JP5803350B2 - Method for producing photosensitive resin composition and method for producing organic film - Google Patents

Description

  The present invention relates to heat resistance, optical characteristics, such as an insulating material for electronic parts and a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, and a high refractive index film and a high dielectric constant film in a liquid crystal display element. The present invention relates to a photosensitive composition used for forming a film having a pattern in which electrical characteristics are required, an organic film formed thereby, and an electronic component having this film.

  Conventionally, the above-described film is formed by depositing an inorganic material on a substrate by a vapor deposition method such as chemical vapor deposition (CVD) or a sputtering method to form an inorganic film, and further forming a pattern thereon using a photoresist or the like. The inorganic film on which the pattern was formed was obtained by wet etching or plasma etching using the pattern as a mask.

  However, in the case of pattern formation by etching of the above inorganic film, expensive vacuum equipment is required and an etching process through a photoresist is required, which increases costs, and also provides safety and a recent environment. Due to the growing interest in the problem, environmental impact has become a problem. As a result, there is an interest in the vacuum removal process in the above-mentioned fields.

  Thus, for example, Patent Documents 1 to 3 are known as a coating type and photosensitive composition. In these techniques, a photosensitive material is obtained by dispersing inorganic fine particles in an alkali-soluble acrylic polymer and adding a polymerizable monomer. However, the obtained pattern size has a resolution of about several hundred μm, it is difficult to obtain a fine pattern of several μm, and since it contains an acrylic polymer, it does not have high temperature resistance, and heat is generated during high-temperature baking at 300 ° C. There existed a problem in which decomposition gas was generated and transparency was lowered due to thermal deterioration.

  In addition, the required characteristics vary depending on the application, and it is necessary to customize the optical characteristics and electrical characteristics of the composition. In the above technique, the amount of inorganic fine particles added is limited, and it is difficult to arbitrarily add inorganic fine particles to customize various characteristics in the film.

JP 2002-365794 A JP 2002-36596 A JP 2003-288813 A

  The present invention has high heat resistance, can be used to form a high-definition relief pattern on a substrate, and is excellent in the optical characteristics and electrical characteristics of the organic film to be formed, and has excellent customizability. Provided are a composition, an organic film comprising the composition, and an electronic component having the organic film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has extremely high heat resistance, enables high-definition pattern formation, and at the same time, can achieve both good optical characteristics and electrical characteristics. Finding a composition and finding that the properties of the composition are excellent even when the amount of fine particles added is increased, and that the composition is highly customizable. A composition capable of solving the above-mentioned problems at a high level is completed. It came to.

  The present inventor combined the alkali-soluble inorganic fine particles (A), the compound (B) having a polymerizable double bond, and the photopolymerization initiator (C) generated by irradiating with ultraviolet rays, thereby developing with an alkaline aqueous solution. Thus, it was found that a negative pattern having a diameter of several μm can be obtained, and at the same time, good heat resistance, optical characteristics, and electrical characteristics are exhibited.

  That is, the present inventor can obtain a film that can achieve both high sensitivity and fine pattern formation with the photosensitive composition containing the above (A) to (C). The present invention was completed on the basis of these findings, showing various properties such as properties, high transparency, high refractive index, and high dielectric constant.

  The present invention provides the following photosensitive composition, an organic film produced using the same, and an electronic component including these.

[1] A photosensitive composition comprising alkali-soluble inorganic fine particles (A), a compound (B) having a polymerizable double bond, and a photopolymerization initiator (C).

[2] The photosensitive composition according to [1], wherein the inorganic element of the alkali-soluble inorganic fine particles (A) includes an element belonging to Groups 1 to 15 of the periodic table.

[3] The inorganic elements of the alkali-soluble inorganic fine particles (A) are Si, Ti, Zr, Sr, Al, Ba, Ca, Fe, Hf, In, La, Mg, Mo, Nb, Pb, Sb, Sn, Ta The photosensitive composition as described in [1] or [2] containing 1 or more chosen from the group which consists of Zn, W, Y, P, Na, K, Ge, Ga, and B.

[4] The content of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A) is 500 parts by weight or less, according to any one of [1] to [3]. Photosensitive composition.

[5] The photosensitive composition according to [4], wherein the content of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A) is 10 to 500 parts by weight.

[6] The photosensitive composition according to any one of [1] to [5], wherein the compound (B) having a polymerizable double bond is a polyfunctional acrylate.

[7] The photosensitive composition according to any one of [1] to [6], wherein the photopolymerization initiator (C) is a compound that generates radicals by ultraviolet rays.

[8] An organic film obtained by curing the coating film of the photosensitive composition according to any one of [1] to [7] by light irradiation to the coating film.

[9] The organic film according to [8], wherein a pattern is formed by light irradiation and development through a mask.

[10] An electronic component having the organic film according to [8] or [9].

Since the photosensitive composition of the present invention contains alkali-soluble inorganic fine particles (A), it has extremely high heat resistance after curing and can be used to form a high-definition relief pattern on a substrate. it can. Further, since the photosensitive composition of the present invention has inorganic solubility in the inorganic fine particles, the photosensitive composition in the photosensitive composition as compared with the conventional photosensitive composition in which the inorganic fine particles are dispersed in the monomer of the alkali-soluble polymer. The content of inorganic fine particles can be further increased. Therefore, the characteristics of the organic film such as optical characteristics and electrical characteristics due to the inorganic fine particles can be widely adjusted by the content of the alkali-soluble inorganic fine particles (A), and the organic film having such characteristics and the organic film are provided. Can be used for electronic components.

<1 photosensitive composition>
The photosensitive composition of the present invention contains alkali-soluble inorganic fine particles (A), a compound (B) having a polymerizable double bond, and a photopolymerization initiator (C). The photosensitive composition of the present invention can be used as a negative photosensitive composition.

  The photosensitive composition of the present invention comprises 20 to 300 parts by weight of a compound (B) having a polymerizable double bond and 100% by weight of alkali-soluble inorganic fine particles (A) and a photopolymerization initiator (C). It is preferable to contain 0.5-10 weight part from a viewpoint of improving the transparency of the organic film obtained from the photosensitive composition of this invention, heat resistance, and developability.

  In particular, in the photosensitive composition of the present invention, it is preferable that the content of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A) is 200 parts by weight or less. From the viewpoint of enhancing the properties.

<1-1-1 Alkali-soluble inorganic fine particles>
The alkali-soluble inorganic fine particles (A) are inorganic fine particles having alkali solubility. For example, the alkali-soluble inorganic fine particles (A) are inorganic fine particles having a group having a hydrolyzability by alkali on the surface by a reaction between the inorganic fine particles and a surface treatment agent such as a metal alkoxide. It is solubilized in alkali by hydrolysis under alkaline conditions.

  The alkali-soluble inorganic fine particles (A) have a thickness of 0.01 to 100 μm formed by applying a solution containing the fine particles to a substrate by spin coating and heating at 100 ° C. for 2 minutes. For example, when the film is immersed in an aqueous solution of 0.4% by weight of tetramethylammonium hydroxide at about 25 ° C. for 5 minutes and rinsed with pure water, it is dissolved in alkali so that the film does not remain.

  Metal oxide particles can be used as the inorganic fine particles. Examples of the inorganic fine particles include titania, zirconia, alumina, barium titanate, strontium titanate, silica, zinc oxide, and composite fine particles thereof. One kind or two or more kinds of inorganic fine particles may be used.

  As the inorganic fine particles, inorganic fine particles having a primary particle size within a range in which desired characteristics are expressed in the organic film of the present invention can be used. Inorganic fine particles are preferable from the viewpoint of increasing the light transmittance of the organic film as the primary particle size is small, but having a certain size is preferable from the viewpoint of preventing aggregation in the solvent. From such a viewpoint, the primary particle diameter of the inorganic fine particles is preferably 500 nm or less, more preferably 10 to 300 nm, further preferably 10 to 100 nm, and more preferably 10 to 50 nm. Even more preferred. In the present invention, the primary particle size of the inorganic fine particles and the primary particle size of the alkali-soluble inorganic fine particles (A) are substantially the same, and the primary particle size of the inorganic fine particles is the same as that of the alkali-soluble inorganic fine particles (A). Mean primary particle size.

  The primary particle size of the inorganic fine particles can be obtained by a normal method, for example, by image analysis of a photographed image using a TEM (transmission electron microscope).

  Preferred inorganic elements used for the inorganic fine particles are elements of Groups 1 to 15 of the periodic table. More preferable inorganic elements include, for example, Si, Ti, Zr, Sr, Al, Ba, Ca, Fe, Hf, In, La, Mg, Mo, Nb, Pb, Sb, Sn, Ta, Zn, W, Y , P, Na, K, Ge, Ga, and B.

<1-1-2 Preparation Method of Alkali-Soluble Inorganic Fine Particles (A)>
The method for preparing the alkali-soluble inorganic fine particles (A) is not particularly limited, but examples are shown below.
Commercially available inorganic fine particle dispersions can be used as the inorganic fine particles. For example, a dispersion of inorganic fine particles having a primary particle size of about several tens of nanometers to several hundreds of μm is reacted with a metal alkoxide, silicon alkoxide, or silane coupling agent, and the surface of the inorganic fine particles in the dispersion is modified. To be used after imparting solubility.

  Specific examples of commercially available inorganic fine particle dispersions include RTS MIBK (titania fine particle dispersion, manufactured by CI Kasei Co., Ltd.), RTTGBL (titania fine particle dispersion, manufactured by CI Chemical Co., Ltd.), ZRMMIBK (zirconia fine particle dispersion, CI eye). Kasei Co., Ltd.), ZRBL (zirconia fine particle dispersion, CI Kasei Co., Ltd.), ALMIBK (alumina fine particle dispersion, CI Kasei Co., Ltd.), CSC1 (titania composite metal oxide fine particle dispersion, catalyst chemical conversion) Industrial Co., Ltd.), PL-2L-PGME (silica fine particle dispersion, manufactured by Fuso Chemical Industry Co., Ltd.), PMA-ST (silica fine particle dispersion, manufactured by Nissan Chemical Industries, Ltd.).

  The surface modification of the inorganic fine particles can be performed using a surface treatment agent that reacts with the inorganic fine particles to form a hydrolyzable group on the surface of the inorganic fine particles. The surface treatment agent may be one kind or two or more kinds. Examples of such surface treatment agents include metal alkoxides, silicon alkoxides, and silane coupling agents. The surface treatment agent is preferably two or more types from the viewpoint of improving alkali solubility.

  As the surface treatment agent, a known compound that binds to the surface of the inorganic fine particles by dehydration condensation can be used. Examples of the metal alkoxide include titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium-tert-butoxide, zirconium tetraethoxide, and zirconium. Examples include tetrapropoxide, zirconium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetraisobutoxide, aluminum ethoxide, aluminum isopropoxide, aluminum-sec-butoxide, and aluminum-tert-butoxide.

Examples of the silicon alkoxide include tris (3- (trimethoxysilyl) propyl) isocyanurate, tetrabutyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetraethyl orthosilicate, tetramethyl orthosilicate, and 3-bromopropyl). Trimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, triethoxyvinylsilane, trimethoxyvinylsilane, benzyltriethoxysilane, cyclohexyltrimethoxysilane, dodecyltrimethoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxy Silane, Octyltriethoxysilane, Octadecyltriethoxysilane, Octadecyltrimethoxysilane, Pentilt Lito Sisilane, triethoxyphenylsilane, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, triethoxymethylsilane, [bicyclo [2.2.1] hept-5-en-2-yl] triethoxysilane, triethoxy- 1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, triethoxyethylsilane, triethoxyfluorosilane, triethoxysilane, trimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, diethoxydimethyl Silane, dimethoxydimethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylphenylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, dimethoxydiphenylsilane, diethoxymethylsilane, dimethoxy Methylsilane, diethoxy methyl vinyl silane, dimethoxy methyl vinyl silane, Jimetokishiji -p- tolylsilane, ethoxyethyl triethylsilane, methoxy trimethylsilane, and include trimethyl silane.

  Examples of the silane coupling agent include 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-glycidyloxypropyldimethoxymethylsilane, 3 -Mercaptopropyldimethoxymethylsilane, diethoxy (3-glycidyloxypropyl) methylsilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, chloromethyltriethoxysilane, 1- [3- (tri Methoxysilyl) propyl] urea, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysila 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- Examples include aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl chloride, and 3-ureidopropyltriethoxysilane. .

  In the surface treatment reaction described above, the total amount of these surface treatment agents is preferably 10 to 300 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the inorganic fine particles. It is more preferable to use ~ 150 parts by weight.

  Furthermore, the surface treatment of the inorganic fine particles is preferably performed in the presence of an acid anhydride. The acid anhydride modifies the surface of the alkali-soluble inorganic fine particles (A), suppresses the change over time of the alkali-soluble inorganic fine particles (A), and the solubility of the alkali-soluble inorganic fine particles (A) in the alkali. It is preferable from the viewpoint of enhancing. One or two or more acid anhydrides may be used. Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, 1,2,3,4-tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2 , 3-dicarboxylic acid anhydride, and bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride. In the surface treatment reaction, the acid anhydride is preferably used in a total amount of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the inorganic fine particles. It is more preferable to use 10 parts by weight.

  In the above reaction in the preparation of the alkali-soluble inorganic fine particles (A), a solvent may be further used. The solvent is preferably a solvent that does not impair the dispersion stability of the inorganic fine particle dispersion and that dissolves the metal alkoxide, silicon alkoxide, and silane coupling agent to be surface-modified. The solvent may be a single type or a mixture of two or more types. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

  Various characteristics such as optical characteristics and electrical characteristics of the organic film of the present invention can be adjusted by the type and content of the alkali-soluble inorganic fine particles (A). For example, the content of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A) is 500 parts by weight or less, satisfying various characteristics generally required for the organic film. It is preferable from a viewpoint to make it, and it is more preferable that it is 10-500 weight part.

  The optical properties and electrical properties of the organic film of the present invention can be adjusted by the kind and content of inorganic fine particles used for the alkali-soluble inorganic fine particles (A). For example, the refractive index and relative dielectric constant of the organic film can be adjusted by the type and content of the alkali-soluble inorganic fine particles (A). For example, the inorganic fine particles used for the alkali-soluble inorganic fine particles (A) are titania, zirconia, alumina, barium titanate, strontium titanate, zinc oxide, or composite fine particles thereof, and 100 parts by weight of the alkali-soluble inorganic fine particles (A). The content of the compound (B) having a polymerizable double bond with respect to is preferably 10 to 100 parts by weight from the viewpoint of increasing one or both of the refractive index and relative dielectric constant of the organic film.

<1-2 Compound (B) having a polymerizable double bond>
The compound (B) having a polymerizable double bond has one or more polymerizable double bonds. The compound (B) having a polymerizable double bond may be a single compound or a mixture of two or more compounds. The polymerizable double bond is a double bond provided for polymerization by the photopolymerization initiator (C) when the coating film of the photosensitive composition of the present invention is irradiated with light, and a double bond between carbons. It may be a double bond between elements other than carbon, or a double bond between carbon and other elements. Examples of the group containing a polymerizable double bond include alkenyl, alkynyl, and a group containing any of these groups, and specifically include acrylic, methacrylic, maleimide, vinyl, vinyl ether, vinyl ketone, styryl. And monovalent groups having a maleic anhydride structure.

Specific examples of the compound (B) having a polymerizable double bond include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin Modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropy Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) acrylate, epichlorohydrin modified dipropylene glycol di (Meth) acrylate, epichlorohydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylol Propane tri (meth) acrylate, propylene oxide modification Trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol acrylate methacrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol Tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate , Hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalate neo Pentyl glycol di (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) Acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, bis [(meth) acryloxyneope Cylglycol] adipate, 2,2-bis [4-((meth) acryloxy) phenyl] propane, (meth) acrylate, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane, 2 , 2-bis [4-((meth) acryloxy) phenyl] methane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] methane, 2,2-bis [4-((meth)) Acryloxy) phenyl] sulfone, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] sulfone, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol (meth) acrylate, Dicyclopentanyl diacrylate, ethylene oxide-modified phosphate di (meth) acrylate, ethylene oxide-modified phosphate tri ( ) Acrylate, caprolactone, ethylene oxide modified phosphoric acid di (meth) acrylate, caprolactone, ethylene oxide modified phosphoric acid tri (meth) acrylate, epichlorohydrin modified di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglu Serol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone modified tris [(meth) acryloxyethyl] isocyanurate, (meth) acrylic Isocyanurate, urethane (meth) acrylate, and the like.

  In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate”. Similarly, “(meth) acryloxy” means “acryloxy” or “methacryloxy”, “(meth) acryl” means “acryl” or “methacryl”, and “(meth) acryloyl” means “ It means “acryloyl” or “methacryloyl”.

  The compound (B) having a polymerizable double bond preferably has one or more (meth) acryloyl groups. The compound (B) having a polymerizable double bond more preferably has two or more polymerizable double bonds, more preferably two or more (meth) acryloyl groups, and is a polyfunctional acrylate. It is particularly preferred.

<1-3 Photopolymerization initiator (C)>
The photopolymerization initiator (C) has a property of initiating polymerization of a polymerizable double bond of the compound (B) having a polymerizable double bond by light irradiation. Various compounds are known for such a photopolymerization initiator (C), and the photopolymerization initiator (C) is preferably a compound that generates radicals by ultraviolet rays. The photopolymerization initiator (C) may be a single compound or a mixture of two or more compounds.

Examples of the photopolymerization initiator (C) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACU) E 907; trade name, manufactured by Ciba Japan Co., Ltd., hereinafter referred to as “IRGACURE 907”), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369) Trade name, manufactured by Ciba Japan Co., Ltd., hereinafter referred to as “IRGACURE 369”), ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butyl) Peroxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di ( Ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloro Methyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl -1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- ( 2-methyl-2-dimethylaminopropionyl) carbazol 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (T-Hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzof Non, 3,4′-di (methoxycarbonyl) -4,3′-di (t-butylperoxycarbonyl) benzophenone, 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxy) Carbonyl) benzophenone and 1,2-octanedione-1- [4- (phenylthiophenyl) -2- (O-benzoyloxime)] (IRGACURE OXE01; trade name, manufactured by Ciba Japan Co., Ltd., hereinafter “OXE01” May be written).

  Among these, when the photopolymerization initiator (C) contains one or both of IRGACURE 907 and IRGACURE 369 with respect to the total weight of the photopolymerization initiator (C), a photosensitive composition to be obtained. This is preferable from the viewpoint of increasing the sensitivity.

The photopolymerization initiator (C) is 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4, One or more selected from the group consisting of 3′-di (t-butylperoxycarbonyl) benzophenone and 4,4′-di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone When it contains 20% by weight or more based on the total weight of the polymerization initiator (C), the viewpoint of improving the adhesion of the organic film obtained from the resulting photosensitive composition and the development margin of the photosensitive composition are widened. It is preferable from the viewpoint.

<1-4 Solvent>
The photosensitive composition of the present invention may further contain a solvent for adjusting the viscosity and concentration. The solvent may be a single compound or a mixture of two or more compounds. Also good. The solvent is preferably a compound having a boiling point of 100 ° C. to 300 ° C. or a mixed solvent containing 20% by weight or more of this compound.

  Examples of the solvent having a boiling point of 100 ° C to 300 ° C include butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, and ethoxyacetic acid. Methyl, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2- Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-eth Ethyl cypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tri Propylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N, N-dimethylacetamide It is below.

  Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether It is more preferable to use at least one selected from diethylene glycol methyl ethyl ether and ethyl lactate since the coating uniformity becomes high. In particular, when a solvent selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, and ethyl lactate is used, the coating uniformity is high and the safety to the human body is high. Therefore, it is even more preferable.

<1-5 Other components>
<1-5-1 Additive>
Various additives can be added to the photosensitive composition of the present invention in order to improve resolution, coating uniformity, developability, and adhesion. Additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorosurfactants, silicon coating improvers, silane coupling agents. Examples thereof include adhesion improvers such as alkoxybenzophenones, thermal absorbents such as epoxy compounds, melamine compounds or bisazide compounds, and alkali solubility promoters such as organic carboxylic acids. The additive may be a kind of compound or a mixture of two or more kinds of compounds. The addition amount of the additive can be determined according to the kind of the additive, and is preferably 0.005 to 10% by weight with respect to the total amount of the photosensitive composition.

  Examples of the polymer dispersant, surfactant, and silicon-based coatability improver include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, manufactured by Kyoeisha Chemical Co., Ltd.), Disperbak 161, Disperse Bake 162, Disperse Bake 163, Disperse Bake 164, Disperse Bake 166, Disperse Bake 170, Disperse Bake 180, Disperse Bake 181 , Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all of these are trade names, manufactured by BYK Japan KK), KP-341, KP-358, KP-368, KF-96- 50CS, KF-50-100CS (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all are trade names, manufactured by Seimi Chemical Co., Ltd.), lid Gento 222F, Footgent 251, FTX-218 (all are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (and above) All are trade names, manufactured by Mitsubishi Materials Corp.), Megafuck F-171, Megafuck F-177, Megafuck F-475, Megafuck R-08, Megafuck R-30 (all trade names, DIC Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl) Polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether , Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palm Tate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxy Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, and alkyl diphenyl ether disulfonic acid salts.

  Examples of the adhesion improver include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, acetoalkoxyaluminum diisopropylate, and tetraisopropyl. Bis (dioctyl phosphite) titanate is mentioned.

Examples of the ultraviolet absorber include Tinuvin P, Tinuvin 120, Tinuvin 144, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 571, and Tinuvin 765 (all of which are trade names, manufactured by Ciba Japan Co., Ltd.).

  Examples of the thermal crosslinking agent include jER807, jER815, jER825, jER825, jER828, jER190P, jER191P, jER1004, jER1256, jER YX8000 (registered trademark; manufactured by Japan Epoxy Resin Co., Ltd.), Araldite CY177, Araldite CY184 (trade name; Ciba Japan Co., Ltd.), Celoxide 2021P, EHPE-3150 (trade name; manufactured by Daicel Chemical Industries, Ltd.), Techmore VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.)).

  Examples of the alkali solubility promoter include polycarboxylic acids such as trimellitic anhydride, phthalic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride, and 2,3,4-trihydroxy. Benzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,3 ′, 4-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxy Benzophenone, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2, 3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) pro 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1- Methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene Examples include phenolic compounds such as -5,6,7,5 ', 6', 7'-hexanol and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan.

  At least one selected from these is preferably used for the additive.

  Among these additives, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene) Fluorine-based surfactants such as oxyethylene ether), fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates, and silicon-based materials such as BYK306, BYK344, BYK346, KP-341, KP-358, and KP-368 Addition of at least one selected from coatability improvers is preferred from the viewpoint of improving the coating uniformity of the photosensitive composition.

<1-5-2 polyvalent carboxylic acid>
A polyvalent carboxylic acid such as trimellitic anhydride, phthalic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride may be added to the photosensitive composition of the present invention. One or more polyvalent carboxylic acids may be used. Of these polyvalent carboxylic acids, trimellitic anhydride is preferable.

  When the polyvalent carboxylic acid is added to the photosensitive composition of the present invention and heated, the carboxyl of the polyvalent carboxylic acid forms an organic film from the photosensitive composition when the photosensitive composition contains an epoxy. When obtained, it reacts with these to further improve the heat resistance and chemical resistance of the organic film.

In the photosensitive composition of the present invention, when a polyvalent carboxylic acid is added, the polyvalent carboxylic acid is added to 100 parts by weight of the total amount of the alkali-soluble inorganic fine particles (A) and the compound (B) having a polymerizable double bond. The acid is preferably 1 to 20 parts by weight.

<1-6 Storage of Photosensitive Composition>
When the photosensitive composition of the present invention is stored in the light-shielded state at a temperature in the range of 5 ° C. to 25 ° C., it is preferable because the temporal stability of the composition is good. If the storage temperature is 5 ° C. to 10 ° C., there is no precipitate and it is more preferable.

  The photosensitive composition of the present invention further has characteristics generally required for a polymer composition used for forming an organic film in an electronic component. The “generally required characteristics” include, for example, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, adhesion to the base of the organic film to be formed, etc. It is.

<2. Organic Film of the Present Invention>
The organic film of the present invention is an organic film obtained by curing the above-described coating film of the photosensitive composition of the present invention by light irradiation on the coating film. The organic film of the present invention has a high resolution at the time of patterning and is optimal for forming a pattern having a small diameter. The organic film of the present invention can be obtained by a known method for obtaining an organic film from a normal negative photosensitive composition except that the photosensitive composition of the present invention is used. That is, the organic film of the present invention is obtained by a method including a step of forming a coating film of the photosensitive composition of the present invention and a step of irradiating light to the obtained coating film. The production of the organic film of the present invention may further include a step of drying the coating film of the photosensitive composition and a step of baking the coating film after light irradiation or development, if necessary.

  In the organic film of the present invention, it is preferable that a pattern is formed from the viewpoint of applying to a film for various uses formed on an electronic component. In the organic film of the present invention in which a pattern is formed, the step of irradiating the light is a step of irradiating light to the coating film of the photosensitive composition through a mask. It is obtained by the above-described method further comprising the step of developing the film with a developer.

  The organic film of the present invention is preferably transparent from the viewpoint of being applied to a film for various uses formed on an electronic component, as in the case where a pattern is formed. The transparent organic film of the present invention can be obtained by using the photosensitive composition of the present invention which does not contain powders such as pigments in the photosensitive composition of the present invention. In addition, as described above, the transparent organic film of the present invention includes, for example, zirconia, alumina, barium titanate, strontium titanate having a primary particle size of 500 nm or less, or composite fine particles thereof as alkali-soluble inorganic fine particles (A). It can be obtained by using the photosensitive composition of the present invention containing 50 parts by weight or more of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A). it can.

  More specifically, the organic film of the present invention is formed as follows. First, the photosensitive composition of the present invention is applied on a substrate such as glass by spin coating, roll coating, slit coating or the like. As a substrate, for example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass, sheets of polycarbonate, polyester, acrylic, vinyl chloride, aromatic polyamide, polyamideimide, polyimide, film or substrate, aluminum plate, Examples thereof include a metal substrate such as a copper plate, a nickel plate, and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. If necessary, these substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, and vacuum deposition. Application of the photosensitive composition to the substrate can be performed by a conventionally known method such as a spin coating method, a roll coating method, or a dipping method.

Next, the coating film obtained on a board | substrate is normally dried at 60-120 degreeC for 1 to 5 minutes with a hotplate or oven. The coating film on the dried substrate is irradiated with ultraviolet rays through a mask having a desired pattern shape as necessary. The amount of irradiation is suitably 5 to 1,000 mJ / cm ^{2 for} i-line.

  When the substrate is irradiated with ultraviolet rays through a mask, the portion exposed to ultraviolet rays becomes a three-dimensional cross-linked product by polymerization of the compound (B) having a polymerizable double bond, so that it becomes insoluble in the developer. The substrate after irradiation with ultraviolet rays is developed with a developer, and the portion of the coating film on the substrate that is not exposed to ultraviolet rays is removed from the substrate. More specifically, the substrate is immersed in a developer by a method usually used for developing the organic film, such as shower development, spray development, paddle development, dip development, and the like, and the insoluble portion is dissolved and removed.

  The patterned transparent film thus obtained can also be used as a patterned insulating film. The shape of the hole formed in the insulating film is preferably a square, a rectangle, a circle or an ellipse when viewed from directly above. Further, a transparent electrode may be formed on the insulating film, and after patterning by etching, a film for performing an alignment process may be formed. Since the insulating film has high sputtering resistance, wrinkles are not generated in the insulating film even when a transparent electrode is formed, and high transparency can be maintained.

  Developers include inorganic alkalis such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Alkaline aqueous solution is mentioned. Further, an appropriate amount of methanol, ethanol, surfactant or the like can be added to the developer. For example, a surfactant may be added to the developer for the purpose of reducing development residue and optimizing the pattern shape. The surfactant can be selected from anionic, cationic and nonionic surfactants. In particular, the addition of nonionic polyoxyethylene alkyl ether is preferable because the pattern shape is improved.

  When the coating film of the photosensitive composition formed on the substrate is irradiated with ultraviolet rays without using a mask, the substrate is placed at 180 to 250 ° C. for 10 to 120 minutes after the ultraviolet irradiation, and the coating film on the substrate is baked. Thus, a transparent film can be obtained. When the coating film is irradiated with ultraviolet rays through a mask, the substrate is placed at 180 to 250 ° C. for 10 to 120 minutes after development, and the coating film on the substrate is baked to form a transparent film having a desired pattern Can be obtained.

  As mentioned above, although the form formed on a board | substrate was specifically shown about the organic film of this invention, the organic film of this invention is formed on a board | substrate also on the layer and electrode which were formed on the board | substrate. It can be formed similarly to the form. In the present invention, the alkali-soluble inorganic fine particles (A) having a large particle size are used, or coloring inorganic fine particles such as a pigment are used as the inorganic fine particles, or a coloring material such as a pigment or carbon black is used as the photosensitive material of the present invention. An opaque organic film can be obtained by further blending into the composition.

Since the photosensitive composition of the present invention can form an organic film excellent in solvent resistance, acid resistance, alkali resistance, heat resistance and transparency, an organic film using the photosensitive composition is a transparent film. It can be used for coatings for various applications in electronic parts such as display elements such as insulating films and protective films. In addition, the organic film of the present invention is less likely to cause surface roughness even if post-treatment such as immersion or contact with a solution such as a solvent, an acid, or an alkaline solution, and heat treatment is performed in a post-production process. As a result, the organic film of the present invention has high light transmittance and can be suitably used for a transparent film. More specifically, the organic film of the present invention can be used, for example, for forming a gate insulating film of a TFT or an auxiliary capacitor for driving a liquid crystal as an application of a liquid crystal display element. For example, as an alternative to a polyimide material, it can be used for insulating films and coverlays.

<3. Electronic component of the present invention>
The electronic component of the present invention has the above-described organic film of the present invention. Examples of the electronic component of the present invention include a liquid crystal display element and a printed wiring board. In the electronic component of the present invention, the organic film of the present invention can be suitably used for various films that require heat resistance, optical characteristics, electrical characteristics, and pattern formation. For example, it can be used for a passivation film, a buffer coat film, an interlayer insulating film, and a planarizing film in an insulating material or a semiconductor device in an electronic component, and further used in a high refractive index film and a high dielectric constant film in a liquid crystal display element. be able to.

  The organic film of the present invention according to the use in the electronic component of the present invention can be realized by the type and content of the alkali-soluble inorganic fine particles (A). For example, in the passivation film, the inorganic fine particles of the alkali-soluble inorganic fine particles (A) are alumina, zirconia, or composite fine particles thereof, and a compound having a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A). It is preferable to use an organic film made of the photosensitive composition of the present invention containing 50 to 200 parts by weight of (B).

  In the buffer coat film, the inorganic fine particles of the alkali-soluble inorganic fine particles (A) are titania, zirconia, alumina, or a composite fine particle thereof. It is preferable to use an organic film made of the photosensitive composition of the present invention containing 50 to 100 parts by weight of the compound (B) having a bond.

  In the interlayer insulating film, the inorganic fine particles of the alkali-soluble inorganic fine particles (A) are zirconia, alumina, or composite fine particles thereof, and have a polymerizable double bond with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A). It is preferable to use the organic film by the photosensitive composition of this invention which contains 50-200 weight part of compound (B) which has.

  Further, in the planarizing film, the inorganic fine particles of the alkali-soluble inorganic fine particles (A) are titania, zirconia, alumina, or composite fine particles thereof, and the polymerizable double particle is 100 parts by weight with respect to 100 parts by weight of the alkali-soluble inorganic fine particles (A). It is preferable to use an organic film made of the photosensitive composition of the present invention containing 100 to 300 parts by weight of the compound (B) having a bond.

  The high refractive index film is a transparent film having a refractive index of 1.6 or more. In the high refractive index film, the inorganic fine particles of alkali-soluble inorganic fine particles (A) are titania, zirconia, alumina, barium titanate, strontium titanate, zinc oxide, or composite fine particles thereof, and alkali-soluble inorganic fine particles (A) It is preferable to use an organic film made of the photosensitive composition of the present invention containing 50 parts by weight or more of the compound (B) having a polymerizable double bond with respect to 100 parts by weight.

  The high dielectric constant film is an organic film having a dielectric constant of 6 or more. In the high dielectric constant film, the inorganic fine particles of alkali-soluble inorganic fine particles (A) are titania, zirconia, alumina, barium titanate, strontium titanate, zinc oxide, or a composite fine particle thereof, and alkali-soluble inorganic fine particles (A) It is preferable to use an organic film made of the photosensitive composition of the present invention containing 50 parts by weight or more of the compound (B) having a polymerizable double bond with respect to 100 parts by weight.

  In the present invention, it is possible to obtain a film composed of alkali-soluble inorganic fine particles (A) by baking the organic film of the present invention at a temperature of 400 ° C. or higher. Therefore, it is possible to obtain a film having a pattern formed substantially consisting of alkali-soluble inorganic fine particles (A), and such a film can also be used for an electronic component in accordance with the characteristics. is there.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.

[Synthesis Example 1] Synthesis of alkali-soluble inorganic fine particles (A1) In a four-necked flask equipped with a stirrer, 1-methoxy-2-propanol as an organic solvent and titania dispersion as inorganic fine particles (primary particle size: 20 nm, 15% by weight gamma) Butyrolactone solution, manufactured by CI Kasei Co., Ltd., trade name Nanotech), 3-aminopropyltriethoxysilane as a silane coupling agent, tetrabutyl orthotitanate as a metal alkoxide, tetrabutyl orthosilicate as a silicon alkoxide, phthalic anhydride as an acid anhydride The product was charged as follows and stirred for 1 hour, then heated to 110 ° C. and reacted for 3 hours.
1-methoxy-2-propanol 30.0 g
Titania dispersion 63.7g
3-aminopropyltriethoxysilane 1.7 g
5.2 g of tetrabutyl orthotitanate
Tetraethyl orthosilicate 1.6 g
Phthalic anhydride 1.1g

  In this example, a catalog value was adopted as the primary particle size of the inorganic fine particles.

  The reaction solution was cooled to room temperature to obtain the reaction solution. The obtained reaction solution was spin-coated on a glass substrate at 800 rpm for 10 seconds, dried on a hot plate at 100 ° C. for 2 minutes, and then immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds. It was confirmed that all the membranes were dissolved.

[Synthesis Example 2] Synthesis of alkali-soluble inorganic fine particles (A2) As inorganic fine particles, a zirconia dispersion (primary particle size: 20 nm, 15% by weight gamma butyrolactone solution, manufactured by CI Kasei Co., Ltd., trade name Nanotech) and metal alkoxide Except that zirconium tetranormal butoxide was used, and the same components as in Synthesis Example 1 were charged in the following weights and reacted under the same conditions.
1-methoxy-2-propanol 30.0 g
Zirconia dispersion 68.0g
3-aminopropyltriethoxysilane 1.7 g
Zirconium tetranormal butoxide 5.8g
Tetraethyl orthosilicate 1.6 g
Phthalic anhydride 1.1g

[Synthesis Example 3] Synthesis of alkali-soluble inorganic fine particles (A3) As inorganic fine particles, titania composite metal oxide fine particle dispersion (primary particle size: 10 nm, 30% by weight gamma butyrolactone solution, manufactured by Catalyst Kasei Kogyo Co., Ltd. (Quin Titanic), 3-glycidoxypropyltrimethoxysilane as a silane coupling agent, tetraethyl orthosilicate as a silicon alkoxide was charged as follows, stirred at room temperature for 1 hour, then heated to 80 ° C. and then 3 hours Reacted.
1-methoxy-2-propanol 30.0 g
Titania composite metal oxide fine particle dispersion 30.0 g
3-glycidoxypropyltrimethoxysilane 1.0 g
Tetraethyl orthosilicate 1.0 g

The reaction solution was cooled to room temperature to obtain the reaction solution. The obtained reaction solution was spin-coated on a glass substrate at 800 rpm for 10 seconds, dried on a hot plate at 100 ° C. for 2 minutes, and then immersed in a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds. It was confirmed that all the membranes were dissolved.

[Comparative Synthesis Example 1] Synthesis of alkali-soluble polymer and dispersion of inorganic fine particles (C1)
In a four-necked flask equipped with a stirrer, 1-methoxy-2-propanol, butyl methacrylate, methacrylic acid, and 2,2′-azobis (isobutyric acid) dimethyl are charged in the following weight, and heated at a polymerization temperature of 90 ° C. for 2 hours. Polymerization was performed.
1-methoxy-2-propanol 20.0 g
Butyl methacrylate 8.5g
Methacrylic acid 1.5g
2,2′-Azobis (isobutyric acid) dimethyl 0.8 g

  The obtained reaction solution was cooled to room temperature to obtain a polymer solution. A part of the reaction solution was sampled, and the weight average molecular weight was measured by GPC analysis (polyethylene oxide standard). As a result, the weight average molecular weight was 3,200.

  10 g of the obtained polymer solution was added dropwise to 22.2 g of a titania dispersion (primary particle size: 20 nm, 15% by weight gamma butyrolactone solution, trade name Nanotech, manufactured by CI Kasei Co., Ltd.) over 1 hour. A fine particle-dispersed alkali-soluble polymer (C1) was obtained.

[Example 1]
[Production of photosensitive composition]
Alkali-soluble inorganic fine particles (A1) obtained in Synthesis Example 1 as alkali-soluble inorganic fine particles, tris (acryloxyethyl) isocyanurate as the compound (B) having a polymerizable double bond, IRGACURE907 as the photopolymerization initiator (C) (Trade name, manufactured by Ciba Japan Co., Ltd.), Megafac R-08 (trade name, manufactured by DIC Corporation, hereinafter abbreviated as “R-08”) as a additive as a solvent, and solvent Diethylene glycol methyl ethyl ether was mixed and dissolved at the following weight to obtain a photosensitive composition.
Diethylene glycol methyl ethyl ether 0.4193g
Alkali-soluble inorganic fine particles (A1) 2.0270 g
Tris (acryloxyethyl) isocyanurate 0.3000g
Irgacure 907 0.0150g
R-08 0.0031g

[Evaluation method]
1) Formation of patterned transparent film The photosensitive composition prepared in Example 1 was spin-coated at 800 rpm for 10 seconds on a glass substrate, and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was exposed in air using a proximity exposure machine TME-150PRC manufactured by Topcon Corporation through a mask for forming a dot pattern with an exposure gap of 100 μm. The exposure amount was 100 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 manufactured by USHIO INC. And a photoreceiver UVD-365PD. The exposed glass substrate was dip-developed with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds to remove the composition in the exposed area. The substrate after development was washed with pure water for 60 seconds and then dried on a hot plate at 100 ° C. for 2 minutes. This substrate was post-baked in an oven at 230 ° C. for 30 minutes to form a patterned transparent film having a thickness of 1.5 μm. The film thickness was measured using a stylus-type film thickness meter profiler P15 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of three measured values was defined as the film thickness.

2) Residual film ratio after development In the substrate of 1) above, the film thickness was measured before and after the development and calculated from the following equation.
(Film thickness after development / film thickness before development) x 100 (%)

3) Resolution The substrate of the patterned transparent film after post-baking obtained in 1) above was observed with an optical microscope at 1,000 times to confirm the size of the bottom surface of the dot pattern. When a dot pattern could not be formed, it was judged as defective (NG: No Good).

4) Transparency TC-1800 manufactured by Tokyo Denshoku Co., Ltd. was used, and the light transmittance at a wavelength of 400 nm was measured using a glass substrate on which a transparent film was not formed as a reference.

5) Heat resistance The substrate of the patterned transparent film obtained in 1) above was additionally baked in an oven at 300 ° C. for 30 minutes, and before and after heating, the light transmittance was measured in the same manner as in 4) above, and after post-baking (additional) The light transmittance before baking) was T1, and the light transmittance after additional baking was T2. It can be determined that the smaller the decrease in light transmittance after post-baking and after additional baking, the better. The film thickness was measured before and after heating, and the film thickness change rate was calculated from the following equation.
(Film thickness after additional baking / film thickness after post-baking) x 100 (%)

6) Relative permittivity Electrodes were prepared above and below the transparent film, and relative permittivity measurement was performed using an LCR meter (4284A) manufactured by Agilent Technologies. The method for producing the transparent film is as follows.

The photosensitive composition was spin-coated at 800 rpm for 10 seconds on a glass substrate on which aluminum was deposited, and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was fully exposed in air using a proximity exposure machine TME-150PRC manufactured by Topcon Corporation. The exposure amount was 300 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 manufactured by USHIO INC. And a photoreceiver UVD-365PD. This substrate was post-baked in an oven at 230 ° C. for 30 minutes to form a transparent film having a thickness of 1.5 μm. Furthermore, aluminum was vapor-deposited on it.

  The film thickness was measured using a stylus-type film thickness meter profiler P15 manufactured by KLA-Tencor Japan Co., Ltd., and the average value of three measured values was defined as the film thickness. Evaluation was performed at 1 kHz.

7) Refractive index The reflective film thickness meter FE-3000 by Otsuka Electronics Co., Ltd. was used, and the refractive index of the transparent film was measured. The measurement wavelength of the refractive index was 600 nm. The method for producing the transparent film is as follows.

The photosensitive composition was spin-coated on a glass substrate at 800 rpm for 10 seconds, and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was fully exposed in air using a proximity exposure machine TME-150PRC manufactured by Topcon Corporation. The exposure amount was 300 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 manufactured by USHIO INC. And a photoreceiver UVD-365PD. This substrate was post-baked in an oven at 230 ° C. for 30 minutes to form a transparent film having a thickness of 1.5 μm.

8) Surface roughness of the film The surface roughness (surface roughness) of the transparent film was measured using a stylus-type film thickness profiler P15 manufactured by KLA-Tencor Japan. The method for producing the transparent film is as follows.

The photosensitive composition was spin-coated on a glass substrate at 800 rpm for 10 seconds, and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was fully exposed in air using a proximity exposure machine TME-150PRC manufactured by Topcon Corporation. The exposure amount was 300 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 manufactured by USHIO INC. And a photoreceiver UVD-365PD. This substrate was post-baked in an oven at 230 ° C. for 30 minutes.

  The evaluation results are shown in Table 1.

[Example 2]
Production of Photosensitive Composition A photosensitive composition was obtained in the same manner as in Example 1 except that the alkali-soluble inorganic fine particles (A2) obtained in Synthesis Example 2 were used as the alkali-soluble inorganic fine particles. The obtained photosensitive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
Production of Photosensitive Composition A photosensitive composition was obtained in the same manner as in Example 1 except that the alkali-soluble inorganic fine particles (A3) obtained in Synthesis Example 3 were used as the alkali-soluble inorganic fine particles. The obtained photosensitive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
Titania dispersion (primary particle size: 20 nm, product name Nanotech, manufactured by CI Kasei Co., Ltd.) as inorganic fine particles, tris (acryloxyethyl) isocyanurate as compound (B), IRGACURE907 (product) as photopolymerization initiator (C) Name, manufactured by Ciba Japan Co., Ltd.), Mega-Fac R-08 (trade name, manufactured by DIC Corporation, hereinafter abbreviated as “R-08”) as a fluorosurfactant as an additive, and diethylene glycol methyl as a solvent Ethyl ether was mixed and dissolved at the following weight to obtain a photosensitive composition. The obtained photosensitive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Diethylene glycol methyl ethyl ether 0.1350g
Titania dispersion 2.0270g
Tris (acryloxyethyl) isocyanurate 0.3000g
Irgacure 907 0.0150g
R-08 0.0031g

[Comparative Example 2]
In the same manner as in Comparative Example 1 except that a zirconia dispersion (primary particle size: 20 nm, manufactured by C.I. Kasei Co., Ltd., trade name Nanotech) was used as the inorganic fine particles, the photosensitive composition was mixed and dissolved in the following weights. Obtained. The obtained photosensitive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Diethylene glycol methyl ethyl ether 0.1350g
Titania dispersion 2.0270g
Tris (acryloxyethyl) isocyanurate 0.3000g
Irgacure 907 0.0150g
R-08 0.0031g

[Comparative Example 3]
A photosensitive composition was obtained in the same manner as in Comparative Example 1 except that the inorganic fine particle-dispersed alkali-soluble polymer (C1) obtained in Comparative Synthesis Example 1 was used as the inorganic fine particles instead of the titania dispersion. The obtained photosensitive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  The photosensitive composition of this invention is applicable to manufacture of the electronic component containing a fine patterned transparent film, for example.

Claims (9)

A method for producing a photosensitive resin composition comprising alkali-soluble inorganic fine particles (A), a compound (B) having a polymerizable double bond, and a photopolymerization initiator (C) ,
By using a surface treatment agent that reacts with the inorganic fine particles to form a hydrolyzable group on the surface of the inorganic fine particles, the surface treatment of the inorganic fine particles is performed in the presence of an acid anhydride, whereby the alkali-soluble inorganic fine particles (A) are obtained. A step of preparing, and
The said manufacturing method including the process of mixing the said alkali-soluble inorganic fine particle (A), the compound (B) which has a polymerizable double bond, and a photoinitiator (C) . The manufacturing method of the photosensitive composition of Claim 1 in which the inorganic element of an alkali-soluble inorganic fine particle (A) contains the 1st-15th group element of a periodic table. The inorganic elements of the alkali-soluble inorganic fine particles (A) are Si, Ti, Zr, Sr, Al, Ba, Ca, Fe, Hf, In, La, Mg, Mo, Nb, Pb, Sb, Sn, Ta, Zn, The manufacturing method of the photosensitive composition of Claim 1 or 2 containing 1 or more chosen from the group which consists of W, Y, P, Na, K, Ge, Ga, and B. The photosensitive composition as described in any one of Claims 1-3 whose content of the compound (B) which has a polymerizable double bond with respect to 100 weight part of alkali-soluble inorganic fine particles (A) is 500 weight part or less. Manufacturing method . The manufacturing method of the photosensitive composition of Claim 4 whose content of the compound (B) which has a polymerizable double bond with respect to 100 weight part of alkali-soluble inorganic fine particles (A) is 10-500 weight part. The manufacturing method of the photosensitive composition as described in any one of Claims 1-5 whose compound (B) which has a polymerizable double bond is polyfunctional acrylate. The manufacturing method of the photosensitive composition as described in any one of Claims 1-6 whose photoinitiator (C) is a compound which generate | occur | produces a radical by an ultraviolet-ray. A step of obtaining a photosensitive composition by the method for producing a photosensitive composition according to claim 1 ,
Obtained to obtain a coating film of the photosensitive composition, and a method for producing the coating film comprising the step of Ru is cured by light irradiation and the organic film. Further comprising the step of mask to form a pattern by developing the light irradiation interposed, a method of manufacturing an organic film according to claim 8.