent Laid-Open No. 4-211255

Patent Document 8: US Patent No. 5075199

Disclosure of the invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and the problem to be solved is to form a patterned insulating film used for a liquid crystal display element, an organic EL display element or the like. A photosensitive resin composition suitable as a material for the substrate and the pixel spacing, specifically, the pattern surface has high water repellency and high oil repellency even after treatment with UV-ozone, etc. It is an object of the present invention to provide a positive photosensitive resin composition that can easily form a pattern with high throughput.

[0011] Further, the present invention is a cured film obtained by using such a positive photosensitive resin composition, and in the production of a substrate using an inkjet, ink droplets are formed on adjacent pixels beyond the bank. It is an object of the present invention to provide a cured film capable of preventing an overflow situation, and various elements and materials made using such a cured film.

Means for solving the problem [0012] As a result of intensive studies to solve the above problems, the present inventors have found the present invention.

That is, the present invention provides, as a first aspect, a positive photosensitive resin composition containing the following component (A), component (B), component (C), component (D), component (E), and solvent (F): object,

Component (A): Functional group for allowing a thermal crosslinking reaction with the compound of component (C), and a functional for curing a film with a thermosetting reaction with the compound of component (D) Alkali-soluble resin having a group and a number average molecular weight of 2,000 to 30,000

Component (B): Siloxane compound having a number average molecular weight of 100 to 2,000

Component (C): Compound having two or more vinyl ether groups in one molecule

Component (D): Compound having two or more block isocyanate groups in one molecule

(E) component: photoacid generator

(F) Solvent

As a second aspect, the functional group capable of performing the thermal crosslinking reaction is at least one selected from the group strength of a carboxyl group and a phenolic hydroxy group, and the functional group for film curing is a phenolic hydroxy group A positive photosensitive resin composition according to the first aspect, which is at least one selected from the group power of an amino group having a hydroxy group and active hydrogen other than

As a third aspect, the positive photosensitive resin composition according to the first aspect or the second aspect, wherein the component (B) is a fluorine-modified siloxane compound.

As a fourth aspect, the positive photosensitive film according to the first aspect or the second aspect, wherein the component (B) is a siloxane compound having a repeating unit represented by the formula (1). Fat composition.

[0013] [Chemical 1]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group or a phenyl group, and ρ represents a positive integer.) As a fifth aspect, the positive component according to the fourth aspect is characterized in that the component (B) is a siloxane compound in which R ¹ and / or R ² in the formula (1) represents a fluoroalkyl group. Photosensitive rosin composition.

As a sixth aspect, the positive photosensitive resin assembly according to any one of the first to fifth aspects, wherein the component (B) is a siloxane compound having no epoxy group. Adult.

As a seventh aspect, based on 100 parts by weight of the (Α) component, 0.1 to 30 parts by weight of the (Β) component, 1 to 80 parts by weight of the (C) component, 1 to 80 parts by weight of the (D) component And the positive photosensitive resin composition according to any one of the first to sixth aspects, comprising 0.5 to 80 parts by weight of the component (ii).

As an eighth aspect, in the positive photosensitive resin composition (i), which is a component-modified fluorine-modified siloxane compound, as the component (G), a fluorine-based alkali-soluble resin other than the component (i) is further added ( Ii) The positive photosensitive resin composition according to any one of the first aspect to the seventh aspect, containing 0.1 to 20 parts by mass based on 100 parts by mass of the component.

As a ninth aspect, as the component (i), the amine compound further contains 0.001 to 5 parts by mass of the component (ii) based on 100 parts by mass of the component (i). The positive photosensitive resin composition as described.

As a tenth aspect, according to any one of the first to ninth aspects, the surfactant is further contained in an amount of 0.2% by mass or less as the component (I) in the positive photosensitive resin composition. A positive photosensitive resin composition.

As a eleventh aspect, a cured film obtained using the positive photosensitive resin composition according to any one of the first aspect to the tenth aspect.

As a twelfth aspect, a partition material for an organic EL display element having the cured film described in the eleventh aspect. As a thirteenth aspect, a liquid crystal display device having the cured film according to the eleventh aspect.

As a fourteenth aspect, an array flattening film for a liquid crystal display comprising the cured film according to the eleventh aspect.

As a fifteenth aspect, an interlayer insulating film comprising the cured film described in the eleventh aspect.

The invention's effect [0015] The positive photosensitive resin composition of the present invention has high storage stability and high sensitivity, and forms a patterned insulating film used for liquid crystal display elements, organic EL display elements and the like. It is suitable as a material for the above and a pixel interval wall material.

[0016] The positive photosensitive resin composition of the present invention has a high water repellency on the pattern surface by using a siloxane compound as the component (B), and the water repellency is not greatly reduced even after ozone treatment. Insulating patterns can be easily formed with high accuracy and high throughput, and submicron holes can be formed inside the pattern.

[0017] In addition, the positive photosensitive resin composition of the present invention uses a fluorine-modified siloxane compound as the component (B), so that it has high water repellency and high repellency on the pattern surface even after prolonged ozone treatment. It is possible to easily form an insulating pattern that does not significantly reduce oiliness with high accuracy and high throughput.

[0018] Further, the cured film obtained using the positive photosensitive resin composition of the present invention has a state in which ink droplets overflow from the bank to the adjacent pixel in the production of a substrate using an ink jet. In addition, various element materials made using such a cured film can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0019] The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a siloxane compound, (C) a compound having a vinyl ether group, (D) A component having a block isocyanate group as a component, (E) a photoacid generator as a component, and (F) a solvent. This is a composition containing an amine compound (H) or a surfactant (I), which will be described later. Hereinafter, details of each component will be described.

[0020] <(A) component>

Component (A) is a functional group capable of undergoing a thermal crosslinking reaction with the compound having a vinyl ether group of component (C) in the structure of the resin, and a block isocyanate group of component (D). It has a functional group for film curing that can undergo a thermosetting reaction with a compound having a molecular weight, and has a polystyrene-equivalent number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 30, It is an alkali-soluble rosin that is 000. [0021] The functional group capable of undergoing a thermal crosslinking reaction reacts with the butyl ether group in the compound of the component (C) under an elevated temperature to cause thermal crosslinking with the compound of the component (C). None, a group capable of forming a resist film, the typical functional group of which is at least one selected from the group of carboxyl groups and phenolic hydroxy groups.

[0022] Further, the functional group for film curing is a thermally crosslinked product formed from the components (A) and (C) described above (in the exposed area, the crosslinked product is further dissociated. In the body), a group capable of undergoing a cross-linking reaction via an isocyanate group in which a block portion is dissociated with the compound of component (D) under a higher temperature, and can cure the film. Such an functional group is at least one selected from the group strength of hydroxy groups other than phenolic hydroxy groups and amino groups having active hydrogen. Here, the amino group having active hydrogen means a primary or secondary amino group capable of releasing hydrogen by reaction. Therefore, the amide group does not have active hydrogen, and therefore does not correspond to an amino group having active hydrogen.

[0023] The resin of component (A) is not particularly limited as long as it is an alkali-soluble resin having such a structure and the type of the main chain skeleton and side chain of the polymer constituting the resin.

[0024] However, the resin (A) has a number average molecular weight in the range of 2,000 to 30,000. If the number average molecular weight exceeds 30,000 and is excessively large, development residues are likely to occur, and the sensitivity is greatly reduced.On the other hand, if the number average molecular weight is less than 2,000 and the number average molecular weight is excessively small, At this time, a considerable amount of film loss occurs in the unexposed area, which may result in insufficient curing.

[0025] Examples of the alkali-soluble coagulant of component (A) include acrylic coagulants and polyhydroxystyrene coagulants. In particular, acrylic resin is more preferred because of its high transparency.

[0026] Further, in the present invention, a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can be used as a component (A) that has a strong alkali-soluble resin. wear. In this case, the alkali-soluble resin of component (A) may be a blend of a plurality of types of specific copolymers.

[0027] That is, the above specific copolymer has a monomer having a functional group for allowing a thermal crosslinking reaction, that is, at least one of a carboxyl group and a phenolic hydroxy group. Group power of monomers having a group of monomers having at least one of an appropriately selected monomer and a monomer having a functional group for film curing, that is, a hydroxyl group other than a phenolic hydroxy group and an amino group having an active hydrogen. Force is a copolymer formed as an essential structural unit with at least one monomer selected as appropriate.

The number average molecular weight is 000 to 30,000.

[0028] The above "monomer having at least one of carboxyl group and phenolic hydroxy group" includes a monomer having a carboxyl group, a monomer having a phenolic hydroxy group, and a carboxyl group and a phenolic hydroxy group. Monomers having both groups are included. These monomers are not limited to those having one carboxyl group or phenolic hydroxy group, and may have a plurality thereof.

[0029] The above-mentioned "monomer having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen" includes a monomer having a hydroxyl group other than a phenolic hydroxy group, and active hydrogen. A monomer having an amino group, and a monomer having both a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen. These monomers are not limited to those having one hydroxyl group other than a phenolic hydroxy group or one amino group having an active hydrogen, and may have a plurality.

[0030] Hereinafter, the ability to give specific examples of the above-mentioned monomers is not limited to these.

[0031] Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N -(Carboxyphenol) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

[0032] Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N (hydroxyphenol) acrylamide, N- (hydroxyphenol) methacrylamide, N- (hydroxyphenol) maleimide and the like. It is done.

[0033] Monomers having a hydroxy group other than a phenolic hydroxy group include, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-ataryl oxy-6-hydroxy norbornene 2, carboxy 6-latatone, 2-hydroxy And ethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy 6-hydroxynorbornene 2 carboxy 6-latathon, and the like.

Furthermore, examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

[0035] The specific copolymer also includes a monomer having a functional group for allowing a thermal crosslinking reaction and a monomer other than the monomer having a functional group for film curing (hereinafter referred to as other monomer). It may be a copolymer formed as a structural unit.

[0036] The other monomer specifically includes at least one of a monomer having at least one of a carboxyl group and a phenolic hydroxy group, and a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen. As long as it can be copolymerized with a monomer having one, it is not particularly limited as long as the properties of the component (A) are not impaired.

[0037] Specific examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

[0038] Examples of the acrylate compound include methyl acrylate, ethyl acetate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenol acrylate, 2, 2,2-trifluoroethyl butyl acrylate, tert butyl acrylate, cyclohexyl acrylate, isobutyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2 ethoxyethyl acrylate Tetrahydrofurfuryl acrylate, 3-methoxy butyl acrylate, 2-methyl 2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl 8-tricyclodecyl acrylate and 8 —Vegetable— Examples include 8-tricyclodecyl acrylate.

[0039] Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropylino methacrylate, benzino methacrylate, naphthino methacrylate, antholinole methacrylate, anthryl methyl methacrylate. Rate, phenol methacrylate, 2, 2, 2—trifluoroethyl methacrylate, tert butyl methacrylate, cyclohexyl methacrylate , Isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate 2-Methyl-2-adamantyl methacrylate, 2-propyl-1-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate Rate and the like.

[0040] Examples of the bur compound include methyl butyl ether, benzyl butyl ether, 2-hydroxyethyl butyl ether, ferro butyl ether, and propyl butyl ether.

[0041] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

[0042] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenolmaleimide, N-cyclohexylmaleimide, and the like.

[0043] The method for obtaining the specific copolymer used in the present invention is not particularly limited. For example, the group power of monomers having at least one of a carboxyl group and a phenolic hydroxy group is selected as appropriate. , At least one monomer appropriately selected from the group of monomers having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen, and optionally a monomer other than the above monomers, and optionally polymerization initiation It can be obtained by subjecting an agent or the like to a polymerization reaction in a solvent at a temperature of 50 to 110 ° C. In that case, the solvent used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include the solvents described in (F) Solvent described later.

[0044] The specific copolymer thus obtained is usually in a solution state in which the specific copolymer is dissolved in a solvent.

[0045] In addition, the solution of the specific copolymer obtained as described above is re-precipitated by adding it with stirring such as jetyl ether or water. The powder of the specific copolymer can be obtained by drying at normal temperature or heat under pressure or reduced pressure. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. One operation If it cannot be sufficiently purified, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be used as a solution by re-dissolving in, for example, a solvent (F) described later.

[0047] <Component (B)>

The component (B) of the present invention is a siloxane compound having a number average molecular weight of 100 to 2,000. The siloxane compound mentioned here refers to an organosiloxane compound, a compound in which a part thereof is substituted with a hydrogen atom or a hydroxy group, and a modified product thereof.

[0048] The siloxane compound as component (B) is a series of heat treatment steps performed in the process of forming a cured film (pattern forming film) from the positive photosensitive resin composition of the present invention, that is, ( In the heat treatment for cross-linking reaction between component A) and component (C), post-exposure heat treatment, and heat treatment for cross-linking reaction with component (D) It is preferable.

[0049] Examples of such siloxane compounds include linear siloxane compounds, branched siloxane compounds, cyclic siloxane compounds, and copolymers thereof. In addition, these siloxane compounds are modified with non-reactive groups such as alkoxy modification, polyether modification, fluorine modification, methyl styryl modification, higher fatty acid ester modification, hydrophilic special modification, and higher alkoxy modification. And siloxane compounds modified with reactive groups such as amino modification, epoxy modification, carboxy modification, carbinol modification, methacryl modification, mercapto modification, phenol modification and the like.

[0050] Specific examples thereof include linear chains such as polydimethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polymethylhydroxysiloxane, polymethylpropylsiloxane, polydiphenylsiloxane, and polymethylbutylsiloxane. Cyclic siloxanes such as cyclic siloxane or copolymers thereof, cyclic polydimethylsiloxane, cyclic polymethylphenylsiloxane, cyclic polymethylhydroxysiloxane, cyclic polymethylethylsiloxane, cyclic polymethylpropylsiloxane, cyclic polymethylbutylsiloxane Non-reactive group-modified siloxane such as alkoxy modified, polyether modified, fluorine modified, methyl styryl modified, higher fatty acid ester modified, hydrophilic special modified, higher alkoxy modified, etc. Examples thereof include reactive group-modified siloxanes such as mino modification, epoxy modification, carboxy modification, carbinol modification, methacryl modification, mercapto modification and phenol modification, and copolymers thereof.

[0051] The above siloxane compounds are readily available as commercial products. Specific examples thereof include L-45 (manufactured by Nippon Car Co., Ltd.), SH200, 510, 550, 710. 705, 11 07 (Toray Dow Co., Ltd.), X-22-22C, 3701E, 3710, 1821, 164S, 170DX, 176DX, 164A, 4952, KF96, 50, 54, 99, 351, Linear siloxane compounds such as 618, 910, 700, 6001, 6002, 8010, KR271, 282 (manufactured by Shin-Etsu Chemical Co., Ltd.), VS-7158 (manufactured by Nippon Car Co., Ltd.), ΒΥ11— Cyclic siloxane compounds such as 003 (manufactured by Toray Dow Cowing Co., Ltd.), L-77, 720, 7001, 7604, Y—7006, L—9 300, FZ—2101, 2110, 2130, 2161, 3704, 3711 3722, 3703, 3720, 37 36, 3705, 3760 (manufactured by Nippon Car Co., Ltd.), SF8427, 8428, 8413, 8417, SH19 3, 194, 190, 192, 556, 3746, 3749, 3771, 8400 , SRX280A, BY16— 03 6 One 848, One 828, One 853B, One 855B, One 839, One 845, One 752, One 750, One 838, — 150B, BX16— 854, —866, SF8421EG, SH28PA, SH30PA, ST89PA, ST103PA (Toray Dow Cowing ES1001N, 1023, X—22—161, —163, —169, —162, —164, KF—860, —101, —102, —6001, —6011, —6 015, one 8001, 1351, 412, 1910, — 905 (Shin-Etsu Chemical Co., Ltd.) and other modified siloxane compounds, FS1265 (Toray Dow Coung Co., Ltd.), FL-5, FL-10, X — Fluorine modified siloxane compounds such as 22—820, X—22—821, X—22—822, FL100 (manufactured by Shin-Etsu Chemical Co., Ltd.), FZ—2203, 2207, 2222 And a copolymer of polysiloxane and polyalkylene oxide, such as those manufactured by KK).

[0052] Among the above siloxane compounds, siloxane compounds having a repeating unit of the structure represented by the formula (1) are particularly preferable.

[0053] [Chemical 2]

[In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group, or a phenyl group, and p represents a positive integer.]

[0055] In the present invention, any siloxane compound having a repeating unit having the structure represented by the above formula (1) may be modified, unmodified, or misaligned.

[0056] Further, when the siloxane compound has an epoxy group, an acid component generated from a photoacid generator (E) described later at the time of exposure may react with the epoxy group. Preference is given to siloxane-free compounds with no groups!

[0057] Examples of siloxane compounds having no epoxy group include unmodified siloxane compounds, alkoxy modification, polyether modification, fluorine modification, methylstyryl modification, higher fatty acid ester modification, hydrophilic special modification, and higher alkoxy. Examples include siloxane compounds modified with non-reactive groups such as modification, and siloxane compounds modified with reactive groups such as amino modification, carboxy modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, etc. It is done.

[0058] Among the siloxane compounds of component (B), unmodified siloxane compounds and carbinol-modified siloxane compounds are easily compatible with component (A). Fluorine-modified siloxane compounds are preferred because they provide oil repellency.

Here, the fluorine-modified siloxane compound refers to the above-mentioned organosiloxane compound, a compound in which a part thereof is substituted with a hydrogen atom or a hydroxy group, and a compound in which those modified products are further modified with fluorine. .

[0059] Specifically, such a fluorine-modified siloxane compound is a siloxane compound in which R ¹ and / or R ² in the formula (1) is a fluoroalkyl group. Here, the introduction amount of the fluoroalkyl group is preferably 10 to 100%, more preferably 20 to 80%. When the amount of fluoroalkyl group introduced is small, the oil repellency is lowered, and when the amount of fluoroalkyl group introduced is too large, resistance to UV-ozone treatment may be lowered.

[0060] In the siloxane compound of component (B) used in the present invention, among the aforementioned compounds, a carbinol-modified siloxane compound or a fluorine-modified siloxane compound, and a siloxane modified only with fluorine Unmodified siloxanes, especially where compounds are more preferred A fluorine-modified siloxane compound obtained by fluorine-modifying a compound, that is, a compound other than fluorine-modified is preferred, and a siloxane compound is preferred.

[0061] The siloxane compound (B) used in the present invention is compatible with each component in the solution of the positive photosensitive resin composition of the present invention, in particular, the alkali-soluble copolymer (A). In addition to the good compatibility with the coalescence and the positive photosensitive resin composition having good stability, the solubility in the developer and the residual pattern which is a non-exposed area (light-shielded part) are also obtained. From the viewpoint of imparting water repellency and oil repellency on the upper surface of the turn, a compound having a number average molecular weight of 100 to 2,000 is preferred.

[0062] The siloxane compound as the component (B) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the alkali-soluble copolymer of the component (A). Particularly preferred is a ratio of 3 to 15 parts by mass.

When the amount of the component (B) compound used is less than the lower limit of the above range, the water repellency on the surface of the pattern may be insufficient. In addition, the size force S of the holes formed inside the pattern may be too small. In addition, when a fluorine-modified siloxane compound is used as component (B), the pattern surface not only has insufficient oil repellency in addition to water repellency, but also has insufficient UV-ozone treatment resistance. It may be.

On the other hand, if the amount of the component (B) compound used exceeds the upper limit of the above range, whitening or film unevenness may occur during coating film formation.

[0063] In the present invention, by appropriately selecting the type and amount of the siloxane compound as component (B), the size of pores generated in the resulting coating film and cured film is controlled. Is also possible.

[0064] <Component (C)>

Component (C) is a compound having two or more butyl ether groups in one molecule. This is the type and structure of any compound having two or more vinyl ether groups in one molecule that can be thermally cross-linked with the alkali-soluble resin (A) at a conventional pre-beta temperature. It is not particularly limited.

[0065] The compound of component (C) is obtained by photo-acidification after thermal crosslinking with the alkali-soluble resin of component (A). The acid generated by exposure in the presence of the generator is separated (decrosslinked) from the alkali-soluble resin of component (A), and then developed using an alkali developer, and the alkali-soluble solution of component (A) is removed. Both fats are removed. Therefore, as this type of compound, a vinyl ether compound generally used as a component of a bull ether type chemically amplified resist can be applied. The use of such a compound has an advantage that the shape of the formed film can be controlled by adjusting the thermal crosslinking density by changing the compounding amount of the compound.

[0066] As the compound of component (C), among the above-mentioned vinyl ether compounds, the compound power represented by formula (2) and formula (3) is developed especially in the exposed area! This is preferable.

[0067] [Chemical 3]

[In the formula, n is an integer of 2 to 10, k is an integer of 1 to 10, and R ³ represents an n-valent organic group.

[0069] [Chemical 4]

[0070] (wherein m represents an integer of 2 to 10)

[0071] n in the formula (2) is more preferably an integer of 2 to 4 as the force n representing the number of butyl ether groups in one molecule. In the formula (3), m represents the number of vinyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.

Specific examples of the compounds represented by the formulas (2) and (3) include bis (4 (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) dibule ether, Dipyric acid dibule ester, diethylene glycol dibutyl ether, tris (4-bi-dioxy) butyl trimellrate, bis (4- (bi-dioxy) butyl) terephthalate, bis (4- (bi-loxy) butyl iso) Examples thereof include phthalate and cyclohexane dimethanol dibutyl ether.

[0073] The compound of component (C) is used in a proportion of 1 to 80 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin of component (A). When the amount of the component (C) compound used is an excessive amount less than the lower limit of the above range, the reduction of the film in the unexposed area becomes significant and the pattern-like relief shape becomes poor. On the other hand, if the amount of the component (C) compound used exceeds the upper limit of the above range, the sensitivity of the film is greatly reduced, and residues between patterns are generated after development.

[0074] <(D) component>

Component (D) is a compound having two or more block isocyanate groups in one molecule. This is because, for example, a conventional post-beta temperature is applied to a film composed of the alkali-soluble resin of component (A) that has been thermally crosslinked with or further decrosslinked with the compound of component (C). As long as it is a compound having two or more block isocyanate groups in one molecule that can be thermally cured by the method, its type and structure are not particularly limited.

[0075] The compound of component (D) has two or more blocked isocyanate groups in which one or more isocyanate groups (-NCO) are blocked by an appropriate protecting group, and is heated at a high temperature during thermal curing. Exposure to the functional group (e.g., phenolic hydroxy group) for thermal curing in the alkali-soluble resin of component (A) via the generated isocyanate group. A hydroxyl group other than the group and an amino group having an active hydrogen), a crosslinking reaction proceeds between, for example, the formula (4)

[0076] [Chemical formula 5] Equation (4)

[In the formula, R ⁴ represents an organic group in the block part] Two or more groups in one molecule (this group may be the same or different! /) Well, there are compounds that have). [0078] The compound of the component (D) having two or more blocked isocyanate groups in one molecule can be obtained by, for example, allowing a suitable blocking agent to act on a compound having two or more isocyanate groups in one molecule. You can get it from Tsujiko.

[0079] The compounds having two or more isocyanate groups in one molecule include, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethyl hexane methacrylate. Examples thereof include diisocyanate and the like, or dimers, trimers thereof, or a reaction product of these with diols, triols, diamines, and triamines.

[0080] Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol. , Phenol, o--trophenol, p-chlorophenol, m- or p-taresol and other phenols, ε-force prolatata and other ratatams, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, Examples include oximes such as cyclohexanone oxime, acetophenone oxime, benzophenone oxime, pyrazoles such as pyrazole, 3,5-dimethylbiazole, and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol. .

[0081] In the compound of component (D), at higher temperatures such as the post-beta temperature, the block portion is thermally desorbed and the crosslinking reaction proceeds via the isocyanate group. In order to prevent crosslinking by isocyanate groups from proceeding at lower temperatures, the component (D) has a temperature at which the thermal dissociation of the block portion is considerably higher than the pre-beta temperature, for example, 120 ° C to 230 ° C. Particularly preferred as the compound.

[0082] Examples of the compound of the component (D) include the following specific examples.

[0083] [Chemical 6]

[0084] In the formula, the isocyanate compound is derived from isophorone diisocyanate.

Examples of such a compound in which the compound of component (D) is more preferable than the point of heat resistance and coating properties include the following. R in the following formula represents an organic group.

[0085] [Chemical 7]

S008

[6 ^] [800]

Z 0090 / L00ZdT / 13d 03 Z68 Dynamic 0Z OAV

In the present invention, the compound of component (D) may be used alone or in combination of two or more. [0089] The compound of component (D) is used in a proportion of 1 to 80 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin of component (A). If the amount of the component (D) compound used is too small below the lower limit of the above range, thermal curing will be insufficient and a satisfactory cured film will not be obtained, while the amount of the compound (D) component used will be If the amount exceeds the upper limit of the above range, the development is insufficient and a development residue is generated.

[0090] <(E) component>

The component (E) is a photoacid generator (PAG). This is a substance that generates acids (sulfonic acids, carboxylic acids, etc.) directly or indirectly by irradiation of light used for exposure. If it has such properties, its type and The structure is not particularly limited.

[0091] The photoacid generator of component (E) includes, for example, diazomethane compounds, form salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin. Examples include tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without particular limitation. In the present invention, the photoacid generator of component (E) may be used alone or in combination of two or more.

[0092] Specific examples of the photoacid generator include the following. However, these compounds are examples of a very large number of applicable photoacid generators, and are not limited thereto.

[0093] [Chemical 10] Formula (5)

Formula (6)

Formula (7)

Formula (8)

Formula (9)

Diphenylo chloride, Diphenylo trifnoroleolomethane sulphonate, Diphenyloyl mesylate, Diphenyloyl tosylate, Difenoredo nyumb mouthmid, Zihu- Rhododonium tetrafluoroborate, diphenyl-hexafluoroantimonate, diphenyl-dioxyhexafluoroarsenate, bis (p-tert-butylphenol) Phosphate, bis (p-tert-butylphenol) iodine mesylate, bis (p-tert-butylphenol) monodontosylate, bis (p-tert-butylphenol) Umtrifluoromethane sulfonate, bis (p-tert-butylphenyl) odonium tetrafluoroborate, Bis (p-tert-butylphenol) jordon chloride, bis (p-chlorophenol) odo-um chloride, bis (p-chlorophenol) jordon tetrafluoroborate, Triphenylsulfuric chloride, triphenylsulfuric acid amide, triphenylsulfo-mutrifluoromethanesulfonate, tri (p-methoxyphenyl) sulfotetrafluoroborate, tri (p-methoxyphenol) L) sulfo-hexafluorophosphonate, tri (ρ-ethoxyphenyl) snorephonium tetrafunoleroborate, triphenyl-norephospho-mum chloride, triphenylphospho-mubromide, tri (p-methoxyphenol) -Lu) phosphonium tetrafluoroborate, tri (ρ-methoxyphenol) phosphomuhexafluorophosphonate, tri (ρ— Ethoxyphenol) phosphonium tetrafunoleroborate,

[Chemical 11]

[Zl ^ [9600]

Z 0090 / L00ZdT / 13d 93 Z68 Dynamic OAV

[0098] [Chemical 14]

[3ΐ ^] [6600]

Hi 0090 women Zdf / e :) d 83 Z68 motion 0ί OAV

[0100] [Chemical 16]

18]

3) 1 ⁾

[0103] The photoacid generator of component (E) is 0.5 to 80 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of the alkali-soluble resin of component (A). used. When the amount of the photoacid generator used as the component (E) is too small below the lower limit of the above range, the (C) component of the compound (C) which has been thermally cross-linked during exposure is exposed to alkali-soluble soot. The dissociation from the fat does not proceed sufficiently, making it difficult to obtain a desired pattern-like relief, while the amount of the photoacid generator used as the component (E) is excessive in excess of the upper limit of the above range. Thus, the storage stability of the positive photosensitive resin composition becomes inferior.

[0104] Ku (F) Solvent>

The positive photosensitive resin composition of the present invention contains (A) component, (B) component, (C) component, (D) component and (E) component, which are dissolved in (F) solvent. It is in the state.

[0105] Therefore, the (F) solvent used in the present invention dissolves the components (A) to (E) and dissolves the components (G) to (I), which will be added later if desired. There are no particular limitations on the type and structure of the solvent as long as it has such a dissolving ability.

[0106] Examples of such a solvent (F) include ethylene glycol monomethyl ether, ethylenic glycolenomonotinoreethenore, methinoreserosonolebacetate, ethinorecerosonolevacetate, diethyleneglycolenomonomono Methylenol ether, diethyleneglycolenomonoethylenate ether, propylene glycol, propyleneglycololemonomethinoleether, propyleneglycololemonomethinoatenoacetate, propyleneglycololepropenoatenoate acetate, toluene, xylene, methyl ether Tyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolatathone, 2-hydroxyethyl ethionate, 2-hydroxyethyl 2-methylpropionate, ethoxyethyl ethoxylate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, acetic acid Ethyl, butyl acetate, ethyl lactate, butyl lactate, Ν, ジメチル dimethylformamide, Ν, ジメチル dimethylacetamide, Ν-methylpyrrolidone and the like.

[0107] These solvents may be used alone or in combinations of two or more.

[0108] Among these (F) solvents, propylene glycol monomethyl ether, propylene glycol Lumonomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactyl, butyl lactate, etc. Preferable from the viewpoint of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0109] Component (G)>

In the positive photosensitive resin composition of the present invention, an alkali-soluble resin other than the component (A) is further blended as the component (G) as long as the effects of the present invention are not impaired. be able to. The blending of the component (G) is preferred in that the positive photosensitive resin composition of the present invention can easily suppress development defects during development and can impart various functional properties. Examples of such component (G) include acrylic resin and hydroxystyrene resin other than component (A), phenol novolac resin, polyamide resin, polyimide precursor, polyimide resin, and these Examples of the alkali-soluble resin include fluorine-based alkali-soluble resins having an organic group substituted with a fluorine atom in the side chain.

[0110] In the other alkali-soluble resin (G) used in the present invention, when the component (B) is a fluorine-modified siloxane compound, the fluorine-based alkali-soluble resin is employed. It is desirable to do.

[0111] In the fluorine-based alkali-soluble resin, the organic group substituted with a fluorine atom is not particularly limited, but a perfluoroalkyl group is particularly preferable.

[0112] As the fluorinated alkali-soluble resin, an acrylic polymer obtained by copolymerizing a monomer having an organic group substituted with a fluorine atom in combination with another monomer (hereinafter simply referred to as "fluorinated copolymer"). U, prefer U).

[0113] Specific examples of the monomer having an organic group substituted with a fluorine atom include pentafluoropropyl acrylate, heptafluorobutyl acrylate, pentadecafluorooctyl acrylate, heptadecafluorodecyl acrylate. , 2- (nonafluorobutyl) ethyl acrylate, 2— (perfluorodecyl) ethyl acrylate, 2- (perfluoro hexyl) ethenorea tantalate, trifanoleo cetylare acrylate , Pentafunoropropyl metatalylate, heptafluorobutyl metatalylate, pentadecafluorooctyl methacrylate, heptadecafluorodecyl methacrylate, 2- (nonafluorobutyl) ethyl Examples include rumetatalylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, trifluoroethyl methacrylate and the like.

Of these, monomers having a perfluoroalkyl group, such as 2- (perfluorodecyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, trifluoroethyl acrylate, 2- (Perfluorodecyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, trifluoroethyl methacrylate and the like are more preferable.

[0115] The above-mentioned fluorine-based copolymer can be obtained by the same method as the method for obtaining the specific copolymer of the component (A). In this case, the monomer component constituting the specific copolymer and the fluorine-containing copolymer are obtained. It would be good if copolymerized with other monomers.

[0116] In the present invention, the other alkali-soluble coagulum of component (G) can usually be contained in an amount of 1 to 90 parts by mass based on 100 parts by mass of component (A).

However, when a fluorine-modified siloxane compound is used as the component (B) and a fluorinated alkali-soluble resin is used as the component (G), the effects of the present invention may be impaired within the above-mentioned range. Therefore, the content of the fluorine-based alkali-soluble coagulant is, for example, 0.1 to 20 parts by mass based on 100 parts by mass of the component (A), and optionally 0.5 to 15 parts by mass, Further, it is preferably 1 to 10 parts by mass. If the amount of the fluorinated alkali-soluble resin used is too small below the lower limit of the above range, poor development may occur during development, while the amount of the fluorinated alkali-soluble resin used is within the above range. If the amount exceeds the upper limit, UV-ozone resistance may decrease.

[0117] <(H) component>

Component (H) is an amine compound. The positive photosensitive resin composition of the present invention may further contain an amine compound for the purpose of enhancing the storage stability, as long as the effects of the present invention are not impaired.

[0118] The amine compound of component (H) is not particularly limited. For example, triethanolamine, tributanolamine, triisopropanolamine, trimethylamine, triethylamine, trinormalpropylamine, triamine. Isopropylamine, tri-normal butylamine, tri-tert-butylamine, trioctylamine, triphenylamine and diazabicyclooctane And tertiary amines such as pyridine and 4-dimethylaminopyridine, and primary amines such as benzylamine and normal butylamine, and jetamine and dinormal butylamine. Second-class amines such as

[0119] The amine compound of component (H) can be used singly or in combination of two or more.

[0120] When the amine compound is used, the content thereof is, for example, 0.001 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A), and optionally 0. 005 to 1 part by mass, and preferably 0.01 to 0.5 part by mass. If the amount of the amine compound used as the component (H) is too small below the lower limit of the above range, the storage stability of the positive photosensitive resin composition cannot be sufficiently increased, while (H When the amount of the component amin compound used exceeds the upper limit of the above range, the sensitivity of the positive photosensitive resin composition may be lowered.

[0121] <(1) ingredient>

Component (I) is a surfactant. The positive photosensitive resin composition of the present invention may further contain a surfactant for the purpose of improving the coating property as long as the effects of the present invention are not impaired.

[0122] The surfactant of component (I) is not particularly limited, and examples thereof include fluorine surfactants, silicone surfactants, and nonionic surfactants. As this type of surfactant, commercially available products such as those manufactured by Sumitomo 3EM Co., Ltd., Dainippon Ink & Chemicals, Inc., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they are readily available. Specific examples include F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3EM) Asahi Guard A G710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC10 6 (manufactured by Asahi Glass Co., Ltd.) and the like.

[0123] The surfactant of component (I) can be used singly or in combination of two or more.

[0124] When a surfactant is used, its content is 100% positive photosensitive resin composition. The amount is usually 0.2% by mass or less, preferably 0.1% by mass or less. Even if the amount of the surfactant (I) used is set to an amount exceeding 0.2% by mass, the effect of improving the coating property becomes dull and not economical.

[0125] <Other additives>

Furthermore, the positive photosensitive resin composition of the present invention can be used, if necessary, as long as the effects of the present invention are not impaired. Adhesion aids such as rheology modifiers and silane coupling agents, facial materials, and dyes. In addition, a storage stabilizer, an antifoaming agent, or a solubility promoter such as a polyhydric phenol or a polycarboxylic acid can be contained.

[0126] <Positive photosensitive resin composition>

The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a siloxane compound, (C) a compound having a vinyl ether group, (D) A compound having a lock isocyanate group, (E) a photoacid generator and (F) a solvent, and (G) an alkali-soluble resin and (H) an amination as desired. It is a composition that can further contain one or more of a compound, a surfactant of component (I), and other additives.

[0127] Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows.

[1]: Based on 100 parts by mass of component (A), 0.1 to 30 parts by mass of component (B), 1 to 80 parts by mass of component (C), 1 to 80 parts by mass of component (D) And a positive photosensitive resin composition containing 0.5 to 80 parts by mass of the component (E) and these components dissolved in the solvent (F).

[2]: In the composition of [1] above (provided that the component (B) is a fluorine-modified siloxane compound), the component (G) (fluorine-based alkali-soluble resin) ) In the range of 0.1 to 20 parts by mass based on 100 parts by mass of component (A).

[3]: A positive photosensitive resin containing 0.001 to 5 parts by mass of component (H) in the composition according to [1] or [2] above based on 100 parts by mass of component (A). Composition.

[4]: A positive photosensitive resin composition further containing 0.2% by mass or less of component (I) in the positive photosensitive resin composition of [1], [2] or [3] above. .

[0128] The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. For example, 1 to 80% by mass In For example, 5 to 60% by mass, or 10 to 50% by mass. Here, the solid content refers to a component obtained by removing (F) the solvent from all components of the positive photosensitive resin composition.

[0129] The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited. Examples of the preparation method include (A) component (alkali-soluble resin) in (F) solvent. Dissolve, and in this solution (B) component (siloxane compound), (C) component (compound having two or more vinyl ether groups in one molecule), (D) component (two in one molecule) (Compound having the above block isocyanate group), (E) component (photoacid generator) and (I) component (surfactant) are mixed at a predetermined ratio to make a uniform solution, or this In an appropriate stage of the preparation method, there may be mentioned a method in which (H) component (amine compound), (G) component (alkali-soluble resin) and Z or other additives are further added and mixed as necessary. It is done.

[0130] In preparing the positive photosensitive resin composition of the present invention, (F) a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In the same way as above, add (B) component, (C) component, (D) component, etc. to the solution of component), and add (F) additional solvent for the purpose of concentration adjustment. May be. At this time, the solvent (F) used in the process of forming the specific copolymer and the solvent (F) used for concentration adjustment at the time of preparing the positive photosensitive resin composition may be the same. However, it may be different.

[0131] Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 µm.

[0132] Coating and cured film>

The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon Z-dioxide-silicon-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, or a glass substrate. , Quartz substrate, ITO substrate, etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-drying with a hot plate or oven, etc. Thus, a coating film can be formed. Thereafter, the coating film is heated to form a positive photosensitive resin film.

[0133] Conditions for this heat treatment include, for example, a temperature of 70 ° C to 160 ° C, and a time of 0.3 to 60 minutes. A heating temperature and a heating time appropriately selected from the above range are employed. The heating temperature and heating time are preferably 80 ° C to 140 ° C and 0.5 to 10 minutes.

[0134] The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 m, for example, 0.2 to 10 m. For example, te from 0.2 to 5 μm.

[0135] Then, the formed positive photosensitive resin film is subjected to an alkali treatment by crosslinking the compound having a butyl ether group as the component (C) to the resin as the component (A) by the heat treatment at the time of formation. A film hardly soluble in the developer. In this case, when the temperature of the heat treatment is lower than the lower limit of the above temperature range, thermal crosslinking is insufficient, and film loss may occur in the unexposed area. In addition, when the temperature of the heat treatment exceeds the upper limit of the above temperature range and is too high, the once formed thermal cross-linked part may be cut again, and the film may be reduced in the unexposed part.

[0136] The positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F laser light using a mask having a predetermined pattern.

2

The exposed portion of the film is soluble in an alkaline developer by the action of the acid generated from the photoacid generator (PAG) of the component (E) contained in the positive photosensitive resin film. It becomes.

[0137] Next, post-exposure heating (PEB) is performed on the positive photosensitive resin film. As heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 80 ° C. to 150 ° C. and a time of 0.3 to 60 minutes are employed.

[0138] Thereafter, development is performed using an alkaline developer. As a result, the exposed portion of the positive photosensitive resin film is removed, and a pattern-like relief is formed.

Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. Examples include alkaline aqueous solutions such as aqueous solutions of quaternary ammonium hydroxides such as urea and choline, and aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.

[0140] Among the above, a 0.1 to 2.38% by mass aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer, and the positive photosensitive resin composition of the present invention. In this case, the alkaline developer can be used to develop well without causing problems such as swelling.

[0141] Further, as a developing method, a V-deviation, such as a liquid piling method, a dating method, or a rocking dipping method, can also be used. The development time is usually 15 to 180 seconds.

[0142] After development, the positive photosensitive resin film is washed with running water for, for example, 20 to 90 seconds, and then air-dried using compressed air or compressed nitrogen or by spinning. The top moisture is removed and a patterned film is obtained.

[0143] Subsequently, the pattern forming film is subjected to post-beta for thermosetting, specifically, by using a hot plate, an oven, or the like, heat resistance, A film having excellent transparency, flatness, low water absorption, chemical resistance, etc. and having a good pattern can be obtained.

[0144] The post beta is generally 5 to 30 minutes on the hot plate and 3 in the oven at the heating temperature selected at a medium temperature in the range of 140 ° C to 250 ° C. If treated for 0 to 90 minutes, the dredging method is used.

[0145] Thus, with such a post-beta, a target cured film having a good pattern can be obtained.

[0146] As described above, the positive photosensitive resin composition of the present invention has a sufficiently high sensitivity and a coating film having a fine pattern in which the film loss in the unexposed area is very small during the image formation. Can be formed.

The cured film has a structure having submicron pores in the film.

[0147] The characteristics of this cured film are excellent in heat resistance and solvent resistance, high water repellency on the film surface, and when a fluorine-modified siloxane compound is used as the component (B). It also has high oil repellency, and can suppress a decrease in water repellency and oil repellency after oxygen plasma treatment.

[0148] Therefore, for example, applications such as an organic EL pixel fractionation bank, an array flat film of a TFT type liquid crystal element, various films in a liquid crystal or an organic EL display, such as an interlayer insulating film, a protective film, Suitable for applications such as insulating films.

Example [0149] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[0150] [Abbreviations used in Examples]

The meanings of the abbreviations used in the following examples are as follows.

MAA: Methacrylic acid

MMA: Methyl metatalylate

HEMA: 2 Hydroxyethyl methacrylate

CHMI: N cyclohexylmaleimide

PFMA: Perfluoroalkyl metatalylate

TMSSMA: Methacrylic acid 3- [Tris (trimethylsiloxy) silyl] propyl ester AIBN: Azobisisobutyronitrile

PGMEA: Propylene glycol monomethyl ether acetate

MAK: methinoreaminoreketone (2-heptanone)

PAG1: Oxime sulfonate photoacid generator: Chinoku 'Specialty Chemicals Co., Ltd.

CGI1397 (Product name)

PVE1: 1,4-cyclohexanedimethanol dibule ether

NCOl: Compound having two block isocyanate groups in one molecule: VE STAGON (registered trademark) B 1065 (trade name) manufactured by Degussa AG

R30: Dai Nippon Ink Chemical Co., Ltd. Mega Fuck R—30 (trade name)

PDMS1: Polydimethylsiloxane, hydroxy-terminated number average molecular weight (hereinafter referred to as Mn)

: 550

PDMS2: Polydimethylsiloxane-co-polydiphenylsiloxane Hydroxy terminal Mn: l, 000

PDMS3: Polydimethylsiloxane Mn: 580

PDMS4: Polydimethylsiloxane bishydroxyalkyl terminal Mn: 5, 600 PDMS5: Polydimethylsiloxane dibule terminal Mn: 250, 000

PDMS6: Polydimethylsiloxane hydroxy-terminated Mn: 8,000

PDFS 1: 50% fluorine-modified polydimethylsiloxane Mn: l, 000 PDFS2: 100% fluorine-modified polydimethylsiloxane Mn: l, 000

[0151] [Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and weight average molecular weight of the specific copolymer obtained in accordance with the following synthesis example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF8034) manufactured by JASCO Corporation and the elution solvent tetrahydrofuran was flowed. The measurement was conducted under the condition that elution was carried out in a column (column temperature 40 ° C) at lmlZ minutes. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

[0152] <Synthesis Example 1>

MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, and MMA 23.7 g are used as monomer components constituting the specific copolymer, and AIBN 5 g is used as a radical polymerization initiator, and these are PGMEA 200 g. The solution of component (A) (specific copolymer) that is Mn4, 100, Mw7, 600 (specific copolymer concentration: 27.5% by mass) ) (P1)

[0153] Synthesis Example 2

MAA 8.0 g, CHMI 12.0 g, HEMA 12.0 g, PFMA 8. Og were used as monomer components constituting the specific copolymer, and AIBN 0.88 g was used as a radical polymerization initiator. Solvent PGMEA 95. A solution of (A) component (specific copolymer) (specific copolymer concentration) of Mn6, 400 and MwlO, 500 by polymerization reaction at a temperature of 60 ° C to 100 ° C in 4g. 30.0% by mass). (P2)

In accordance with the composition shown in the following Table 1, (B), (C), (D), (E) and (F) solvent, and (I) component are added to the solution of component (A). By mixing at a ratio and stirring at room temperature for 3 hours to obtain a uniform solution, positive photosensitive resin compositions of Examples and Comparative Examples were prepared.

[0155] [Table 1] (A) fi¾ »© 赚 (B) component (C) component (D) component (E) component (F) solvent (I) component

(g) (g) (g) (g) (g) (g) (g)

PI PDMS1 PVE1 NCOl PAGl PGMEA

Example 1

15 0. 21 0. 62 0. 41 0. 21 5. 75

PI PDMS1 PVE1 NCOl PAGl PGMEA

Example 2

15 0. 41 0. 62 0. 41 0. 21 5. 75

PI PDMS2 PVE1 NCOl PAGl PGMEA

Example 3

15 0. 21 0. 62 0. 41 0. 21 5. 75

PI PDMS2 PVE1 NCOl PAGl PGMEA

Example 4

15 0. 41 0. 62 0. 41 0. 21 5. 75

PI PDMS3 PVE1 NCOl PAGl PGMEA

Example 5-15 0. 21 0. 62 0. 41 0. 21 5. 75

PI PD S3 PVE1 NCOl PAGl PGMEA

Example 6

15 0. 41 0. 62 0. 41 0. 21 5. 75

PI PDMS4 PVE1 NCOl PAGl PGMEA

Comparative Example 1

15 0. 21 0. 62 0. 41 0. 21 5. 75

PI PD S4 PVE1 NCOl PAGl PGMEA

Comparative Example 2

15 0. 41 0. 62 0. 41 0. 21 5. 75

PI PDMS5 PVE1 NCOl PAGl PGMEA

Comparative Example 3

15 0. 21 0. 62 0. 41 0. 21 5. 75

PI PDMS6 PVE1 NCOl PAGl PGMEA

Comparative Example 4

15 0. 21 0. 62 0. 41 0. 21 5. 75

PI PVE1 NCOl PAGl PGMEA R30 Comparative Example 5 ―

15 0. 62 0. 41 0. 21 5. 75 0.0028

P1 / P2 PVE1 NCOl PAGl PGMEA R30 Comparative Example 6

14.3 / 0.7 0. 62 0. 41 0. 21 5. 75 0.0028

[0156] Regarding the obtained compositions of Examples 1 to 6 and Comparative Examples 1 to 6

Each was evaluated for solution stability, sensitivity, film loss (in unexposed areas), contact angle, pores, MEA resistance and heat resistance with acrylic resin.

[0157] [Solution stability evaluation]

Regarding the positive photosensitive resin composition obtained above, after the preparation of this composition, the transparent and homogeneously dissolved composition is indicated as “O”, and the white turbid or insoluble matter is precipitated as “X”.

[0158] [Evaluation of sensitivity]

After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-beta is applied on a hot plate for 120 seconds at a temperature of 110 ° C. 2.

The coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The UV intensity at 365nm is 5.

Irradiate with 5mWZcm ² UV light for a certain period of time, then hot play at 110 ° C for 120 seconds Post-exposure heating (PEB) was performed on the substrate. Thereafter, the film was developed by immersing it in an aqueous solution of 0.4% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, followed by washing with ultrapure water for 20 seconds. The lowest exposure amount (mjZcm ² ) at which the undissolved portion remained in the exposed area was taken as the sensitivity.

[0159] [Evaluation of film loss]

The coating film was formed. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[0160] [Evaluation of contact angle]

After coating the positive photosensitive resin composition on a quartz substrate using a spin coater, pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was heated at a temperature of 230 ° C. for 30 minutes to perform post-beta and form a cured film having a thickness of 1.9 m. The contact angle of water and methylene iodide on the cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd.

[0161] [Evaluation of plasma treatment resistance]

The coating film was formed. This coating film was heated at 230 ° C. for 30 minutes to perform post-beta, and a cured film having a thickness of 1.9 m was formed. This coating film was cleaned with ozone for 5 minutes using UV-312 manufactured by Technovision Co., Ltd. The contact angle of water on the ozone-cleaned membrane was measured using the Drop Master manufactured by Kyowa Interface Science Co., Ltd. in the same manner as in the above [Evaluation of Contact Angle].

[0162] [Evaluation of pores]

The coating film was formed. By heating this coating film at 230 ° C for 30 minutes, And a cured film having a thickness of 1.9 m was formed. The cross section of the coating film was checked for the presence or absence of pores and the pore diameter using a scanning electron microscope (hereinafter referred to as SEM). The notation “ku 100” in Table 2 below means that there are holes with a diameter of less than lOOnm.

[0163] [MEA resistance assessment]

A positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-betaged on a hot plate for 120 seconds at a temperature of 120 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, post-baking was performed by heating at a temperature of 230 ° C for 30 minutes to form a cured film having a thickness of 1.9. This coating film was immersed in monoethanolamine heated to a temperature of 60 ° C. for 20 minutes, and then washed with pure water for 20 seconds. Then, after drying for 10 minutes on a hot plate at a temperature of 180 ° C., the film thickness was measured. The film thickness after post-beta and MEA treatment were marked with MEA resistance x when there was no change in film thickness after drying, and X when X was reduced.

[0164] [Evaluation of heat resistance]

In the above [Evaluation of MEA resistance], a cured film having a film thickness of 1.9 / zm was formed in the same manner except that the substrate was changed to a quartz substrate-powered silicon wafer. The cured film was scraped to make a sample, and DTA-TG measurement was performed. The temperature at which the mass of the sample decreased by 5% by mass was designated as “5% mass decrease temperature”.

[0165] [Evaluation results]

The results of the above evaluation are shown in Table 2 below.

[0166] [Table 2] Contact angle 0 5% Mass Solution Film reduction Pore diameter MEA

Reduced temperature stability after Dallas' ma treatment, m) Water ^ H ₂ I ₂ (nm) resistance

Water (° C) Example 1 ○ 25 None 100 ° 74 ° 92. <100 ○ 305 Example 2 ○ 25 None 101 ° 76 ° 94 ° <500 O 305 Example 3 ○ 32 None 100 ° 76. 93 ° <50 ○ 305 Example 4 ○ 32 None 103 ° 78 ° 93 ° <150 ○ 305 Example 5 ○ 27 None 101 ° 75 ° 94 ° <10 ○ 305 Example 6 ○ 27 None 103 ° 77 ° 94 ° <20 ○ 305 Comparative Example 1 X-― ― ― ― One Comparative Example 2 X One ― ― ―-Comparative Example 3 X ― ― ― ―-One-Comparative Example 4 X ― One ― ― ― Comparative Example 5 ○ 27 None 72 ° 42 ° 43 ° No hole O 305 Comparison 6 ○ 27 None 94 ° 73 ° 67 ° No hole ○ 305

* “No film loss” means that no film loss is observed in the measurement results, that is, there is no film loss that is actually a problem.

In Examples 1 to 6, a uniform solution without gelation or separation was obtained after preparation of the positive photosensitive resin composition.

In addition, all of the positive photosensitive resin compositions of Examples 1 to 6 have high sensitivity, no film loss that is actually a problem in the unexposed area is observed, and the surface is high both before and after the plasma treatment. The film had water repellency, and pores were formed in the film.

[0168] On the other hand, Comparative Examples 1 to 4 had a low solution stability of the positive photosensitive resin composition and were unable to obtain a uniform solution.

In addition, in the positive photosensitive resin composition of Comparative Example 5, no vacancies were formed in the film with low water repellency on the film surface.

Furthermore, the positive photosensitive resin composition of Comparative Example 6 was strong in that the surface water repellency was high but the UV plasma resistance was low, and no voids were formed in the film.

[0169] Synthesis Example 3

MAA 15.5 g, CHMI 35.3 g, HEMA 25.5 g, and MMA 23.7 g are used as monomer components constituting the specific copolymer, and AIBN 5 g is used as a radical polymerization initiator, and these are used as solvent PGMEA 185 g. A solution of component (A) (specific copolymer) (Mn4, 100, Mw7, 600) by polymerizing at a temperature of 60 ° C to 100 ° C. (Constant copolymer concentration: 35.0% by mass). (P3)

[0170] <Synthesis Example 4>

MAA 7.5 g, MMA 20. Og, H EMA 10. Og, and PFMA 12.5 g are used as monomer components constituting the specific copolymer, and AIBN 1.59 g is used as a radical polymerization initiator. A solution of component (A) (specific copolymer) that is Mnl2, 600, Mw20, 300 (specific copolymer concentration) by polymerizing at a temperature of 60 ° C to 100 ° C in 154.7 g of solvent PGMEA : 25.0% by mass). (P4)

[Synthesis Example 5]

MAA 3. Og, MMA 3.0 g, HE MA 4. Og, TMSSMA 9. Og were used as monomer components constituting the specific copolymer, and AIBN 0.96 g was used as a radical polymerization initiator. Of the component (A) (specific copolymer) of Mn8, 200, Mwl2, 900 (specific copolymer) by polymerization reaction at a temperature of 60 ° C to 100 ° C in 59.9 g of solvent PGMEA Combined concentration: 25.0 mass%) was obtained. (P5)

According to the composition shown in Table 3 below, the solution of component (A) is mixed with component (B), component (C), component (D), component (E) and solvent (F), in Example 7. Furthermore, by mixing a fluorine-based alkali-soluble resin as a component (G) at a predetermined ratio and stirring at room temperature for 3 hours to obtain a uniform solution, the positive photosensitive resin of each Example and each Comparative Example A composition was prepared.

[0173] [Table 3]

(A) component (B) component (C) component (D) component (E) component (F) solvent (G) component solution (g) (g) (g) (g) (g) (g) (g )

P3 PDFS1 PVE1 NCOl PAG1 MAK P4 Example 7

11. 8 0. 21 0. 62 0. 41 0. 21 0. 83

P3 PDFS 1 PVE1 NCOl PAG1 MAK

Example 8

11. 8 0. 21 0. 62 0. 41 0. 21 5. 33

P3 PDFS 1 PVE1 NCOl PAG1 MAK

Example 9

11. 8 0. 41 0. 62 0. 41 0. 21 6. 03

P3 PDFS2 PVE1 NCOl PAG1 MAK

Example 10

11. 8 0. 62 0. 41 0. 21 6. 03

P3 PDMS6 PVE1 NCOl PAG1 PGMEA-Comparative Example 7 o

11. 8 0. 21 0. 62 0. 41 0. 21 5. 33

P3 PDMS6 PVE1 NCOl PAG1 PGMEA

Comparative Example 8

11. 8 0. 31 0. 41 0. 21 5. 63

P3 / P4 P dVE1 NCOl PAG1 PGMEA

Comparative Example 9

5. 9/8. 2 0. 62 0. 41 0. 21 2. 54

P3 PVE1 NCOl PAG1 PGMEA

Comparative Example 10

11. 8 0. 62 0. 41 0. 21 4. 50

P3 / P5 PVE1 NCOl PAG1 PGMEA

Comparative Example 11

5. 9/8. 2 0. 62 0. 41 0. 21 2. 54

[0174] For the compositions of Examples 7 to 10 and Comparative Examples 7 to 11, solution stability with acrylic resin, sensitivity, film reduction (in the unexposed area), and contact angle, respectively. The plasma treatment resistance and heat resistance were evaluated. n

[0175] [Solution stability evaluation]

[0176] [Evaluation of sensitivity]

After coating the positive photosensitive resin composition on a silicon wafer using a spin coater, pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C. to form a coating film with a film thickness of 2.5 μπιι. The film thickness was measured using F20 manufactured by FILMETRICS. The coating light intensity at 365nm by Canon KK ultraviolet irradiation apparatus PLA-600FA in irradiates a predetermined time ultraviolet rays 5. 5mWZcm ^2, next! Post-exposure heating (PEB) was performed on a hot plate for 120 seconds at a temperature of 110 ° C. After developing for 60 seconds by immersing in 0.4% by weight aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), it was washed with ultrapure water 2 (^ The sensitivity was defined as the lowest exposure amount (mj / cm ² ) at which no undissolved portion remained in the exposed area. [0177] [Evaluation of film loss]

The coating film was formed. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Next, by measuring the thickness of this film, the degree of film reduction in the unexposed area due to development was evaluated. The film thickness in this evaluation is made by FILMETRICS

Measured using F20.

[0178] [Evaluation of contact angle]

After coating the positive photosensitive resin composition on a quartz substrate using a spin coater, pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was heated at a temperature of 230 ° C. for 30 minutes to perform post-beta and form a cured film having a thickness of 1.9 m. The contact angles of water and dodecylbenzene (DB) on the cured film were measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd.

[0179] [Evaluation of resistance to plasma (ozone) treatment]

After coating the positive photosensitive resin composition on a quartz substrate using a spin coater, pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C to form a coating film with a thickness of 2.5 μm. . This coating film was heated at 230 ° C. for 30 minutes to perform post-beta to form a cured film having a thickness of 1.9 μm. This coating film was subjected to ozone cleaning for 15 minutes using UV-312 manufactured by Technovision. The contact angle of water on the ozone-cleaned membrane was measured by the same method as in the above [Evaluation of contact angle] using Drop Master manufactured by Kyowa Interface Science Co., Ltd.

The contact angle measurement results of the cured film formed from the positive photosensitive resin composition of Example 7 before and after the ozone cleaning treatment (5 minutes, 10 minutes, 15 minutes) are shown. [Fig. 1] (Water) and [Fig. 2] (Dodecylbenzene).

[0180] [Evaluation of heat resistance]

In the above [Evaluation of Contact Angle], a cured film having a film thickness of 1.9 / zm was formed in the same manner except that the substrate was changed to a quartz substrate-powered silicon wafer. The cured film was scraped to make a sample, and DTA-TG measurement was performed. The temperature at which the mass of the sample decreased by 5 mass% was defined as the 5% mass decrease temperature. [0181] [Result of evaluation]

The above evaluation results are shown in Table 4 below.

[0182] [Table 4]

* “No film loss” means that no film loss is observed in the measurement result, that is, there is no film loss that is actually a problem.

[0183] In Examples 7 to 10, a uniform solution without gelation or separation was obtained after the preparation of the positive photosensitive resin composition.

In addition, all of Examples 7 to 10 were highly sensitive, and no film reduction that was actually a problem was observed in the unexposed areas, indicating good heat resistance. And even after UV ozone treatment, the decrease in high water repellency and high oil repellency of the cured film surface was suppressed.

[0184] In addition, the measurement results of the contact angle before and after the ozone cleaning treatment of the cured film, which is the positive photosensitive resin composition of Example 7, showed that both water (Fig. 1) and dodecylbenzene (Fig. 2) were ozone cleaned. The contact angle did not decrease over time, but rather the contact angle tended to increase as the cleaning process progressed.

[0185] On the other hand, Comparative Example 7 and Comparative Example 8 have low solution stability of the positive photosensitive resin composition, and cannot obtain a uniform solution, and cannot obtain a coating film and a cured film. Katsutsu.

In Comparative Example 9, the surface water repellency and oil repellency were high, but the ozone treatment resistance was low. Comparative Example 10 was low in water repellency, oil repellency and ozone treatment resistance.

Comparative Example 11 had high surface water repellency but poor ozone treatment resistance and low oil repellency. Industrial applicability

[0186] The positive photosensitive resin composition according to the present invention forms a hardened film such as a protective film, a flattened film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. In particular, it is suitable as an insulating material for TFT type liquid crystal elements, protective film for color filters, array flat film, uneven film under reflective film for reflective displays, insulating film for organic EL elements, etc. It is also suitable as a material for forming the film, and also suitable as various electronic materials such as a microlens material.

Brief Description of Drawings

[0187] [Fig. 1] Contact angle of water before and after ozone cleaning treatment (5 minutes, 10 minutes, 15 minutes) of the cured film formed from the positive photosensitive resin composition of Example 7 Θ (° FIG.

[Fig. 2] Contact angle Θ (°) of dodecylbenzene before and after ozone cleaning treatment (5 minutes, 10 minutes, 15 minutes) of the cured film formed from the positive photosensitive resin composition of Example 7 FIG.

Claims

The scope of the claims

[1] A positive photosensitive resin composition containing the following component (A), component (B), component (C), component (D), component (E) and solvent (F).

Component (C): Compound having two or more vinyl ether groups in one molecule

(E) component: photoacid generator

(F) Solvent

[2] Since the thermal crosslinking reaction can be performed, the functional group is at least one selected from the group strength of a carboxyl group and a phenolic hydroxy group, and the functional group for film curing is other than a phenolic hydroxy group. 2. The positive photosensitive resin composition according to claim 1, which is at least one selected from the group of an amino group having a hydroxy group and active hydrogen.

[3] The positive photosensitive resin composition according to claim 1 or 2, wherein the component (B) is a fluorine-modified siloxane compound.

[4] The positive photosensitive resin composition according to claim 1 or 2, wherein the component (B) is a siloxane compound having a repeating unit represented by the formula (1).

[Chemical 1]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group or a phenyl group, and p represents a positive integer.)

The positive photosensitive resin composition according to claim 4, wherein the component (B) is a siloxane compound in which R ¹ and Z or R ² in the formula (1) represents a fluoroalkyl group. object

[6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the component (B) is a siloxane compound having no epoxy group. .

[7] Based on 100 parts by weight of component (A), 0.1 to 30 parts by weight of component (B), 1 to 80 parts by weight of component (C), 1 to 80 parts by weight of component (D), and The positive photosensitive resin composition according to any one of Claims 1 to 6, comprising 0.5 to 80 parts by mass of the component (E).

[8] In a positive photosensitive resin composition in which the component (B) is a fluorine-modified siloxane compound!

The component (G) further contains 0.1 to 20 parts by mass of a fluorine-based alkali-soluble resin other than the component (A) based on 100 parts by mass of the component (A). The positive photosensitive resin composition according to any one of the above.

[9] As component (H), an amine compound is further added based on 100 parts by mass of component (A).

The positive photosensitive resin composition according to any one of claims 1 to 8, which is contained in 5 parts by mass.

[10] The component according to any one of [1] to [9], wherein a surfactant is further contained as a component (I) in an amount of 0.2% by mass or less in the positive photosensitive resin composition. Positive photosensitive resin composition.

[11] A cured film obtained by using the positive photosensitive resin composition according to any one of claims 1 to 10.

[12] A partition material for an organic EL display device having the cured film according to claim 11.

[13] A liquid crystal display device having the cured film according to claim 11.

[14] An array flat film for a liquid crystal display comprising the cured film according to [11].

[15] An interlayer insulating film comprising the cured film according to [11].