TW201140243A - Photosensitive resin composition - Google Patents

Abstract

Disclosed is a photosensitive resin composition-that can form a minute pattern by means of photolithography, can form a insulating film without heat treatment above 200 DEG C, and has no problems of carrier being trapped and charge mobility decreasing when used as a gate insulating film of an organic thin-film transistor-containing a photo-radical generating agent and a polysiloxane compound having units represented by the belowmentioned general formulae (1-4). (In formula 1, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkylene group having a carbon number of 1-5 that may have a substituent alkyl group. In formula 2, R3 represents a hydrogen atom or an alkyl group having a carbon number of 1-4. In formula 3, R4 represents an alkyl group having a carbon number of 1-6 or a cycloalkyl group having a carbon number of 5-6. In formula 4, R5 represents a hydrogen atom or an alkyl group having a carbon number of 1-4.)

Description

[Technical Field] The present invention relates to a photosensitive resin composition using a polyoxyalkylene compound, and further to a negative resist using the photosensitive resin composition (especially Is permanent photoresist). [Prior Art] In recent years, research on liquid crystal display devices and EL (Eiectr® mine LUmine SCenCe) electroluminescent devices has been popular in the industry, and electronic paper, which can be driven by low power consumption, has attracted attention. E-paper can be made into a thin film-like thickness, which has the advantage of low power consumption and image retention even when the power is turned off, and can be expected to be applied to an electronic book or a poster. When a plastic film is used as the display substrate of the electronic paper, and the organic thin film transistor is used as the driving portion of the display device, the texture is soft, and even if the bending is performed, the quality of the GG, ..., and the shell texture can be improved. The scope of application has also expanded to promote universal access. The gate insulating film of the organic thin film transistor is generally subjected to CVD (chemical; apor deposition^^^^^^^)^^, b^. nitriding, oxidizing I, 袅, --料 (10) & In addition, since the CVD method requires a large-scale vacuum system, the CVD method requires a large-scale vacuum system. Therefore, the inorganic materials are hard, and , used in plastic film and other flexible beauty; t. bending and damage. In the case of a young substrate, there are many cases where the organic material is coated or printed, and it is cheaper and larger! Made in the field, and its flexibility or 154534.doc 201140243 Therefore, the industry is prevailing in the research of organic thin-wall materials. The membrane transistor has excellent adhesion to the plastic film, and the organic electronic paper for the gate insulating film needs a fine display device. For the gate insulating film of the organic thin film transistor used here, it is necessary to have a smear-shaped cream. The clothes are formed into a fine pattern. As a method of forming the fine pattern, there is a photolithography method, and it is a photosensitive resin 钽 character D which can form a gate insulating film by photolithography, and is known to contain an alkoxy decane. A condensate and a photoacid generator, a ruthenium salt, and a photosensitive resin composition such as a hydrazine and a base generator (for example, refer to Patent Documents 1 to 3). However, in such a photosensitive resin composition, a current is generated due to a residual photoacid generator, a test agent, and the like, and the photosensitive resin composition is hardened by cross-linking of an alkoxyalkyl group. , It is necessary to carry out the heat treatment of ~~. Therefore, a plastic film such as a polycarbonate or a polyethylene terephthalate cannot be used as a substrate. As a photosensitive resin composition which can enter a green shadow (four) and obtain an insulating film having high insulating properties; see a photosensitive resin composition containing a polyoxyalkylene compound having an epoxy group and a photoacid generator, However, the insulating film obtained from such a photosensitive resin composition has a problem that a hydroxyl group formed by ring opening of an epoxy group traps a plant formed on a semiconductor layer, and the charge mobility is lowered. [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] Therefore, an object of the present invention is to provide a photosensitive resin composition which can be formed into a fine pattern by photolithography without exceeding 2 Å. The heat treatment is performed to form an insulating film, and the carrier is trapped to reduce the charge mobility when it is not used as a gate insulating film of an organic thin film transistor. [Technical means for solving the problem] The inventors of the present invention conducted diligent research in view of the above circumstances, and as a result, completed the present invention. In other words, the present invention provides a photosensitive resin composition containing a polyoxyalkylene compound having a unit represented by the following general formulae (1) to (4) and a photo-radical generating agent: [Chemical Formula 1] R1 0 I II 2 H2C=C—C—〇—R—S i 03/2 (1) wherein R is a hydrogen atom or a methyl group, and R 2 represents a alkylene group having a carbon number of 1 to 5 which may have a substituted alkyl group. R2^-Si03/2 (2) (wherein R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms); [Chemical 3] [R^SiO^ (3) (wherein R4 represents a burnt group of 1 to 6 or a ring-burning group of 5 or 6) 154534.doc 201140243 [Chem. 4]

(wherein R5 represents a hydrogen atom or an alkyl group having a carbon number of 4). [Effect of the Invention] The effect of the present invention is to provide a photosensitive resin composition (especially a negative photosensitive resin composition) and a negative photoresist (especially a permanent photoresist) using a photosensitive resin composition, which is photosensitive The resin composition can be made not only transparent! The insulating layer which is excellent in resistance to temperature change at the time of fabricating the substrate and which is resistant to change over time as a permanent photoresist. [Embodiment] Hereinafter, the present invention will be described in detail based on preferred embodiments. First, a polyoxyalkylene compound having a unit represented by the above formulas (1) to (4) (hereinafter sometimes referred to as a polyoxyalkylene compound of the present invention) will be described. In the above formula (1), R1 represents a hydrogen atom or a methyl group, and a methyl group is preferred in terms of good storage stability. R2 represents a stretching group having a carbon number of 15 which may have a substituted alkyl group. Examples of the alkylene group having a carbon number of 丨5 include a methylene group, a propyl group, a butyl group and a pentyl group. Although it is preferably a carbon number in terms of heat resistance, it is industrially easy. In terms of obtaining, it is preferred to extend ethyl propyl and butyl, more preferably ethyl and propyl are preferably propyl. Examples of the substituted alkyl group which R may have include a methyl group, a 2-group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group, but are resistant to 154534.doc 201140243. It is preferred that it does not have a substituted alkyl group. In the above formula (2), R3 represents a hydrogen atom or an alkyl group having a carbon number of 丨4, and examples of the alkyl group having a carbon number of 1 to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Isobutyl, second butyl and tert-butyl groups, and the like. The material r3 is preferably a hydrogen atom in terms of industrial availability and good heat resistance.

In the above formula (3), R4 represents an alkyl group of carbon number 6 or a cycloalkyl group having 5 or 6 carbon atoms. Examples of the alkyl group of the carbon number 6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group: an isopentyl group, and a neopentyl group. a group, a 2-pentyl group, a third pentyl group, a hexyl group, a 2-hexyl group and the like; and examples of the cycloalkyl group having a carbon number of 5 or 6 include a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, and a cyclopentylmethyl group. Wait. R4 is preferably an ethyl group or a methyl group, and more preferably a methyl group, in terms of good heat resistance. In the above formula (4), V represents a hydrogen atom or a carbon group of carbon number. Examples of the condensing group of carbon number 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third butyl group. As r5, it is industrially easy to obtain and heat resistance is good, and it is preferably a hydrogen atom. In the polyoxanthoxy compound of the present invention, the content of the monoterpene represented by the above formula (1) is preferably 〇.bu 5 mmGl/g, more preferably G5~3 face (10), preferably i~2.5 mmoI /g. The content of the unit represented by the above formula (7) = the total number of units represented by the above formulas (1) to (4), preferably jin. 8' is more preferably ^ Μ 'best is G tai ^ The sum of the units of the formula (7) and the number of units indicated by the above formulas (1) to (4) is preferably 〇.(4).8, more preferably GW, and most preferably 5 to 〇6. The content of the unit represented by the above formula (4) is more than the combination of the number of units represented by the above-mentioned 154534.doc 201140243 formula (υ~(4). 〇1~0.6, more preferably 0 03~0 4 Preferably, 〇〇5 〜 乂 为 又 又 又 又 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The photosensitive tree of the invention, the full &&& and the use of the five materials are different, and when used as a negative photoresist, it is preferably: 〇 _ 3 to 5.0, more preferably 〇 5 to 3, preferably 15 to 2.5. When the photosensitive resin composition of the present invention is used as a rod of a lens or an optical waveguide 7 τ heart-shaped material, it is preferably 0.3 to 7.0. More preferably, 〇-3~5' is preferably Ο". ^ When the molecular weight of the polyoxy siloxane compound of the present invention is too small, the coating property or film forming property of the photosensitive resin composition of the invention is changed. If not, the mass average molecular weight of the polyoxygenated compound of the present invention is preferably 1000 to 100,000. 2000~50000 is good, most preferably 3〇〇〇~⑽I, Moreover, in the present invention, the mass average molecular weight, refers to four gas. Cardiff pyran (hereinafter referred to as THF) as a solvent Gpc (Gei

Chromatog-raphy, gel permeation chromatography) was analyzed by polystyrene for 2 mass average molecular weight. In the case where the polyoxyalkylene compound of the present invention has a residual stanol group (SiOH group), the storage stability of the photosensitive resin composition of the present invention is lowered by the presence of a stanol group, and thus the polymerization of the present invention The content of the stanol group in the siloxane compound is preferably 1 〇 mm 〇 1 /g or less, more preferably 0.1 mmol / g or less. Further, the stanol group can be used by using a near-infrared spectrophotometer (refer to Japanese Patent Laid-Open Publication No. 2001-208683, Japanese Patent No. 154534.doc 201140243, No. 2003-35667) or 9Si-NMRf inflammation as α The analysis of the apparatus of the Japanese Patent Publication No. 2007-2 17249 箄w3 曰 专利 特 ) ) 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏 宏The chemical compound or the hydrolyzed vinegar makes the unit t-emulsion compound of the present invention preferably in terms of adhesion, and further has the following formula (5): E5: E~S'〇3 /2 C5) (Formula t, E represents a group having an epoxy group). In the above formula (5), "E" represents a group having an epoxy group, and examples of the epoxy group include, for example, a group represented by the following formulas (6) to (8), and the effect of improving the adhesion is good. It is preferably a group represented by the following general formulae (7) and (8), more preferably a base represented by the following general formula (7): [Chem. 6] A r h2c-ch+ch2-0+rl_ (8) ' R6 represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group, and the claws represent 0 or 1);

[7 7 (7) (wherein R 7 represents a hydrogen atom or a methyl group, Rs represents an alkyl group which may have a carbon number of a substituted alkyl group] to 5, and η represents 0 or 1); 154534.doc 201140243 [Chemical 8] (8) (wherein R9 represents an alkylene group having 1 to 5 carbon atoms which may have a substituted alkyl group). In the above formula (6), R6 represents a stretching group having a carbon number of 1 to 5 which may have a substituted alkyl group. Examples of the alkylene group having 1 to 5 carbon atoms include an anthracenylene group, an ethylidene group, a propyl group, a butyl group, and a pentyl group. Although the heat resistance is preferably a small carbon number, In terms of industrial availability, it is preferably an ethyl group, a propyl group and a butyl group, more preferably an ethyl group and a propyl group, and most preferably an ethyl group. Examples of the substituted alkyl group which may be contained in R include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. However, in terms of heat resistance, it is preferably Does not have a substituted alkyl group. m represents ..., and m is preferably 1 in terms of easy availability of the raw material. In the above formula (7), r7 represents a hydrogen atom or a methyl group, and r8 represents an alkylene group which may have an alkyl group of from 1 to 5. The alkylene group having a carbon number of 1 to 5 may be an ethyl group, a propyl group, a butyl group and a pentyl group. Although it is heat resistant, 3 is preferably a carbon number, but it is preferably a stretch. Emei ^ fruit is easy to be paid for methyl ethyl, propyl and butyl, propyl, most with 盏 / a 尺 马 伸 乙基 乙基 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 。 及 。 。 。 As R8, there may be mentioned, and the substituted alkyl group, such as earth, ethyl, propyl, isopropyl, butyl, etc., as the butyl group, the isobutyl group and the third group, in terms of heat resistance. In the sense that n represents 〇 or 1, # h 杈 preferably does not have a substituted alkyl group. However, in the case where the raw material is easily obtained, in the case where the compound of the present invention is in the form of a unit of the formula, the content of the unit represented by the above formula (: has the above formula (1) is 154534. .doc 201140243 Clearing 4 * The effect of the improvement of the joint is small, and when there is a case where the salty well # of the present invention is used, the mountain resin composition is hardened; 7, out,! Therefore, the δ of the unit represented by the above formula (7) is preferably from 2,000 to 50,000, more preferably from 3,000 to 20,000, in terms of % roll equivalent. & 1 main horse two!: polyoxalate compound can be passed through Formula (10) Training Table = 钱 化合物 化合物 或 齿 齿 齿 齿 齿 齿 齿 齿 齿 齿 齿 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 ] ] ] ] ] ] ] ] ] ]3 (1 a) (wherein R and R have the same meanings as in the above formula (1), and χΐ represents a dentate atom or an alkoxy group having a carbon number of 1 to 4);

Si-fx2L (2

G (wherein R3 is the same as in the above formula (2)), and χ2 represents a halogen atom or an alkoxy group having 1 to 4 carbon atoms; [Chemical 11] R^2~Si-{-X3]2 (3 a) (wherein R4 is the same as the above formula (3), and J 3 is the same as ''3' means a halogen atom or an alkoxy group having a carbon number of 1 to 4);

Si+X4]2 (4 154534.doc •11-201140243 (wherein R5 has the same meaning as the above formula (4), and χ4 represents a self-atomic atom or a carbon alkoxy group). The alkoxydecane compound represented by la) may, for example, be (acryloxymethyloxy)trimethoxynonane or (2-propyleneoxypropyl)dimethoxyoxydecane' (3-propenyloxyl). Propyl)trimethoxydecane, (3-propyleneoxypropyl)triethoxydecane, (methacryloxycarbonyl)trimethoxydecane, (2-mercaptopropoxypropyl) Trimethoxy decane, (% methacryloxypropyl) trimethoxy decane, (3-methacryloxypropyl) triethoxy decane; as represented by the above formula (la) Examples of the decane compound include (3. propylene methoxy propyl) trichloro decane, (3 fluorenyl propylene oxypropyl) trioxane, etc., and the alkoxy group represented by the above formula (la). The decane compound or the halogenated decane compound is preferably (3-methacryloxypropyl) three in terms of good reactivity and easy control of the reaction. Oxydecane and (3-methacryloxypropyl)triethoxydecane, more preferably (3-methacryloxypropyl)trimethoxydecane. As the above formula (2a) Examples of the alkoxylate compound represented by the group include phenyl trimethoxy decane, phenyl triethoxy decane, phenyl triisopropoxide, and 4-mercaptophenyl trimethoxy decane. And 4-mercaptophenyl triethoxy zeoxime, 4-methylphenyl triisopropoxy decane, etc.; as the halogenated decane compound represented by the above formula (2a), for example, phenyl tris, Anthracite, 4-methylphenyltrichloromethane, etc., as the alkoxylate compound or the tooth fossil compound represented by the above formula (2&), in terms of good reactivity and easy control of the reaction, Preference is given to phenyltrimethoxy decane and phenyltriethoxy decane, more preferably phenyltrimethoxy decane. 154534.doc -12- 201140243 Alkoxydecane represented by the formula (3a) Examples of the compound include dimethyldi M ^ 4 - decyl hexane, dimethyl diethoxy decane, and dimethyl ketone. t*· π-ethylphenyl bis-oxy decane, diethyl diethoxy hydrazone J, bis 7 _ earth-isopropoxy zeshi, dipropyl bis, dipropyl bis - aryl decane, dipropyl diisopropoxy decane, etc.; as a compound of the above formula (3 a) - the above-mentioned fossilized compound, for example, dimethyl-chloro fever, -7 « Ο monoethyldichlorodecane, dipropyldichlorodecane, etc. as an alkoxy compound or i fossilized oxime represented by the above formula (9)) is excellent in reactivity and easy to control. t, preferably dimethyl-methoxydecane and dimethyldiethoxydecane, more decyloxydecane. For example, diphenyl bis (4-methyl as the alkoxy 7 compound represented by the above formula (4a) is exemplified by diphenyl dimethoxy decane, dipyridyl diethoxy decane - isopropoxy alcohol. , bis(4_mercaptophenyl)dimethoxy sulphide m

G-phenyl phenyl) diethoxy ketone, bis (4-methylphenyl) diisopropoxy oxalate, etc., as the cleavage compound represented by the above formula (4a), for example, diphenyl group Dichloro (tetra), bis (4-methylphenyl) three gas and so on. The alkoxylate compound or the functionalized fossil compound represented by the above formula (4a) is preferably diphenyl-methoxy-stone and diphenyl-di, in terms of good reactivity and easy control of the reaction. The ethoxylated stone is more preferably diphenyl dimethyl-based. In the case where the compound of the silk group (IV) represented by the above formulas (1a) to (4a) or the functional compound is hydrolyzed and condensed, it is preferred to carry out the reaction using a catalyst such as an acid or a base. As a solvent which can be used in the reaction, it can be listed as 154534.doc 13 201140243 · water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, diterpene One type of these may be used for the calcination, tetrahydrofuran, toluene, xylene, cyclohexane, etc., or two or more kinds may be used in combination. In order to use a solvent other than water, it is preferred to carry out a reaction by adding an appropriate amount of water in order to promote the hydrolysis condensation reaction. In the hydrolytic condensation reaction of the oxyalkylating compound or the halogenated dreaming compound, the alkoxy fluorene group or the dentate oxime group is hydrolyzed to form a stanol group by using water, and the stanol groups formed, or stanol The group is condensed with an alkoxyalkyl group or with a halogenated alkyl group to form a fluorenylalkyl group (Si〇si*). Examples of the catalyst for the hydrolysis condensation reaction include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid; tannic acid, acetic acid, oxalic acid, citric acid, methyl acid, benzenesulfonic acid, p-toluenesulfonic acid, and monoisopropyl phosphate. Organic acids such as esters; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia; and amine compounds (organic bases) such as trimethylamine, triethylamine monoethanolamine, and diethanolamine, etc., which can be used. - Kinds, or two or more types may be used in combination. The temperature of the hydrolysis condensation reaction varies depending on the kind of the solvent, the kind and amount of the catalyst, and the like, but is preferably 0 to 80 ° C, more preferably 5 to 5 ° C, and most preferably 8 to 30 t. When the alkoxylated compound or the compound of the compound represented by the above formulas (1a) to (4a) is hydrolyzed and condensed, each of the oxy-oxyl compounds or the halogenated compound can be subjected to a halogenation reaction; The reaction 'may be carried out after mixing and mixing'. In terms of production in which the unevenness of the reactants is small and the production is measurable, it is preferred to carry out the reaction after mixing. - the 4th month of the oxylate compound further has the above formula (7)

In the case of the unit shown, in addition to the alkoxy group represented by the formula (la) to (4a), 154534.doc _ 14· 201140243 decane compound or dentate decane compound, Hydrolysis condensation of an alkoxydecane compound or a dentate decane compound represented by the above formula (5 a): [Chem. 13] E-Si-fx5]3 (5 a) (wherein E and the above formula (5) has the same meaning, and χ5 represents a halogen atom or an alkoxy group having 1 to 4 carbon atoms). Examples of the alkoxydecane compound or the halogenated decane compound represented by the above formula (5a) include 3,4·epoxybutyltrimethoxydecane, 2-glycidoxypropyltrimethoxydecane, and 3 • glycidoxypropyl trimethoxy decane, 2-glycidoxy 丨 曱 曱 曱 乙基 ethyl trimethoxy decane, 3-glycidoxy propyl triethoxy decane, 2 _ (3, 4 _ Epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3,4-epoxycyclohexyltrimethoxynonane, 3,4-ring Oxycyclohexyltriethylsulfanyl decane, 2-(3,4-epoxy-4-mercaptocyclohexyl)propyltrimethoxy decane, and the like. In the case where the polyoxyalkylene compound of the present invention is obtained by a hydrolysis condensation reaction of an alkoxydecane compound or a dentate decane compound, the method may leave a sulphur-based alcohol group. Since the storage stability of the photosensitive resin composition is lowered, it is preferred to cap the stanol group. In the case of capping the stanol group, the following method can be employed: a method for alkylating a trimethyl hydrazine with trimethylchlorodecane or hexamethylene diazoxide; using a formic acid ester, a raw acetic acid vinegar, and a fourth Alkoxylated toluene ketones 15, carbonic acid g, etc. Hydrolyzability 154534.doc -15- 201140243 A method of alkoxylation of an ester compound. Next, 'the photoradical generator of the invention' is a photoradical generator which refers to a compound which initiates radical polymerization by irradiation of an energy ray. Examples of the energy ray include ultraviolet rays, electron beams, and ruthenium. Rays, radiation, high-frequency waves, etc. Examples of the photoradical generator include an acetophenone photoradical generator, a benzoin photoradical generator, a benzophenone photoradical generator, and a thioxanthene photoradical generator. A fluorenylphosphine oxide-based photoradical generator or the like. As the photo-radical generating agent, one type may be used alone or two or more types may be used in combination. Examples of the acetophenone-based photoradical generator include diethoxy phenethyl hydrazine, 2-hydroxy-2-methyl-1-phenylpropane hydrazine ketone, and 4, isopropyl group. 2-hydroxy-2-mercaptopropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-nonanone, p-dimethylene Amino acetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrisacetophenone, p-azidobenzylidene phenylacetone, 1-hydroxycyclohexyl phenyl ketone, 2-A (曱 thio) phenyl]-2-morpholinylacetone _; [, 2 _ benzyl 2 dimethylaminomorpholine phenyl) butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, Concentrates of benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 2_hydroxy-2_mercapto-oxime-^-ethlyl-(1-indolylvinyl)phenyl]acetone. Examples of the above-mentioned priming photo-radical generating agent' include, for example, dip-ethyl oxime (also known as oxime) and bis(4-methoxyphenyl)ethanedione (also known as fentanyl). Wait. Examples of the above-mentioned benzophenone oxime-based radical generating agent include benzophenone, phthalic acid phthalic acid ester, mithicone, and 4,4, _ double (diethyl 154534.doc 201140243) 4~ Benzene fluorenyl _4. _ methyl group, for example, 2-chloro. Sesame, thioxanth-2-isopropenyl)benzophenone, 4,4'-dichlorobenzophenone- Ben Sulphur & $ et al. Examples of the thioxanthone-based photoradical generator ketone, 2-methylthioxanthone, 2-ethylthioxanthone, ketone ketone, and 2,4-diethylpyrone. Ο

Examples of the fluorenyl phosphine oxide-based photoradical generator include methyl benzhydryl diphenyl phosphine oxide, 2,4,6-trimethyl phenyl lysine diphenyl phosphine oxide, and 2, 4 , a fluorenylphosphine oxide such as 6-trimethylbenzimidylphosphonium methacrylate or the like, a light-based generator; bis (2,4,6•trimethylbenzoic acid-based early benzene) A bis-indenylphosphine oxide-based photoradical generator such as phosphine oxide or bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylphosphonium phosphine oxide. When the photosensitive resin composition is cured and used as a gate insulating film for an organic thin film transistor, as the photoradical generating agent, it is preferable to obtain a high f-load mobility. The photoradical generator is more preferably a monodecylphosphine oxide photoradical generator, and is preferably 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Two or more kinds are used in combination. In the case of a photo-radical generator, at least one of them is a mercaptophosphine oxide-based photoradical generator. The photosensitive resin composition of the present invention is cured to be used as a lens or a light. In the case of a transparent material such as a conductive material, it is preferred that the photo-radical generating agent is a cured product having high transparency, and is preferably an acetophenone-based photoradical generator and a fluorenylphosphine oxide-based light. The radical generator, more preferably an acetophenone-based photoradical generator, is preferably hydroxycyclohexyl phenyl ketone. When two or more photoradical generators are used in combination, it is preferably 154534. Doc -17· 201140243 At least one of them is an acetophenone-based photoradical generator. The content of the photo-radical-generating agent in the photosensitive resin composition of the present invention is based on the light-free production of wow-nan 丨## & , ^ The type of the seat j, the type of the radical polymerizable group of the photosensitive resin composition of the present invention, and the type and strength of the 壬At Θ green 3 ^ / lingual 旎I line 'However, it is preferably O.NiO parts by mass, more preferably 02 to 7 parts by mass, most preferably 0.3 to 5 parts by mass, based on the parts by mass of the polyoxo-oxygen compound ι 本 of the present invention. If the content of the generating agent is less than 1 part by mass, there is a case where the hardening is insufficient, and if In the case of 1 part by mass, it is not possible to obtain an effect which is commensurate with the amount of the compound, and may adversely affect heat resistance, transparency, etc. The photosensitive resin composition of the present invention may further contain an organic solvent. Examples of the solvent include aromatic benzene compounds such as benzene, xylene, toluene, ethylene stupid ethylene, dimethyl benzene, diethylbenzene, and tetrahydronaphthalene; pentane, isopentane, hexane, isohexane, and heptane; , isopentane, octane, isooctane, decane, isodecane, decane, isodecane, isododecane, cyclohexane, nonylcyclohexane, menthane, decahydronaphthalene, etc. a compound; an ether solvent such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran or dioxane, acetone, thiol Ketone solvents such as ketone, decyl isobutyl ketone, diethyl ketone, dipropyl steel, decyl amyl ketone, cyclohexanone; ethyl acetate, cerium acetate _, butyl acetate, propyl acetate, Ester solvent such as cyclohexyl acetate; propylene glycol monomethyl acetate, ethylene glycol monoethyl ether Glycol ester solvents burn ester, dipropylene glycol ether acetate unitary said Yue, an ethylene glycol monoethyl ether acetate. These solvents may be used singly or in combination of two or more. 154534.doc -18- 201140243 In the case where the photosensitive resin composition of the present invention is used by a coating method or a printing method, the content of the above organic solvent is relative to the mass of the polysulfide compound of the present invention. The portion is preferably 5 to 200 parts by mass, more preferably 1 part by mass to 1 part by mass.

In the photosensitive resin composition of the present invention, in addition to the above organic solvent, a photosensitizer, a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, an antifoaming agent, a pigment, or the like may be formulated as needed. Any component such as a dye. The amount of the optional components is preferably 0. ooiq by mass based on 100 parts by mass of the polysiloxane compound of the present invention. The photosensitive resin composition of the present invention is a method of forming a layer of the photosensitive resin composition of the present invention on a substrate such as a substrate, and then curing the layer of the photosensitive resin composition of the present invention by irradiation with an active energy ray. There is no particular limitation, for example, dip coating, flow coating, brush coating, spray coating, spin coating, I coating, bar coating, etc. can be used, if formed by screen coating or light transfer, etc. Patterned film. The object to form the layer of the photosensitive resin composition of the present invention is not particularly limited, and a crystal plate, a glass plate, a metal plate or the like can be used depending on the application. The thickness of the layer of the photosensitive resin composition of the present invention formed on the object is different from that of the insulating film or the organic thin film transistor used for the semiconductor element, and the thickness of the edge film of the semiconductor film. Taking 1() nm~1G μη as the standard, in the case of the core portion of the optical waveguide, it is based on ^200 μηι. When the photosensitive resin composition of the present invention contains an organic solvent, the layer of the photosensitive resin composition of the present invention is formed and then subjected to heat treatment (may not be pre-baked) to remove the organic solvent of the layered towel. Heat treatment I54534.doc 19 201140243 The condition is appropriately selected according to the boiling point or vapor pressure of the organic solvent to be used, the thickness of the layer of the photosensitive resin composition of the present invention, and the heat-resistant temperature of the object forming the layer. Heat treatment at ~140 ° C for 30 seconds ~ 1 〇 minutes as standard. Examples of the light source that irradiates the active energy ray to the layer of the photosensitive resin composition include an ultrahigh pressure mercury lamp, a Deepuv lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal toothed lamp, an excimer laser, etc., and the light source is based on photoradicals. The photosensitive agent of the generating agent or sensitizer is appropriately selected. The irradiation energy of the active energy ray is appropriately selected depending on the thickness of the layer of the photosensitive resin composition or the kind or amount of the photo-based radical generator. Although the layer of the photosensitive resin composition is hardened by irradiation of the active energy ray, it may be subjected to heat treatment (sometimes referred to as post-baking) to improve the adhesion between the layer of the hard layer and the object such as the substrate. The heat treatment is preferably carried out in an atmosphere of an inert gas such as nitrogen, helium or argon at a temperature of 60 to 200 < t for 1 minute to 2 hours. The coating film obtained from the photosensitive wax composition of the present invention can be photolithographically etched and used as a negative photoresist (especially permanent photoresist). When the photosensitive resin composition of the present invention is used as a negative-type photoresist, when the coating film formed by applying the 2 2 optical resin composition of the present invention onto a substrate is irradiated with an active amount line, 'After coating the photosensitive resin composition with a mask, and selectively irradiating the active energy ray, the light-shielding portion (unhardened portion Γ: organic solvent, developer, etc. is dissolved, dispersed, and removed (sometimes A patterned hardened film is formed by ''''person=)'. As an organic solvent for dissolving and dispersing the light-shielding portion, for example, an aqueous test solution, an acidic water 154534.doc 20·201140243 solution, acetone, Methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol n-propanol, present, propanol monodecyl ether, propylene glycol monomethyl acetate, ethyl acetate, butyl acetate, toluene, o-di Toluene, m-diphenylene oxide, p-xylene, 1,3,5-trimethylbenzene, 1,3,4-trimethylbenzene, etc. The cured film obtained by the photosensitive resin composition of the present invention is transparent Properties, insulation, refractive index, heat resistance, weather resistance, chemical properties Different, it can be used as a sealing material for led, etc., an optical waveguide, an optical transmissive mirror, an insulating film for a semiconductor device, especially when used as a gate insulating film of a transistor, the carrier is trapped to lower the charge mobility. The problem is small, and it can be excellently used as a gate insulating film of an organic thin film transistor. [Examples] Hereinafter, the present invention will be further described by way of examples and comparative examples, but the present invention is not limited thereto. Example A: Production of Polyoxane Compound A] In a reaction vessel equipped with a stirrer, a thermometer and a reflux, 3 〇 methacryloxypropyltrimethoxy decane 124 2 g (0 5 mol) was added. , phenyl dimethoxy decane 39.7 g (〇 2 mol), dimethyl dimethoxy decane 132 2 g (ll mole), diphenyl dimethoxy decane 75 3 g (〇 2 Mo 3) Butanol 300 g as a solvent. After stirring and heating to Sichuan, 100 parts of a 12% aqueous phosphoric acid solution was added dropwise, and further reacted at 80 t for 1 hour. After adding 3 〇〇g of toluene, stirring was stopped. The separated aquifer is removed. The toluene layer is washed 3 times with water 1 〇〇〇g after nitrogen The solvent was removed under reduced pressure at 4 〇t:, 300 g of triethyl orthoformate was added thereto, and 154534.doc -21 · 201140243 was treated at 1301 for 1 hour, and then under a nitrogen stream at 80 ° C. The volatile component such as unreacted triethyl orthosilicate was distilled off under reduced pressure to obtain the polyoxymethane compound A of the present invention. The mass average molecular weight was 75 00 by GPC analysis, and 1H-NMR was used. (Nuclear magnetic resonance spectroscopy) analysis revealed that no decyl alcohol group was detected. [Production Example B to I: Production of Polyoxane Compound B to I] In the production example A, the alkoxy group shown in Table 1 was used. The same operation as in Production Example A was carried out except for the decane compound, and the polyoxy siloxane compounds B to I shown in Table 1 were synthesized. The value of the table t indicates the reaction of the alkoxydecane compound. Among the polyoxyalkylene compounds of Table 1, the polyoxyalkylene compounds A to E are the polyoxyalkylene compounds of the present invention, and the polyoxyalkylene compounds F to I are the polyoxanthene compounds for comparison. Further, the analysis results of the mass average molecular weight and the calcined alcohol group content are shown in Table 2. [Table 1] Polyoxane compound ABCDEFG Η I 3-Methyl propylene methoxy propyl trimethoxy decane 25 25 25 15 15 - - - Phenyl trimethoxy decane 10 10 25 15 70 10 10 10 10 dimethyl dimethoxy decane 55 54 20 20 5 55 53 55 55 diphenyl dimethoxy decane 10 10 30 50 10 10 10 10 10 2-(3,4-epoxycyclohexyl)ethyl three曱 矽 - - - 1 - - - 25 - - - 3 - (glycidoxypropyl) ethyl trimethoxy decane 25 - vinyl methoxy dimethoxy decane - - - - - - 25 - - 曱Diethoxy decane 25 - 154534.doc -22- 201140243 [Table 2]

Mass average molecular weight, calcined alcohol-based polyoxyalkylene compound A 7500, no polyoxyalkylene compound B 7600, no polyoxyalkylene compound C 5600, no polyoxyalkylene compound D 3200, no polyoxyl Alkane compound E 8300 No polyoxyalkylene compound F 7600 was detected. Polyoxyalkylene compound G 7500 was not detected. Polyoxyalkylene compound was not detected. 700 7700 No polyoxyalkylene compound I 7900 was detected. [Examples] 1 to 7 and Comparative Examples 1 to 5] Poly(2,6-dimethoxybenzoquinone) as a ruthenium radical generator using polyoxy siloxane compounds A to I, acrylates A and B described below Phenylphosphine oxide (hereinafter referred to as photoradical generator 1), 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as photoradical generator 2), [4-(2-chloro) as a photoacid generator Peptidyl-4-benzylidene phenylthio)phenylbis(4-chlorophenyl)phosphonium hexafluoroantimonate], platinum-divinyltetramethyldioxane as a hydrogenation catalyst And a butyl acetate as a solvent, and the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were prepared according to the composition of Table 3 or thermally hardened. Resin composition. 154534.doc -23- 201140243 [Chem. 14] 0

II ch2=ch-c-o-ch2ch

Acrylate A ο ιι CHf〇—C—CH=CH2 Ο

II c2h5-c-ch2-o-c-ch=ch2 0

II CH^O—C—CH=CH2 [Table 3]

Acrylate B Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 5 Polyoxane Compound A 100 - 100 Polyoxane Compound B - 100 - 100 - - - - - - - - Calcined compound C - 100 polyoxyalkylene compound D 100 polyoxanthene compound E - 100 polyoxy siloxane compound F - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Polyoxyalkylene compound Η - 50 - - - Polyoxane compound I - - - - - - - - - 100 - - Acrylate A 100 Acrylic vinegar B 100 Photo radical generator 1 5 5 Photo radical Producer 2 - - 5 5 5 5 5 - - - 5 5 Photoacid generator 3 - 3 - - Hydrogenation catalyst - 0.001 - - - Solvent 150 150 150 150 150 150 150 150 150 150 100 154534.doc - 24-201140243 <Evaluation of the photosensitive resin composition as the gate insulating film> The photosensitive resin composition or the thermosetting resin composition obtained in the above Examples and Comparative Examples was used as the characteristics of the gate insulating film. Evaluation, by the following method FIG 1 represents the organic thin film transistor. An extraction electrode having a width of 2 mm and a thickness of about 100 nm was formed as a gate electrode 4 by vapor-depositing chromium (Cr) on the glass substrate 6. The photosensitive resin composition of the examples 1 and 2 and the comparative example 1 and the thermosetting resin composition of the comparative example 2 were spin-coated, and the air-dried resin composition of the comparative example 2 was spin-coated, and the air-drying was carried out after the film thickness was about 1 μη. In Examples 丨 and 2 and Comparative Example, 500 mj/cm 2 was irradiated with a high-pressure mercury lamp, and in Comparative Example 2, the atmosphere was heated at 150 ° C for 2 hours, thereby hardening the compositions to form a gate. Insulating film 5. On the gate insulating film 5, a solution of poly(3-hexyl)thiophene in xylene was spin-coated at a film thickness of 3 〇 nm and air-dried to form an organic semi-V body film 1. In order to activate the poly(3-hexyl) porphin, it was annealed at 150 C for 30 minutes under nitrogen gas. The source electrode 2 and the drain electrode 3 having a channel width of 2 mm, a thickness of about 3 〇 nm, and a channel length of 100 μΐ are formed by evaporation of gold (Au) on the organic semiconductor ruthenium film 1, and the examples and comparisons are made. In Examples 1 and 2, 12 bottom gate/top contact type organic thin film transistors were fabricated, respectively. With respect to the organic thin tantalum transistors of the actual target examples 1 and 2 and the comparative examples 1 and 2, the transfer characteristics were measured using a semiconductor parameter analyzer (manufactured by Keithley Co., Ltd., product name: SCS42), and the charge mobility μ was calculated. Furthermore, the charge mobility is defined by the following formula, specifically, the saturation region I54534 when the square root of the absolute value of the drain current Id is the vertical axis and the gate voltage Vg is plotted on the horizontal axis. .doc -25- 201140243 The slope of the domain map is used to determine the charge mobility μ. The measurement was carried out under a nitrogen atmosphere and under a light-shielding state. The charge mobility μ is set to the average value of the organic thin film transistors for which the transfer characteristics are successfully measured, and the number of organic thin film transistors which have failed to measure the transfer characteristics due to current leakage is the number of defective products. The results are shown in Table 4. 〇[Number 1] ID=WCp(VG-VT)2/2L Id ·> and polar current W: channel width of the transistor L: channel length of the transistor C: static of the gate insulating film Capacitance Vg: gate voltage VT: threshold voltage of transistor μ: charge mobility [Table 4] Charge mobility (μ) Number of defective products Example 1 5.3χ10'3 0/12 Example 2 3.8χ10'3 0/ 12 Comparative Example 1 8.7xl〇·4 0/12 Comparative Example 2 2.3 χ 4 '4 6/12 <Evaluation of Thermal Coloring Property of Photosensitive Resin Composition> On a glass substrate of 2.5 cm square, after drying The photosensitive resin compositions of Examples 3 to 7 and Comparative Examples 1 and 154534.doc -26-201140243 Ο 3 5 were applied by spin coating so that the solvent was volatilized by a film thickness of about 500 μm. The test piece was heat-treated at C for 3 minutes. A light I of __ is disposed on the upper portion of the glass substrate after the heat treatment, and a mercury lamp is used to irradiate the ultraviolet ray, and then the test piece is immersed in the sinter which is added with ethyl acetate to remove the unhardened portion, and the air-dried material is used. As a test piece for heating coloring property evaluation. The test pieces were all colorless and transparent, and the refractive index of the cured product at a wavelength of 837 nm is shown in Table 6. The test piece was taken out and the hate of the thief was taken out for 15 days, and the color of the cured product was visually observed, and the heat coloring property was evaluated according to the following evaluation criteria. The results are shown in the table $. <Evaluation Criteria> ◎ - No coloration was observed. 'The heat coloring property was low. 〇 : Slightly colored 'Thermal coloration is slightly higher. △: Significant coloring, high heat coloring property. ❹ I54534.doc :··················································· [Table 5] Example Refractive Index Example 3 1.515 Example 4 1.513 Example 5 1.557 Example 6 1.566 Example 7 "1.520 Comparative Example 1 1.512 " Comparative Example 3 1.511 Comparative Example 4 1.506 Comparative Example 5 1.550 -27 - 201140243 As shown in the results of Table 4, the gate insulating film obtained by curing the photosensitive resin composition of the present invention can obtain a high charge mobility. In contrast, a polyoxyalkylene compound having an epoxy group is obtained. A gate insulating film (Comparative Example) obtained by curing a photosensitive resin composition of a photoacid generator and a polysiloxane compound having a vinyl group, a polyoxyalkylene compound having a SiH group, and hydrogenation of hydrazine The gate insulating film obtained by curing the thermosetting resin composition of the catalyst (platinum catalyst) (Comparative Example 2) only obtains a low charge mobility, and in particular, the latter has a problem that the defective product rate is high. As a result of 5, the photosensitive resin composition of the present invention can be used as a negative photoresist, and the cured product has a high refractive index and is low in heat coloration even at a high temperature (Examples 3 to 7). In this case, the cured product obtained by curing the photosensitive resin composition different from the photosensitive resin composition of the present application has a high heat coloring property (Comparative Example), which indicates that the photosensitive property of the present invention is obtained. When the resin composition is used for a transparent high refractive index material such as a lens, an optical waveguide, or the like, it can be used without losing transparency even if it is high: [Simplified drawing] The photosensitive resin of Examples 1 and 2 and Comparative Examples 1 and 2 was not shown as a schematic cross-sectional view of the organic thin film transistor of the bottom gate/top corner of the gate insulating film. Description of component symbols: Organic semiconductor germanium (layer) source electrode > and electrode 154534.doc •28· 201140243 Gate electrode insulating layer (gate insulating film) Support (substrate) 4 5 6 Ο

G 154534.doc -29-

Claims (1)

201140243 VII. Patent application scope: 1. A photosensitive resin composition containing a polyoxyalkylene compound having a unit represented by the following general formulae (1) to (4) and a photo radical generating agent: R1 0 un I II 2 H2C=C—C—0—R—S i 03/2 (1) (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents a carbon number which may have a substituted alkyl group of 1 to 5 R2O'Si03/2 (2) (wherein R3 represents a hydrogen atom or an alkyl group having a carbon number of 44); [Chemical 3] [R^SiO^ ο) (wherein, R represents an alkyl group having a carbon number of 6~6 or a cycloalkyl group having a carbon number of 5 or 6), 〇[Chemical 4] (wherein R5 represents a hydrogen atom or an alkyl group having a carbon number of 4). 2. The photosensitive resin composition according to claim 1, wherein the polyoxan compound having the unit represented by the above formula:) is further represented by the following formula (5): 154534.doc 201140243 E-Si〇3/2 (6) (wherein E represents a group having an epoxy group). 3. If you are asking for it! In the photosensitive resin composition, the polyoxosiloxane compound having the unit represented by the above formula (1) (4) is an alkoxydecane compound represented by the following formulas (1a) to (4a) or Hydrolytic condensation of a halogenated decane compound: [Chem. 6] R1 0 u\ II 2 , n2c-c-C-0-R-si -|-X1 ]3 (la) (wherein R1 and R2 are in communication with the above The formula (1) has the same meaning, 乂, represents a halogen atom or an alkoxy group having a carbon number of 1 to 4); [Chem. 7] R30_s(tetra)(2a) (in the formula, R has the same meaning as in the above formula (2), χ 2 And a halogen atom or a carbon number of 1 to 4; * a carbon number of 1 to 4 alkoxy); [Chemical 9] 154534.doc 201140243 (wherein π and the above formula (4) means (four), a prime atom or an alkoxy group having a carbon number of 1 to 4). The composition of the present invention has a mass percentage of from 1 to 10 parts by mass based on 100 parts by mass of the polyoxazane compound having the above-mentioned composition. Ο 154534.doc