TW201207561A - Photosensitive composition, cured film obtained from the composition, and display device having the cured film - Google Patents

Abstract

A positive photosensitive composition capable of forming a cured film having excellent liquid repellency and UV ozone ashing resistance is provided. The photosensitive composition includes a polymer (A) containing a siloxane structure and a 1, 2-quinone diazide compound (B). The polymer (A) containing a siloxane structure uses a radical polymer in which the monomers contain a specific siloxane compound and an alkali-soluble radical polymer monomer. The specific siloxane compound has two radical-polymerizable positions. The alkali-soluble radical polymer monomer has ability to make the polymer (A) alkali-soluble and radical polymerizable.

Description

201207561 The Pi wall material can be formed into a patterned film by a known method of the above-mentioned (four) graded polymer composition and a photosensitive composition. In the barrier material, the characteristics of the liquid substance which is not attached to the nozzle head of the ink jet apparatus, that is, the ink repellency, are required (for example, refer to Japanese Patent Laid-Open No. Hei 11-281815 and Japanese Patent Laid-Open No. Hei 2) 〇〇4 149699). Further, in the semiconductor manufacturing*LCD manufacturing process or the like, an ozone ashing treatment step is performed to improve the ink coating property or wettability of the opening portion to which the liquid material is to be applied. At this time, since the surface of the barrier material is also treated, it is required to reduce the barrier of the barrier material, but it is resistant to such a treatment, and the barrier material which can reduce the surface repellency can be suppressed. As described above, the use of the photocurable polymer composition and the photosensitive composition is not only a material constituting the layer of the display member, but also extends to the manufacture of the display element. The use of this kind of expansion 'requires more performance than the previous ones for the optical hard recording polymerization quilting and the sensation composition. SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive composition which can form a cured film excellent in liquid repellency and ozone ashing resistance. Further, an object of the present invention is to provide a cured film of such a positive photosensitive composition and a display element having such a flaw. In order to solve the above problem (4), the inventors of the present invention conducted a keen study, seeing that the polymer obtained by using the multi-functional Shixia Oxygen-based early body copolymerization in the photosensitive composition can be used for secret money. Resistant to a cured film excellent in ozone ashing, thereby completing the present invention as shown below. 4 201207561.

[1] A photosensitive composition comprising: an inclusion compound (A) and a 1,2-diazide quinone compound* (B), wherein the polymer (4) is a monomeric mixture of the following compounds (1) The oxiranated person represented by the formula (1), the free radical (A), the soluble solubility test and the radical polymerizable polymerizable monomer, the test/combination free radical [Chemical 1]

Si-rA^

(1) In the formula (1), R1 to R4 each independently represent hydrogen, or any of the fluorene groups which may be substituted by fluorine and which are not continuous may also be an alkyl group having an oxygen = month & , Αι and Α2 respectively represent radical polymerization = official anti-base ' η represents 1 to i, an integer of 〇〇〇. [2] The photosensitive composition according to [1], wherein the alkali-soluble radical t-bonding monomer comprises a radical selected from a radically polymerizable green body having an unsaturated carboxylic acid and having an unsaturated carboxylic acid anhydride. One or more of the group consisting of a base polymerizable monomer and a radical polymerizable monomer having a transradical group. [3] The photosensitive composition according to [1] or [2] wherein the alkali-soluble radical polymerizable monomer comprises a radical polymer monomer represented by the formula (2), 5 201207561. JO^OUplf [Chemical 2]

In the formula (2), R5 to R7 respectively represent hydrogen, or any of the hydrogens may be substituted by fluorine, and the carbon number is 1 to 3, and R8 to R12 respectively represent hydrogen, and dentate ' _CN ' _CF3 ' -OCF3, The radical "any methylene group may be substituted by _c〇0-, -OCO-, -CO- and any hydrogen may be substituted by a ketone with a carbon number of 1 to 5 or any hydrogen. An alkoxy group having a carbon number of 1 to 5 which can be substituted by a functional element. Among them, at least one of r8 to r12 is a hydroxyl group. [4] The photosensitive composition according to any one of [1] to [3] wherein the polymer (A) having a siloxane structure further comprises oxime represented by the formula (1). A radical polymer of a radical polymerizable monomer other than an alkyl compound and an alkali-soluble radical polymerizable monomer. The photosensitive composition according to [4], wherein the other radical poly-sigma monomer comprises a 7-city compound represented by the formula (1), [Chemical 3] 201207561 -5〇y〇upif in the formula (3) R13 to R17 each independently represent an arbitrary hydrogen group which may be substituted by fluorine, and any methylene group may be substituted with an oxygen group having an alkyl group having 1 to 30 carbon atoms or a number of valences of 1 to 500 (alkyl/hyun). Oxy) decyloxy, A3 represents a radical polymerizable functional group, and η represents an integer of 0 to 1,000. [6] The photosensitive composition according to [5], wherein the other radical polymerizable monomer is a oxoxane compound represented by the formula (3) wherein η is ruthenium. [7] The photosensitive composition according to [6], wherein R13 to R15 of the formula (3) are each represented by the following formula (5), [Chemical 4]

(5) In the formula (5), the alkyl group of 20 or the carbon number 21 to R23 independently represents hydrogen, and the alkoxy group having a carbon number of 1 to 〜 20 (wherein the terminal R21 to 乂, one疋 The alkyl group or the alkoxy group), m represents an integer of from 1 to 500. [8] The photosensitive composition according to any one of [4], wherein the other radical polymerizable monomer contains a (meth)acrylic acid derivative. The photosensitive composition according to any one of [1] to [8], which further comprises a soluble polymer (c), wherein the alkali-soluble polymer (c) = formula (1) The radical polymer of the monomer other than the oxalate compound is represented and has alkali solubility. [10] The photosensitive composition according to [9], wherein the alkali-soluble polymer (C) is selected from the group consisting of a radically polymerizable monomer having an unsaturated carboxylic acid, and having an unsaturated state. A radical polymer of a monomer having at least one of a group consisting of a radical polymerizable monomer of a carboxylic anhydride and a radical polymerizable monomer having a phenolic radical. [11] The photosensitive composition according to any one of [1] to [10] which further contains a solvent. [12] A cured film obtained by calcining a film of the photosensitive composition according to any one of [1] to [11]. [13] A display element having the cured film according to [12]. [Effects of the Invention] The photosensitive composition of the present invention is a solvent-soluble radical polymer containing a monomer of the compound represented by the formula (i), and thus can be formed into a uv ozone ash by applying a type of anti-radiation (tetra) A cured film excellent in liquid repellency in the case of any treatment before and after the treatment. [Embodiment] The photosensitive composition of the present invention includes: a driving material rA, a compound (Β). The oxygen-sintering structure 4 j (A) may be a species of two or more and the u•dimer (B) may be a polymer which may be two oximes and a nitrogen oxime (4) Xiao = (B) is obtained by mixing. (10) M. Polymer containing a siloxane structure (A) 8 201207561. The free polymer of the monomer (4) is a linear bond containing the following compounds and two free radicals having a stone number of 2 or more. (hereinafter, the "oxygenated polymer (A) represented by the formula (1) of the energy base) has a base-polymerizable monomer (a_1)"), and has an alkali-soluble and radical polymerizable base which imparts radical polymerizability. Solubility U-2)"). The early body (hereinafter also referred to as "the polymer of the radical polymerizable monomer monomer (4) having the polymerizable property of the radical polymerizable property 4 means that the thickness of the structure comprising the magnetotelluric structure by spin coating is 0 01 μηι : and heated at 100 ° for 12 minutes before the formation. The film of the second Qing, when washing, for example, around the pit, there is no residual film. ~ Behind the 5 knife, the difference is pure water and M Base polymerizable monomer U-2) ::r,. ==Polymerizable monomer (5)) Content fine ^ wt%^〇°wt〇/0 〇1 Consider, consisting of containing second oxygen sintering It: filling St Self-synthesis monomer in the early body (: 1 1 W: / 〇 ^ 5 〇 Wt% ^ 〇 · 5 - 〇 ^ 30 w; 2 is better than 1 wt0 /. ~ 20 wt%. V more 201207561 1-1-1. Radical polymerizable monomer (al) The radical polymerizable monomer (a-1) is a compound having a linear oxime structure of 2 or more and a radical polymerizable functional group. , expressed in terms of formula. [Chemical 5]

(1) In the formula (1), R1 to R4 each independently represent hydrogen, or any hydrogen which may be substituted by fluorine and which is not continuous, any of the fluorenylene groups may be substituted by an oxygen having 1 to 30 carbon atoms. . Such an alkyl group includes, for example, a fluorinated alkyl group or an alkoxy group having a carbon number of 丄-20. In the formula (1), A1 and A2 each represent a radical polymerizable functional group. A1 and A2 may be the same or different. The radical polymerizable functional group can be used in a radically polymerizable monomer (a-1) having a radically polymerizable structure. Examples of such a radical polymerizable functional group include a known radical polymerizable functional group, and examples thereof include a vinyl group, an anthracene, a vinylene group, a vinylidene group, and a mercapto group. An acrylonitrile group, a styryl group, and the like. The radical polymerizable functional group may further have a substituent in the range in which the radical polymerizability is obtained. Examples of such a substituent include an alkylene group having 2 to 10 carbon atoms; an alkoxy group such as a methoxy group or an ethoxy group; and a branched alkyl group such as an isopropyl group and a different 201207561 joyoupif butyl group. It is better to obtain good from 5 in the formula (1), and n is an integer. From the viewpoint of the developability, n is preferably 2 to 5 Å, 〜300, and still more preferably 1 〇 to 15 〇. The radically polymerizable monomer (a-1) may, for example, be a univalent monomer having a methacryl fluorenyl group at both ends of the formula (1_〇). The deterioration caused by the next job's addition to the (four) water-soluble solution, which is high in color (highly visible), easily obtains a pattern-like transparent film, and exhibits solvent resistance, high water resistance, and acid resistance. From the viewpoint of the photosensitive composition having a high adhesion to the substrate or the cured film, it is preferred to use a Wei-shirt monomer for the radical polymerizable monomer (al). In the formula (1-1), η represents an integer of 1 to ι, 〇〇〇. [Chem. 6]

(1-1) A radically polymerizable monomer (a-Ι) is also commercially available. The compound represented by the formula (Ul) is, for example, Silaplane FM7711 (trade name, manufactured by CHISSO CORPORATION). 1-1-2. Radical polymerizable monomer (a_2) The radically polymerizable monomer (a_2) has alkali solubility and radical polymerizability which impart solubility to the polymer (a). Radical polymerizable monomer (a_2) 201207561 Solubility refers to a salt which forms a water-soluble salt by a base even in the form of a radical polymerizable monomer. Providing that the structure has a moiety which is free from a radical, such as a free radical polymerizable monomer (a_2), and a radical polymerizable monomer Body ^ The nature of free radical polymerization. The Aβ x danta early body enters the 人 仃 人 官 官 官 官 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基Dissolved in the site of the shot and the free filament (4) coated with such a radical polymerizable monomer (a 2), such as a free-filament monomer which can be deuterated and tickered, contains an unsaturated Wei polymerizable monomer, and contains __ The self-rotating polydition of the base is composed of a radical polymerizable monomer having an unsaturated Wei, for example, a saturated spheroidal free-synthesis monomer = t: a sour liver, a radical polymerization containing a desired thiol group J lifts the horse: the vinyl group of the fiber base has a base group == a vinyl group with a phenolic hydroxyl group Shu may hinder compound. For formula (2) is the [η D 11 D 12 of

12 (2) 201207561 ^oyoupif In the formula (2), R5 to R7 respectively represent hydrogen, or any hydrogen which may be substituted by fluorine with an alkyl group having 1 to 3 carbon atoms, and R8 to R2 represent hydrogen, respectively. , -CN, -CF3, -〇CF3, hydroxy, any methylene group may also be substituted by -oco-, -Co- and any hydrogen may be substituted by halogen with an alkyl group having an alkyl number i~5. Or any hydrogen may be substituted with a halogen to have an alkoxy group having a carbon number of 丨~5. Wherein at least one of R8 to R12 is a hydroxyl group. From the viewpoint of improving alkali solubility, it is preferred that R5 to R7 and R8 to R12 other than the substituent are hydrogen. The compound of the formula (2), for example, is exemplified by 4-phenylphenyl ketone ketone. The vinyl ketone having a phenolic hydroxyl group can be obtained by synthesis by a known method' or can be obtained in the form of a commercially available product. For example, 4 phenyl ethyl ketone can be obtained by the following method as described in Japanese Patent Laid-Open Publication No. Hei-4-189715: a gas of 2·chloroethyl·4·methoxyphenyl ketone; a burning solution; In the pure addition of the mixture, the resulting mixture is shouted, the acid vinegar is cooled and the mechanical phase is extracted, and the phase obtained by the water-soluble material is made acidic by hydrochloric acid, and then the extraction machine is further mixed with acetic acid. The styrene is derived from the age of the miscellaneous, and the polymerizable double bond of ethylene. Having a succinct record ^ List _ phenyl benzene, styrene, and 1-1 _ 3 · other radical polymerizable monomers (a-3) 3 containing Wei Shao structure of polymer (A) From the viewpoint of increasing the number of additions, it is preferred to include a Wei-Structure J = ), and the step comprises a radical polymerizable monomer U.1) and from: 13 201207561 -^ν^ν/νρίί* , the monomer (a_2) radical polymerization (5)) self-material polymer. The high-cut-cut structure of the polymer (4) is ^^ two fine. From the point of view of the characteristics of the polymer α containing the Shihe oxygen structure, or the considerations, the composition of the structure of the structure of the stone-like oxygen-burning body is tested. The free radical polymerized body heart = two: = the soul of the single Zhao Zhong, More preferably 70.0 wt% ~ 99 5 w _ wt% ~ " 9 wt% ~ 99.0 wt%. Further preferably, the radical polymerizable monomer represented by 80.0 radically polymerizable monomer (for example, an oxime-emitting compound, an epoxy-containing compound), an N-substituted maleimide, a monomer, and a methyl group are radically polymerizable. monomer.匕&1% pentyl [Chemical 8]

- wherein the formula (3) + R to R17 independently represent any hydrogen, and the fluorine is substituted, and the methylene group of 3⁄4 may be substituted by oxygen, or the base of the group. The f-number of Wei 1~500 three (silk/alkoxy) is an alkyl group, an A-radical polymerizable functional group, and an integer of 0 to 1,000. Wherein ' is preferably when η is G, and Rl3 to Rl5 are each a group represented by the formula 201207561. jo^uupif (5). Further, the radical polymerizable functional group A3 has the same meaning as the radical polymerizable functional group in the above formula (1). Further, "tris(alkyl/alkoxy)" means three groups including one or both of an alkyl group and an alkoxy group. [化9] (p^22,

Si—〇]—(5) R23 In the formula (5), R21 to R23 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms (wherein the terminal R21~) At least one of R23 is the alkyl group or the alkoxy group). m represents an integer from 1 to 500. The alkoxyalkyl compound represented by the formula (3) is, for example, α-butyl-ω-(3-mercapto propyleneoxypropyl)polydimethyloxane represented by the formula (3-1). Product name: FM07U, manufactured by CHISSO CORPORATION). It is considered to be free from the viewpoint of containing the flaws and improving the surface liquid repellency.化h3〒h3 2 十〒-oj—〒—C4Hg \ ChVn CH3 ch3 (3-1) h2c=c-c-o-ch2ch2ch

II 〇 Furthermore, a oxane compound represented by the formula (3) and n is 0, for example, 15

201207561 ^ ^ AX exemplified by 3-methacryloxypropyltrimethoxydecane (trade name: S710 &gt; CHISSO CORPORATION t ϋ ) &gt; 3-propenyl bis(dimethyl decyloxy) decane (commodity Name: TM0701T, manufactured by CHISSO CORPORATION), and 3_mercaptopropoxy methoxymethyl λ dimethoxy Wei (trade name: ΚΒΜ_5 () 2, manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, from the point of view of improving the solubility of the test developer, it is difficult to make 3-methyl-propyloxypropyl three? Oxygen Wei. Examples of the epoxy group-containing radical polymerizable monomer include glycidyl (mercapto)acrylate, decyl glycidyl (mercapto) acrylate, and (3,4-epoxycyclohexyl methacrylate). And 3·ethyl_3_(indenyl)propene rare earth oxymethyl epoxide I These compounds are readily available, and the solvent resistance, water resistance, acid resistance and resistance of the resulting patterned transparent film are improved. The viewpoint of alkalinity, heat resistance, and transparency is preferable. The (fluorenyl) acrylic acid derivative may be a derivative having a polymerizable double bond of (meth)acrylic acid. For example, a (meth)acrylic acid derivative Examples thereof include methyl methacrylate formazan, ethyl propyl acetoacetate, isopropyl methacrylate, n-propyl decyl acrylate, n-butyl decyl acrylate, isobutyl methacrylate, hydrazine. Alkyl methacrylate such as butyl acrylate, hexyl methacrylate or ethyl hexyl acrylate; thiol acrylate having aromatic ring, such as benzyl methacrylate or phenoxyethyl methacrylate Alkyl ester; hydroxy decyl acrylate, methacrylic acid - 2-hydroxyethyl ester, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxyamyl decyl acrylate, hydroxyhexyl methacrylate, etc., alkyl methacrylate having a hydroxyl group; Dialkylaminoalkyl decyl acrylate such as diamylaminoethyl acrylate 201207561 joyoupif ester; and aryl methacrylate such as phenyl methacrylate. N-substituted maleimide, for example, N-fluorenyl Maleic imine, N-ethyl maleimide, N-butyl maleimine, N-cyclohexyl maleimide, N-benzyl maleimide, N-benzene Kamalyimide, n-(4-ethylmercaptophenyl)maleimide, N-(2,6-diethylphenyl)maleimide, n-(4-dimethylamine -3,5-di-diphenyl) maleimide, Ν-(ΐ·anilinonaphthyl-4) maleimide, Ν-[4-(2-benzo. oxoyl) Phenyl]maleimine, and fluorenyl-(9-acridinyl)maleimide. Examples of the radical polymerizable monomer containing a dicyclopentyl group include dicyclopentyl acrylate and methyl group. Dicyclopentyl acrylate. Resistant to the cured film formed by the photosensitive composition from the south From the viewpoint of the nature, it is preferred that the radical polymerizable monomer (a-3) contains one or both of a fluorene-substituted maleimide and a radical-polymerizable monomer containing a tricyclic ring. The structure of the polymer (Α) monomer, 2 = the structure of the polymer (4) alkali solubility from the viewpoint of 冋 'ϋ from (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid: oysters and have a secret The styrene derivative is contained in the monomer or more. The polymer (Α) of the structure can be obtained by: adding a radical polymerizable monomer (6)) and self = ((4)' and if necessary, adding the self-preserving body to make these compounds free-hearted - h U-flat (a-3), proceed. Polymerization by a radical poly 5 4 radical can be carried out by a known method. 17 201207561. The polymerization of the polymer (4) of the package 4 is particularly advantageous. However, it is difficult to carry out radical polymerization using a solution solution. The poly & temperature is particularly limited by the polymerization initiator used, and is particularly limited to the range of 耽~15 generations: poly: no special mosquitoes, pass f! Hours ~ 24 hours range. Further, the edge polymerization s can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure. The solvent to be used freely is preferably a solvent which can dissolve the ruthenium-based precursor and the product. The solvent may be one type or two or more types. Examples of the solvent include decyl alcohol, ethanol, "tetrahydrofuran, ethanol monoethylidene, glyceryl ether, diethoxypropionic acid ethanol, acetone, 2-butanone, ethyl acetate, propyl acetate-nitrile, dioxins. Alkane, toluene, xylene, cyclohexanone, ethyl ketone monodecyl ether, propylene glycol monoterpene ether acetate, diethylene glycol decyl ethyl ether, decyl 3-methoxypropionate, vinegar, and hydrazine , Ν-dimercaptodecylamine = a polymerization initiator used in the base polymerization, for example, a compound derived from ridge, an azobisisobutyronitrile or the like; and a peroxide initiator such as a peroxide The amount of the monomer used in the =::r is 1. The weight of the two = 1 weight loss 30 parts by weight, more preferably 5 parts by weight to 25 weight / 疋 and, in the radical polymerization, in order to adjust the molecular weight , ° ° = 3: transfer agent. The amount of chain transfer agent added relative to the formation of I: sheep, , # 1GG weight of 4 parts is preferably part by weight, more preferably 0.005 parts by weight ~ 0.03 weight里刀. 〇.05 self-exposure part in alkaline developer until dissolved maiden corpse, 18 201207561 jo^uupif when and the surface of the film during development From the viewpoint of being difficult to roughen, it is preferred that the polymer (A) having a siloxane structure has a weight average molecular weight of 1'GGG to 100, 〇〇〇. Further self-developing residue becomes extremely small from the viewpoint of 'weight The average molecular weight is more preferably 1,5 〇〇 5 〇, 〇〇〇, and even more preferably 2,000 〜 2 〇, 〇〇〇. The weight average molecular weight can be determined by GPC analysis based on polystyrene standards. For example, polystyrene having a molecular weight of 500 to 150,000 (for example, PL2010-0102 (S-M2-10) standard manufactured by Polymer Laboratories) can be used, and the tube can be used as Shodex PLgel MIXED-D (Polymer Laboratories). Manufactured, the mobile phase at the time of the measurement may be THF. The weight average molecular weight may be determined under such conditions. Further, the monomer of the polymer (A) containing a siloxane structure may be confirmed to contain ruthenium The specific structure including the ruthenium atom in the polymer (A) of the oxyalkylene structure is confirmed by a known analysis method derived from the structure of the radical polymerizable functional group, for example, by using Si-CH3 which detects 1H-NMR. Peak and It is confirmed by measuring the peak of ethylene or propylene. 1-2. 1,2-diazide compound (B) 1,2·diazide compound (B) A compound used as a photosensitizer in the field of resists. Examples of the 1,2-diazide compound include a hydroxybenzophenone compound and hydrazine, 2 benzoquinone diazide _4 sulfonic acid or 1,2- alum, diazide _5. sulfonic acid ester, hydroxy benzophenone compound and 1,2-diazepine naphthoquinone_4_sulfonic acid or L2-diazide naphthoquinone _5_sulfonate Acid ester, phenol 201207561 compound and 1,2-cracked diazide _4_sulfonic acid or l,2-benzoquinonediazide_5-supply acid ester, phenolic compound and 1,2-diazide Naphthoquinone-4-sulfonic acid or 1,2-diazepinenaphthoquinone-5-cross-acid ester, a compound in which a hydroxyl group of a phenol compound is substituted with an amine group, and a 1,2-benzene-containing diazide-4-sulfonate Acid or a 1,2-benzoquinonediazide-5-sulfonic acid ore, a phenolic compound having a hydroxyl group substituted with an amine group and hydrazine, 2_diazepinenaphthoquinone-4-sulfonic acid or 1, 2_Diazonaphthoquinone-5-protonic acid sulfonamide. Examples of the perylene diphenyl hydrazine compound include 2,3,4-trisylbenzophenone, 2,4,6-trihydroxydibenzophenone, 2,2,4,4,_tetrahydroxy phenanthrene. Phenylketone, 2,3,3',4-tetrahydroxybenzophenone, and 2,3,4,4'-tetrahydroxydibenzophenone. Examples of the phenol compound include bis(2,4-dihydroxyindolyl)decane, bis(p-phenylphenyl)methane, tris(p-phenyl)methane, and 1Λ1 tris(p-phenylene bromide, Bis(2,3,4-tridecylphenyl)-methyl, 2,2-bis(2,3,4·trihydroxyphenyl)propene, 1,1,3·3 (2,5-di Methyl 4-4 phenyl), phenylene propylene, from (10)-(10), phenyl) small methyl ethyl] phenyl] ethylene phenol, bis (2,5-dimethyl·4 _Phenylphenyl)·2-Phenylphenyl-based, for example, 3|· tetramethyl-1,1'· snail two _5,6,7,5',6,7,_ Alcohol, and tribasic•7,2,,4,-trihydroxyflavone. One base is self-raising and the composition of the silk is transparent, although it is preferable to use di-2-azide stack: two laughing sulfonic acid vinegar , 2,3,4·trihydroxybenzophenone _, and vinegar of 2 醌-5-sulfonic acid, 2,3,4, tetrahydroxydibenzopyrene 1,2-mononaphthoquinone Acid ester, 2,3,4 盥methylethyl] benzyl]ethylene] bispan and bismuth fragrant broth 201207561 Km/ self 曰, and 4,4'm[4-pyridylbenzene a group consisting of η-mercaptoethyl]phenyl]ethylidene]bisphenol and 1,2-diazide naphthoquinone-5-sulfonic acid vinegar 1-3. Other components The photosensitive composition may further contain the above-mentioned polymer (A) containing a oxoxane structure and the 1,2· bis-stuff gas compound (8) in a range in which the effects of the present invention are sufficiently obtained. The other components may be, for example, a soluble polymer (6), a solvent, an additive, and a polybasic acid-fastening needle. 1-3-1. Alkali-soluble polymer (c) Further improving the alkali solubility of the photosensitive composition From the viewpoint of easily obtaining a pattern-like permeability and improving the properties of a cured film such as solvent, high water resistance, high acidity, high hardness, and high age resistance, a photosensitive composition is preferred. Further, the substance further contains an alkali-soluble polymer (8). The hetero-polymer (c) may be of two or more kinds. Further, the "alkali-soluble" in the alkali-soluble polymer (c) means that it is to be spin-coated. The decrease of the soluble polymer (c) is as follows: a film having a thickness of 0.01 μm to 1 μmη formed by heating under the arm for 1 minute, for example, 2.38 wt% of tetradecyl hydrogen at about 25 ° C. Immersion in aqueous ammonium oxide solution 5 After the bell's cleaning by pure water, no film remains. A free radical polymer can be used in the soluble polymer (C), which is a method in which the obtained polymer has alkali solubility. 'Separating two or more kinds of radicals contained in the radical polymerizable monomer (a_2) or the radical polymerizable body (a 2) and the free silky monomer (a_3) towel 21 201207561. : Sexual early body The radical polymerization is carried out. Such a radical polymerization is considered to have a physical property of the photosensitive composition of the present invention having the use amount of the alloy (A) to obtain a desired function (C). )in. In the case where the base is soluble in the alkali-soluble polymer (C), the conjugate monomer (a-2) can be used as the free-filament property of the reduction, and the alkali solubility of the photosensitive composition can be improved. In view of the above, the monomer of the polymer (C) is one or more selected from the group consisting of (?)-acid anhydride, warp vinyl, and 4-phenylene. From the viewpoint that the self-exposed portion is in the expansive developing solution until the development time of the dissolution is appropriate and the surface of the film is difficult to be roughened at the time of development, the weight average molecular weight of the soluble polymer (C) and the stone containing the stone are preferably considered. The polymer (A) of the oxygen-oxygen structure is similarly 1, _~; from the point of view of the smear of the smear of the smear of the smear of the smear of the smear; The best is 2,000~2〇, _. Check the solubility of the polymer* (C)! The average molecular weight can be determined, for example, by Gpc analysis under the same conditions as the polymer (A) having a 7-oxo (tetra) structure. The soluble polymer (C) can be obtained, for example, by the same polymerization method as the polymer (4) containing a decane structure. Further, the monomer of the soluble polymer (C) can be estimated, for example, by measuring the gas generated by thermal decomposition by GC-MS when the alkali-soluble polymer (C) is thermally decomposed. 1-3-2. Solvent 22 201207561. o〇yO\)pii The photosensitive composition preferably further contains a solvent. The solvent is preferably a ~τ-dissolved photosensitive composition_polymer containing a oxy-combustible structure (A), a 1,2-azide g-kun compound (Β), and a soluble polymer (c) = dissolve,. Further, the solvent preferably has a boiling point of 1 〇 (rc 〜 3 〇 (the solvent of rc can be one type of solvent or two or more types. The boiling point is 10 (TC~30 (the solvent of TC is, for example, butyl acetate) Ester, propylene, acetoacetate, ethyl acetoacetate, decyl oxyacetate, ethyl oxyacetate, oxymethyl ester, methyl methoxyacetate, ethyl decyloxyacetate, decyloxyacetate ~, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, 3,3-oxypropionic acid 醆曰t3.oxypropionic acid ethyl ester, 3_methoxypropionic acid methyl ester, 3_decyloxypropyl ester , 3_ethyl ethoxypropionate, ethyl 3-ethoxypropionate, 2-oxypropene = methyl, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-曱oxy oxime ester '2-methoxypropionic acid ethyl ester, 2-methoxyoxypropionic acid propyl ester, 2_B=base acid formazan, 2-ethoxypropionic acid ethyl vinegar, 2_ Ethyloxy 2-indole propionate 2厶 gas base-2·mercaptopropionate ethyl ester, decyloxy-2-methylpropionic acid methyl ester, oxy-2-methyl propionate ethyl ester, C Methyl decanoate, ethyl acetonate, propionate-, propylene sulfonate, ethyl acetacetate, ethyl acetate, ethyl 2-oxo-butoxybutyrate Oxane, ethylene glycol, diethylene glycol, triethanol propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monobutyl ether, propylene glycol mono(tetra), propylene glycol monomethyl-acid, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, mono-ol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monoterpene ether, ^ ~ alcohol monoterpene ether acetate , diethylene glycol monoethyl ether, diethylene glycol monoethyl, kiln 9, monoethylene glycol monobutyl ether, monoethylene glycol monobutyl acetate, two 23 201207561. ethylene glycol diterpene ether benzene - B * a drunk diethylene, xylene, γ · butyl vinegar, bis = diol methyl ethyl ether, self-improving to form a photosensitive composition of di-diethyl acetamide. Consider, better 岐 solvent is selected Self-coating-sexual view, ether acetic acid brewing, di-diol monoethylation, shouting, propylene glycol monomethyl ethoxy propionate, vinegar mono-I: oxypropionic acid methyl vinegar, 3 · ether acetate vinegar, The consideration of the safety of the human body of the bismuth dimethyl sulfonate, the second, the acetic acid vinegar, the diethylene glycol monobutyl vinegar and the acetic acid butyl 1 : 二卜, from the monomethylhydrazine acetic acid brewing, 3_methoxypropane=疋f agent is selected from the group consisting of propylene glycol diethylene glycol methyl methacrylate, lactic acid ethyl hydrazine, 3 · ethoxy propionate ethyl vinegar, <Group> or more. &lt;Consisting of Japanese and acetic acid TS::: is a point containing 2〇Wt% or more is hidden ~ 3 (8). C = mixing of the agent. Solvent. Mixed solvent The boiling point of the solvent other than fresh c ~ war tyros can be prepared as a known solvent or two or more. 1-3-3. Additive resolution, coating uniformity, heterogeneity, and adhesion In view of the fact that the composition of the sensitized f composition and the cured film formed are further improved, it is preferred that the sensitization composition further contains an additive. The additive can be used in the field of the anti-side agent, in the photosensitive composition. Or various additives for the characteristics of the cured film. The additive may be singly or in combination of two or more. Examples of such an additive include acrylic, styrene, polyethyleneimine or polyamine I polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, and oxirane resins. Coating property 24 201207561 jeyoupif Two-component hard-burning coupler special splicing improver, alkoxy benzophenone and other purple ray absorbers, aggregation inhibitors such as sodium polyacrylate, epoxy compounds, melamine compounds Or a thermal crosslinking agent such as a double azide, and an organic carboxylic acid specific solubility promoter. More specifically, the additive may, for example, be p〇ly£j〇w No. 45,

Polyflow KL-245, Polyflow No.75, Polyflow No.90,

Polyflow No. 95 (all of which are trade names, manufactured by Kyoeisha Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all of which are trade names, manufactured by BYK-CHEMIE JAPAN KK), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS ( All of the above

Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all of which are manufactured by AGC SEIMI CHEMICAL Co., Ltd.), Ftergent 222F, Ftergent 251, FTX-218 (above) All are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are manufactured under the trade name, Mitsubishi Material Co. Ltd.). ), Megafac F-171, Megafac F-177, Megafac F-475, Megafac R-08, Megafac R-30 (all of which are trade names, manufactured by DIC Corporation), fluoroalkylbenzenesulfonate, halothane Carboxylic acid salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkane sulfonate, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), halothane 25 201207561 A Jiazhi: salt, it burns amine sulfonate, polyfluorene polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether polyoxyethylene nonyl phenyl ether, good mystery, polyoxyethylene laurel μ take the fine oil of women's oil, polyoxyethylene three wire _, polyoxyethylene recording 蠛 _ polyoxyethylene stearyl hydrazine, polyoxyethylene酸酸0的,聚氧乙妇油', polyoxyethylene stearic acid s, polyoxyethylene laurylamine, sorbitan lauric acid vinegar, sorbitol liver citrate, sorbitol needle hard Fatty acid vinegar, sorbitol liver vinegar, sorbitol liver fatty acid vinegar, polyoxyethylene sorbitol = laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, a polyoxyethylene sorbitan oleate, a polyoxyethylene oxime, a silk benzene salt, and a silk diphenyl ether salt. Preferably, the additive is one or more selected from the group of compounds. In view of coating uniformity, it is more preferable that the additive is one or both of a fluorine-based surfactant and a silicone resin-based coating property improving agent. More specifically, the coating of the photosensitive composition is improved. From the viewpoint of uniformity of cloth, it is more preferable that the additive is selected from the group consisting of a fluoroalkyl benzene ore self-salt salt, a gas-burning acid salt, a gas-burning polyoxyethylene sulfonium, a smoldering base, a fluorocarbon Base beet test, fluorine calcination acid salt, diglycerin four (gas-fired polyoxyethylene shunt), fluorine-like triammonium , fluoroalkylamine base acid salt; one or more groups of BYK306, BYK344, BYK346, KP-341, KP-358, and κρ-368. 1-3-4. From the viewpoints of heat resistance and chemical resistance of a cured film formed of a photosensitive composition having a soil oxygen, and prevention of photosensitivity caused by decomposition of the 1,2-diazide compound (B) during storage The composition is considered to be in the color of the photosensitive composition of the epoxy group, and it is preferable to react with the epoxy group in the photosensitive composition having the epoxy group. . The multiple ship anhydride may be of one type or two or more types. Examples of the polyindole may include a trimellitic material, a phthalic acid needle, and a 4-methylic acid anhydride. Preferred among the plural axes 17 is trimellitic anhydride. 1-4. The content of each component in the photosensitive composition is preferably from the viewpoint of exhibiting the liquid repellency of the cured film, and the content of the polymer (A) containing a siloxane structure in the photosensitive composition is preferably 2 〇 wt% ~ 80 wt%, more preferably 3 〇 wt 〇 / o ~ 7 〇 wt%, more advanced steps are 40 wt% ~ 60 wt%. From the viewpoint of forming a fine pattern in the cured film, the content of the 1,2-diazide ruthenium compound (B) in the photosensitive composition is relative to the polymer (A) containing the yttrium-oxygen structure and the soluble polymerization. The total amount of the component (c) is preferably 5 parts by weight to 5 parts by weight, more preferably 10 parts by weight to 40 parts by weight, still more preferably 15 parts by weight to 3 parts by weight. . In the photosensitive composition, the content of the soluble polymer (c) is determined when the content of the polymer (A) containing a siloxane structure is 100 parts by weight from the viewpoint of sufficiently exhibiting an effect of improving alkali solubility. It is preferably 20 parts by weight to 150 parts by weight 'more preferably 50 parts by weight to 12 parts by weight, still more preferably 70 parts by weight to 1 part by weight. From the viewpoint of improving the uniformity of coating of the photosensitive composition, and from the viewpoint of safety of the human body, it is preferable that the photosensitive composition is 27 201207561. The content of the solvent of JO^UV/pif is photosensitive. The content of all the solid components in the composition is from 5 wt% to 50 wt%, more preferably from 1 wt% to 45 wt%, still more preferably from 15 wt% to 4 wt%. /. The amount. The content of the additive in the photosensitive composition is higher than that of the polymer (4) and the soluble polymer (c) m^100 parts by weight of the composition and the characteristics of the hard (10). Preferably, 0.01 parts by weight is called part by weight = it is heavy, and the part is ~α7 parts by weight, and more preferably (10) 5 parts by weight to 9.5 parts. From the viewpoint of improving the composition of the above-mentioned Wei film, it is preferable that the photosensitive group money towel 0 yuan New Society contains the polymer of the Shi Xiwei structure (4) and the total of the soluble polymer is 100 parts by weight. Yes! The parts by weight are 3% by weight, more preferably 2 parts by weight to 2 parts by weight, more preferably 15 parts by weight. J疋) More serious injury 1-5. Preservation of photosensitive composition Self-stabilizing the touch of the composition of the rhyme composition ====Production - 2. Curing film of the present invention The cured film of the present invention can be obtained by the above Hair film for the job. Total 鸠 === The insulating film of the small holes below. Here, the insulating film is, for example, a film (interlayer insulating film) which is provided for insulating the wiring between the layers of the layered wiring, and the cured film of the insulating film or the like can be used as an anti-corrosion film. It is formed by a usual method of forming a cured film in the field of a button, and can be formed, for example, in the following manner. First, a film of a photosensitive composition is formed. The film of the photosensitive composition can be formed by applying a photosensitive composition onto a substrate such as glass by a known method such as spin coating, stick coating or slit coating. A preferred coating method can be, for example, spin coating, roll coating, or slit coating. Examples of the substrate include transparent glass substrates such as white glass, blue glass, and ceria coated green glass, and polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, and poly A synthetic resin sheet such as amidoxime or polyimine, a film or a substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate or a stainless steel plate, and another ceramic plate, a semiconductor substrate having a photoelectric conversion element. On these substrates, a chemical treatment such as a decane coupling agent, electropolymerization treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition or the like may be performed as needed. Next, the film of the photosensitive composition is dried. The film of the photosensitive composition can be dried, for example, by heating a substrate having a film of a photosensitive composition by a hot plate or an oven. Usually at 60. (:~120. (:: 1 minute to 5 minutes of drying. ', ruler' is the mask of the desired pattern shape and the dry photosensitive composition is applied. The radiation f ϊϋ ' of the film may be, for example, a photosensitive film which is separated from the substrate by a mask. The irradiation condition depends on the photosensitive composition , =, for example, the photosensitive composition contains u-two. (Β), so the i-line is suitably 5 mJ/cm2~1, 〇〇〇29 201207561, mJ/cm2. In addition, when the cured film having no pattern is formed, the irradiation step of the radiation is not required. The film of the photosensitive composition irradiated with the radiation is washed by the developer to develop the film. The 1,2-diazide compound (B) in the film of the photosensitive composition irradiated with radiation rapidly becomes a ruthenium carboxylic acid. In the state of being dissolved in the developing solution, the portion irradiated with the radiation in the film is rapidly dissolved in the developing solution. The developing method is not particularly limited, and known methods such as dipping development, dip development, and shower development can be used. Any of the methods. In the case of forming a cured film having no pattern, the development step is not required. ° The developer is preferably an alkali solution. The developer may be suitably used as an aqueous solution of alkali. Hydrogen oxyhydroxide, tetrahydroammonium hydroxide, 2·erythryl trimethylammonium hydroxide, Wei sodium, sodium carbonate, carbon _, potassium hydrogencarbonate, sodium hydroxide, and hydroxide are unloaded. Specifically, it may be exemplified by tetramethyl hydroxide, tetraethyl:=ammonium, di- 2, ethyltrimethyl hydroxide, bis- and carbon _'sodium hydroxide or potassium hydroxide. The iri low-developing silk or the realization of the figure-like shape can also be used as a sexual agent. In these _, especially if the interface of adding non-= is active, the viewpoint of improving the resolution is better. Next, the cleaning of the film to be developed is carried out by, for example, washing the film with the substrate by pure 30 201207561, water, and then irradiating the surface of the film to be cleaned. Residual 1,2-diazide ruthenium compound is deactivated by irradiation of the radiation. Irradiation of the radiation, for example, when the radiation is ultraviolet light, is performed by irradiating the film with an exposure amount of 100 mJ/cm 2 . Next, it is difficult to perform calcination on the radiation to obtain a cured film. It can be obtained by heating the crucible for 10 minutes to 12 minutes in (10). C~. By using the step, the cured film is obtained as a transparent film patterned by Jun. Film!^ Γ Capture pattern The transparent film can also be used as a pattern-like insulation = the shape of the hole formed on the edge film, which is square, rectangular, circular or elliptical in shape: the outer trailing edge is a transparent electrode, The film is engraved and patterned. The insulating film has a high minerality, and the transparent film is not wrinkled, and can be kept high. 3. The cured film of the display element device of the present invention. In addition, the use of the cured film of the present invention in the same manner as in the display is similar to that of the element, and can be similarly known to the display. For example, as described above, the display element can be formed on the substrate 201207561t with the (four)-shaped Weilang element surface slab substrate aligned with the two colors previously formed on each substrate to combine other components other than the substrate: The injection port is sealed, whereby liquid is produced in the manufacture of the liquid crystal display element, and the liquid crystal is performed by dispersing the liquid crystal on the element substrate, and then the two ":: color 遽 first substrate are superposed, and the liquid crystal is not leaked. The liquid crystal display element can be produced as such. The liquid crystal, that is, the liquid crystal compound and the composition containing the same are not particularly limited. Any liquid crystal compound and liquid crystal composition can be used. The composition can be formed, for example, with various properties such as a fine-dissolving ship which is generally required for a patterned transparent film and an insulating film, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, and enthalpy, and A cured film excellent in liquid repellency. Further, the photosensitive composition of the present invention has developability and chemical resistance in addition to the above-described high liquid repellency and UV ozone ashing resistance. The general characteristics required for the properties of the resist, the male, the bismuth, etc., also have at least sufficient performance as a resist material. Therefore, the photosensitive composition of the present invention can form a liquid-repellent property. Further, the cured film is excellent in pattern formability. Further, since the film can be used as a transparent film, an insulating film or a protective film, it can be used as a display element. The cured film of the present invention is formed of the photosensitive composition of the present invention. Therefore, even in a solvent, an acid, an alkali solution or the like, it is difficult to produce surface roughness by being subjected to treatment such as impregnation, contact, heat treatment, etc. Therefore, the light transmittance in the too hardened film is high, and a high display element can be obtained. Further, the cured film of the present invention is excellent in liquid repellency of the photosensitive grade product, and prevents the liquid material of the pattern (open π portion) of the film from adhering to the pattern during the manufacturing process of the display element. The desired material is opened upwards. The 15 knives are able to obtain the desired performance efficiently, and the productivity of this product is further improved. 4 Waiting for the display [Example] To: The invention is further exemplified by the examples and is not limited to the examples.

[Synthesis Example 1] A polymer comprising a decane structure (A was charged as a glycol methyl ethyl sulphate in a 4-necked flask equipped with a win, and on the other hand, llg of the bis-diethyl group was tested below The weight is described as a mixture of white earth as a radical polymerizable monomer (a·1), which is represented by the formula (1-1), α, ω, 3 曱 丙 丙 醯Ι Γ: Γ: iOTSS 〇 C 〇 RP 〇TM ΡΜ;7Π: 篁平 Un'_), 4-carbophenyl ketone as a radical polymerizable, glycidyl methacrylate as a radical polymerizable monomer (5), 3·Methyl propylene 醯 ^聚言, 2, 2, _ Qing A heart ^ S 曰 ' Add the amount of the mixture to the small axis: in the solvent, after the drop, take a step under the boot力^ 33 201207561. JO^UUjjif Diethylene glycol methylethyl 趟-ν' 广1 1,11 .〇g oxime (M) of α,ω-bis(3-methylpropenyloxypropane Poly) fluorenyl 0.675 g 6.075 g 2.025 g 4.725 g 2.025 g 3-decyl propylene methoxy propyl trimethoxy decane 4-phenyl phenyl keto keto thioglycol 2, 2 - Azobis(2-mercaptopropionic acid g) 1] }—c—〇—Qh6—

^Ηβ—〇 C II 〇

Ch3 The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of a polymer (A1) containing no oxoane structure containing no dimethyl 2,2,-azobis(2- mercaptopropionate) dinonyl ester. . A part of the reaction liquid was sampled, and the weight average molecular weight was measured by gpc analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (A1) containing the siloxane structure was 4 Å. [Synthesis Example 2] Synthesis of polymer (A2) containing a siloxane structure The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1. Diethylene glycol methyl ethyl ether ll. Og α,ω-bis(3-mercapto propylene methoxypropyl) polydimethyl methoxy oxane of formula (1-1) 0.675 g N-cyclohexyl horse醯iimide 4.725 g 34 201207561 joyoupif 4.725 g 3.375 g 2.025 g Free 2,2,-azobis(2_ mercaptobutyl dicyclopentyl methacrylate 2,2'-even gas double (2-曱) Glycolic acid g) Dimethyl hydrazine is obtained by cooling the obtained reaction liquid to room temperature, and obtaining a polymer containing a cerium-burning structure (a small amount of 2,2,- methoxypropionic acid) A3) 33.3 Wt% solution. A part of the reaction liquid was sampled, and the weight average molecular weight was measured by Gpc analysis (polystyrene standard). The weight average molecular weight of the polymer (A2) of the gentleman's fruit packet 3 stone-oxygen structure is 31 〇〇. [Synthesis Example 3] Synthesis of alkali-soluble polymer (ci) Using α·butyl _ω·(3_mercaptopropyloxypropyl) polydimethyl oxime represented by the formula (3-1) Alkane (FM071, manufactured by CHISSO CORPORATION, number average molecular weight: woo) instead of α,ωκ3_methacryloxypropyl)polydimethyloxane, and the mixed solution was prepared by using the following components under the following weights; Polymerization was carried out in the same manner as in Synthesis Example 1. Diethylene glycol decyl ethyl ether ll.og Formula (3-1) α-butyl-ω_(3-mercapto propylene methoxypropyl) poly&gt;^ oxooxane 0.27 g 3·A Propylene methoxy propyl trimethoxy decane 6.48 S 4-hydroxyphenyl vinyl ketone 1.35 g thioglycolic acid glycidyl ester 5.40 β 2,2'-azobis(2-methylpropionate Dimethyl ester 2.025 g [Chemical 12] ch3

H2C=C-C-0-CH2CH2CH ο / c , r ch3.

i-〇V CH3/n CH3

Si-C4H9 CH3 (3-1) 35 201207561

x]I The obtained reaction solution was cooled to room temperature to obtain a 33 3 wt% solution of an alkali-soluble polymer (C1) containing no dimethyl 2,2,-azobis(2-methylpropionate). A portion of the reaction solution was sampled, and the weight average molecular weight was determined by GPC analysis (polyphenylene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C1) was 2,8 Å. [Synthesis Example 4] Synthesis of alkali-soluble polymer (C2) The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1. ~ Diethylene glycol decyl ethyl ether 11Qg 0.675 g 6.075 g 2.025 g 4.725 g 2.025 g α-butyl-ω-(3-methylpropenyloxypropyl) polydifluorene of formula (3-1) 3-oxomethoxy-3-methoxy methoxysulfate 4-hydroxyphenyl vinyl ketone glycidyl 2,2'-azobis(2-mercaptopropionate) Diterpene ester The resulting reaction solution was cooled to room temperature to obtain 33.3 wt% of the soluble polymer (C2) which was free of 2,2,-ocean bis(2-methylpropionic acid δ) Each of the solutions was sampled, and the weight average molecular weight was determined by GPC analysis (polyphenylene hydride standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C2) was 3,5 Å. [Synthesis Example 5] Synthesis of alkali-soluble polymer (C3) The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1. Diethylene glycol decyl ethyl ether U.Og 36 201207561. α-butyl-c〇-(3-mercapto propylene methoxypropyl) polydifluorene of formula (3-1) 0.675 g 4.725 g 4.725 g 3.375 g 2.025 g 矽 矽 N N-cyclohexylmaleimide hydrazide dicyclopentyl acrylate methacrylic acid 2,2'-azobis(2-mercaptopropionate) dinonyl ester The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of an alkali-soluble polymer (C3) containing no 2,2,-azobis(2-mercaptopropionate) dinonyl ester. A part of the reaction liquid was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the alkali-soluble polymer (C3) was 2,8 Å. [Synthesis Example 6] Synthesis of the soluble polymer (C4) The mixed solution was prepared by using the following components under the following weight, and polymerization was carried out in the same manner as in Synthesis Example 1. Diethylene glycol decyl ethyl ether ll.Og N-cyclohexylmaleimine 4.725 g Dicyclopentyl decyl acrylate 5.400 g Methacrylic acid 3.375 g 2,2'-azo double (2-A Propyl ester) diterpene ester 2.025 g The obtained reaction solution was cooled to room temperature to obtain a soluble polymer containing 2,2'-azobis(2-mercaptopropionate) dinonyl ester ( C3) 33.3 wt〇/〇 solution. A portion of the reaction liquid was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the soluble polymer (C4) was 2,8 Å. 37 201207561 [Comparative Synthesis Example 1] a polymer containing a siloxane structure (m, a mixture of the following components, using the following components to prepare the mixed solution, and a 4-neck flask in the reaction of the solution and the subsequent reaction In the same manner as in Synthesis Example 1, ll.og 6.75 g 1.35 g 5.4 〇g 2.025 g of diethylene glycol decyl ethyl ether σ was prepared in the same manner as in Synthesis Example 1. 3-mercapto acryloxypropyltrimethoxydecane 4-hydroxyphenyl vinyl ketone glycidyl methacrylate 2,2'-azobis(2-mercaptopropionate) dimethyl ester _ The resulting reaction solution was cooled to room temperature to obtain a 33.3 wt% solution of a polymer containing a oxoxane structure containing no dimethyl ester of 2,2,-methoxypropionate. A portion of the reaction solution was sampled. The weight average molecular weight was measured by Gpc analysis (polystyrene standard), and as a result, the weight average molecular weight of the polymer (D1) having a siloxane structure was 2,7 Å. [Example 1] [Positive type photosensitive property] Manufacture of the composition] The copolymer (A1) obtained in Synthesis Example 1, the copolymer (C4) obtained in Synthesis Example 6, 4,4-[1-[4-[1-[4-Phenylphenylmethyl]phenyl]ethylidene]bisphenol and 〇1,2- a stack of compounds a condensate of flavonol-5_sulfonate (average esterification rate = %, hereinafter referred to as "PAD"), as an additive interface 7 (trade name TM coffee _ JAPANK.K•, the following heart &lt;, ', BYK344'), diethylene glycol decyl ethyl ether as a solvent was mixed and dissolved under the following weight of 38 201207561. The positive photosensitive composition 1 having a solid concentration of 35 wt% was obtained. Alcohol methyl ethyl hydrazine 451 g 33.3 wt% solution of a polymer containing a decane structure (A1) 3.00 g 3.00 g 0.400 g 0.007 g

33.3 wt% solution of soluble polymer (C4) PAD BYK344 [Evaluation method of positive photosensitive composition] 1) Method of forming patterned transparent film Spin-sensitive composition 1 was spin-coated on a glass substrate at 600 rpm In seconds, the plate was dried with a hot plate of lOOt: 2 minutes. The substrate is used in a mask for forming an air interposer pattern, and a proximity exposure machine TME-l50PRC manufactured by T0PC0N Co., Ltd. is used to emit light, g, h, i by blocking the light of a wavelength blocking filter of 350 nm or less. The line is exposed by the exposure gap ΙΟΟμηι. The exposure amount was set to i5 〇 mJ/cm 2 . The exposure amount was measured by an integrated light meter υιτ·1〇2 manufactured by Ushio Inc. and a light receiving unit UVD-365PD. The exposed glass substrate was immersed and developed in an aqueous solution of ruthenium hydride in 〇 4 for 6 sec seconds to remove the resin composition of the exposed portion. The developed substrate was washed in pure water for 6 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. The substrate was exposed to the entire surface at 300 mJ/cm 2 without interposing the mask in an exposure machine, and then baked in an oven at 230 ° C for 30 minutes to form a pattern having a film thickness of 3 μm. 201207561 2) The residual film rate after development was measured before and after development, and was calculated according to the following formula. (Thickness after development/film thickness before development) χ1〇〇 (%) The stylus type film thickness of P-15 manufactured by -1^01·—Co., Ltd. was defeated at 3 points, and the average value was taken. 3) Resolution Observe the above at 400 times with an optical microscope! In the middle of the case, the substrate is __ hole. The case where the hole pattern is not formed is described as defective (10)) The mask of the glaze 4) Adhesiveness The 余 余 纽 纽 藉 藉 藉 藉 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The evaluation was carried out by attaching an adhesive tape to a patterned transparent film having 100 grids of 1 mm square formed by cutting. (Polyester tape N〇% manufactured by Sumitomo 3M Co., Ltd.: adhesion; 5.5 N/cm ")), expressed as the number of remaining grids after tape peeling. 5) The UV/03 ashing treatment forms a transparent film in the same manner as in the above 1) except that the pattern is not formed, that is, the exposure is not performed, and the following apparatus is used under the following conditions. The resulting transparent film was processed. Device: PL2003N-12 (PHOTO SURFACE PROCESSOR, manufactured by SEN LIGHTS Co., Ltd.) Settings: UV wavelength (254 nm), exposure (525 mJ/cm2) 201207561^ In addition, UVC manufactured by CUSTOM Co., Ltd. -254 and measure the exposure at 254 nm. 6) Contact angle The contact angle of pure water of the transparent film before and after the UV/03 ashing treatment of the above 5) was measured in a 25 t environment by a Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd. The value after attaching pure water for 1 second was taken as the contact angle value. The composition of the photosensitive composition 1 and the results obtained by the above evaluation methods are shown in Table 1. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A1 100 100 100 A2 100 80 100 C1 120 100 C2 100 100 100 C3 100 100 100 C4 100 100 100 D1 100 Residual film rate after development [%] 82 80 78 86 76 75 73 71 85 Resolution [μιη] 7 7 7 7 7 7 7 7 7 ί Daddy [-] 100/100 100/100 100/100 100/ 100 100/100 100/100 100/100 100/100 100/100 Contact angle uv/o3 before ashing 95 97 95 96 96 98 97 92 85 [degrees] uv/o3 after ashing 85 86 86 87 86 69 78 71 [Example 2 to Example 5 and Comparative Example 1 to Comparative Example 4] The photosensitive composition 2 to photosensitive composition as a polymer solution was prepared in the same manner as in Example 1 by the combination and amount shown in Table 1. 5 and the comparative soluble composition 1 to the comparative soluble composition 4 were evaluated. The composition and evaluation results of the photosensitive compositions are shown in the Table. It can be seen from Table 1 that in Examples 1 to 5, compared with Comparative Example 1 to Comparative 201207561 叩ιί Example 4, high tentacles can be obtained even after UV/〇3 ashing treatment. [Industrial Applicability] As described above, the photosensitive composition of the present invention can be treated by the known method of 7 and V, and the obtained hardened film has sufficient material as a barrier material. Liquid dialing. Further, in the circuit board manufacturing process or the like, it is possible to suppress the liquid repellency of the surface of the barrier material caused by the υν/0 3 ashing treatment to improve the wettability, and to maintain sufficient liquid discharge after the treatment. Sex. [Simplified description of the diagram] None. [Main component symbol description]

Ml 〇42 201207561 Invention patent specification (Do not change the format and order of this manual, please do not fill in the ※ part) π From a 哚. / / / 4 ^f-7^ (2006.01) ※Application date: ※工PC classification: First, the name of the invention: (Chinese / / English)

Sl!^ c ^s4 photosensitive composition, cured film obtained from the composition, and display element having the cured film

PHOTOSENSITIVE COMPOSITION, CURED FILM OBTAINED FROM THE COMPOSITION, AND DISPLAY DEVICE HAVING THE CURED FILM II. Abstract of the Invention: A positive photosensitive composition which can form a cured film excellent in liquid repellency and uv ozone ashing resistance is provided. A photosensitive composition comprising a photosensitive composition comprising a polymer (A) comprising a decane structure and a 1,2-diazide compound (B), and a polymer comprising a siloxane structure (A) A radical polymer using a monomer containing a compound having two radical polymerization sites, an alkali-soluble radical having an alkali solubility and a radical polymerizability imparting solubility to the polymer (A) Polymerizable monomer. A positive photosensitive composition capable of forming a cured film having excellent liquid repellency and

Claims (1)

(2) 20120756 lit R10 (In the formula (2), R5 to r7 each represent an aryl group, or an arbitrary hydrogen group may be substituted by fluorine to have an alkyl group having 1 to 3 carbon atoms, and R8 to Rn each represent hydrogen, and halogen '-CN '-CF3 ' - OCF3 'trans group, any methylene group can also be substituted by: ^仏, -OCO-, -CO- and any hydrogen can also be substituted by halogen, the carbon number of 5, or any hydrogen can also be The alkoxy group substituted with a carbon number of 1 to 5; wherein at least i of R8 to R12 is a hydroxyl group. 4. The feeling of any one of the above claims, the composition of The polymer (a) comprising the oxoxane structure is a free-form containing free radical compound represented by the formula (1) and free of other free-filaments of the solvent-soluble radical polymerized lysine. a polymeric composition, such as Ganshen, a photosensitive composition according to item 4 of the patent scope of the present invention, which is represented by a silk composite material (1), which is a silk oxide compound. R14 / (3) R13-Si4〇- R15\ R17 (wherein (3) + ' R13 to R17 each independently represent any nitrogen also 201207561. It may be substituted by fluorine and any methylene group may be substituted by oxygen. An alkyl group having 1 to 30 carbon atoms or a trimethyl (alkyl/alkoxy)decaneoxy group having a number of 1 to 500, a3 represents a radical polymerizable functional group, and n represents an integer of 〇1 to 1,000). 6. The photosensitive composition according to claim 5, wherein the other radical polymerizable monomer is a oxoxane compound represented by the formula (3) wherein 11 is 0. 7. The photosensitive composition according to claim 6, wherein R13~ of the formula (3) are respectively represented by the following formula (5), (In the formula (5), R21 to R23 each independently represent hydrogen, a carbon number of i to 20, or an alkoxy group having a carbon number of 1 to 2 (wherein at least one of β to R23 at the end is a The alkyl group or the alkoxy group), m represents an integer of from 1 to 500). The photosensitive composition according to any one of claims 4 to 7, wherein the other radical polymerizable monomer comprises a (mercapto)propionic acid derivative. 9. The photosensitive composition according to any one of claims 1 to 8, further comprising a soluble polymer (C) which is a formula (1) A free radical polymer of a monomer other than the represented oxoxane compound, and having a solubility. The photosensitive composition according to claim 9, wherein the alkali-soluble polymer (C) comprises a radically polymerizable monomer selected from the group consisting of unsaturated carboxylic acids, A radical polymer having one or more monomers of a group consisting of a radically polymerizable monomer of an unsaturated carboxylic anhydride and a radical polymerizable monomer having a phenolic hydroxyl group. 11. The sensitizing composition according to any one of the preceding claims, which further comprises a solvent. A cured film obtained by calcining a film of the photosensitive composition according to any one of the above claims. A display element having a cured film as described in claim 12 of the patent application. 46.07-0707 The UV light ashing resistance is provided. The photosensitive composition includes a polymer (A) containing a siloxane structure and a 1,2-quinone diazide compound (B). The polymer (A) containing a siloxane structure uses a radical polymer in The alkali-soluble radical polymer monomer has ability to make the polymer (A) alkali-soluble and radical polymerizable. The specific siloxane compound has two radical-polymerizable positions. 4. Designated representative circle: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: fe. 、5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Yi Yi 2 201207561 is the No. 6 Chinese Reward No Face Correction Page Correction date · On the 26th of the year, the exposure amount at 254 nm was measured using 'uvc_254 manufactured by CUSTOM Co., Ltd.'. 6) Contact angle The contact angle of the pure water of the transparent film after the UV/03 ashing treatment of the above 5) was measured at 25 ° C by a Dr〇p Master 500 manufactured by Kyowa Interface Chemical Co., Ltd. The value after attaching pure water for 1 second was taken as the contact angle value. The composition of the photosensitive composition 1 and the results obtained by the above evaluation methods are shown in Table 1. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A1 100 100 100 A2 100 80 100 C1 120 100 C2 100 100 100 C3 100 100 100 C4 100 100 100 D1 100 Residual film rate after development [%] 82 80 78 86 76 75 73 71 85 Resolution [μιη] 7 7 7 7 7 7 7 7 7 Adhesion [-] 100/100 100/100 100/100 100/100 100 /100 100/100 100/100 100/100 100/100 Contact angle [degrees] uv/o3 before ashing 95 97 95 96 96 98 97 92 85 uv/〇3 after ashing 85 86 86 87 86 69 78 71 62 [Example 2 to Example 5 and Comparative Example 1 to Comparative Example 4] The photosensitive composition 2 to the photosensitive composition 5 as a polymer solution were prepared in the same manner as in Example 1 by the combination and amount shown in Table 1. The comparative soluble composition 1 to the comparative soluble composition 4' was evaluated. The composition and evaluation results of the photosensitive compositions are shown in Table 1. As can be seen from Table 1, in Examples 1 to 5, compared with Comparative Example 1 to 201207561, the Chinese manual of No. 100126616 has no scribe correction date: (10) October 26, compared with Example 4, even in uv / 〇 3 ashing treatment can also obtain a high contact angle. [Industrial Applicability] As described above, the photosensitive composition of the present invention can be treated by the known lithography method (4), and the obtained hard ray has a liquid barrier property as a barrier material. In the manufacturing process of the circuit board, etc., it is possible to suppress the two wet conditions (4), and the liquid repellency of the barrier material caused by the ashing of the ash/v3 is maintained, and sufficient liquid repellency is maintained after the treatment. [Simple description of the diagram] None. [Main component symbol description] Ml 〇*\\\ 42 201207561 ^ο^υυριίΐ Date of revision: 10() October 26th' is the Chinese patent scope of No. 100126616. No slash correction. 7. Patent application scope: 1. A photosensitive composition comprising: a polymer comprising a oxoxane structure (A) and a 1,2- azide stilbene compound (b), wherein the polymer comprising the oxalate structure (A) has a formula ( 1) a cerium oxide compound represented by the above, and a radical polymer having a monomer which imparts solubility to the polymer (A) and an alkali-soluble radical polymerizable monomer which is radically polymerizable, (1) (In the formula (1), R1 to R4 each independently represent hydrogen, or any hydrogen which may be substituted by fluorine and which is not continuous, may be an alkyl group having 1 to 30 carbon atoms which may be substituted by oxygen. A1 and A2 respectively represent a radical polymerizable functional group, and η represents 1 to 1, and an integer of 〇〇〇). 2. The photosensitive composition according to claim 1, wherein the alkali-soluble radically polymerizable monomer comprises a radically polymerizable monomer selected from the group consisting of unsaturated carboxylic acids and has an unsaturated state. One or more of the group consisting of a radically polymerizable monomer of a carboxylic anhydride and a radically polymerizable monomer having a phenolic hydroxyl group. 3. The photosensitive composition according to claim 1, wherein the alkali-soluble radical polymerizable monomer comprises a radical polymer monomer represented by the formula (2), 43 201207561 is the 100126616 No. Chinese patent range without marking correction D12 (In the formula (2), R5 to R7 respectively represent hydrogen, or any hydrogen may be substituted by fluorine, and the number of carbon atoms is 1 to 3, r8 to r12 are divided into gas, and the element '-CN '-CF3 ' -0CF3 'trans group, any methylene group may be substituted by _c〇〇_, -OCO-, -CO- and any hydrogen may be substituted by halogen with a carbon number of 丨~5, or any Hydrogen may also be substituted with dentate after several 丨~5 of the alkyl group; wherein at least i of R8 to R12 is a hydroxyl group). 70. The sensation composition according to the above aspect of the invention, wherein the polymer (A) comprising a oxoxane structure further comprises a Wei-free compound m-capacity free radical represented by (1) A radical polymer of a monomer other than a polymerizable monomer other than the polymerizable monomer. 5. The photosensitive composition according to claim 4, wherein the other radical polymerizable monomer comprises a compound of the formula (3) (In the formula (3), Ri3 to Rn each independently represent a carbon number in which any gas can be substituted by fluorine and any of the fluorenylene groups can be substituted by oxygen. i~^ also 44 201207561 w ^ is the Chinese patent No. 100126616 Fan _ no face correction This revision date: October 26, 100, the hospital base, or the number of 1 1 to 500 ( (Hyun / alkoxy) oxalatyloxy, 八 3 represents a radical polymerizable functional group, η represents 〇~1, an integer of 〇〇〇). 6. The photosensitive composition according to claim 5, wherein the other radical polymerizable monomer is! The oxoxane compound represented by the formula (3) of 0. 7. The photosensitive composition according to claim 6, wherein R1 2 3 4 5 6 to Ri5 of the formula (3) are respectively represented by the following formula (5). (In the formula (5), R2i to R23 each independently represent hydrogen, an alkyl group having a carbon number of i20, or an alkoxy group having a carbon number of 1 to 20 (wherein at least one of R2! to R23 at the terminal is the said The alkyl group or the alkoxy group), m represents an integer of from 1 to 500). The photosensitive composition according to any one of claims 4 to 7, wherein the other radical polymerizable monomer comprises a (meth)acrylic acid derivative. The luminosity-sensitive composition according to any one of claims 1 to 7, further comprising an alkali-soluble polymer (C), the alkali-soluble polymer (C) * A radical polymer of a monomer other than the Wei-sinter compound of the formula (1), and having an alkali solubility. 6 10. If the photosensitive composition described in the scope of claim 9 is 201207561, the Chinese patent scope of No. 100126616 is not corrected by the slash correction date. On October 26, the soluble polymer is tested. (C) is a group comprising a radically polymerizable monomer selected from a radically polymerizable monomer having an unsaturated carboxylic acid, a radically polymerizable monomer having an unsaturated carboxylic acid anhydride, and a radical polymerizable monomer having a phenolic hydroxyl group. One or more monomeric free radical polymers. The photosensitive composition according to any one of claims 1 to 7, further comprising a solvent. A cured film obtained by calcining a film of the photosensitive composition according to any one of claims 1 to 11. A display element having a cured film as described in claim 12 of the patent application. 46