TW201232182A - Positive photosensitive resin composition and permanent resist - Google Patents

Abstract

The present invention provides a positive photosensitive resin composition, which is applicable to the formation of interlayer insulating film of high heat resistance, high solvent resistance, high transmittance, and low dielectric constant, and having a larger developing margin during the development process to form a good pattern shape even if more than the optimum developing time has elapsed. Specifically, The present invention is to provide a positive photosensitive resin composition containing polysiloxane compound having carboxyl group and/or phenolic hydroxyl group as a base resin, and photosensitive diazonium compound as the photosensitive component and organic solvent, characterized by containing the epoxy siloxane compound formed by linking the residue, which is obtained by removing vinyl groups from a compound having 2 to 4 vinyl groups in one molecule, with a group represented by the following formula (1), or formed by linking the group represented by the following formula (1) with the group represented by the following formula (2), wherein, R1 represents the same or different alkyl group with 1 to 4 carbon atoms or an aryl group of 6 to10 carbon atoms, E represents an epoxy group, a represents a number of 2 to 5, b represents the number of 2 to 6 that will make (a-b +1) become a number of 0 to 4, and R1, E and a have the same meaning as in the above-mentioned formula (1).

Description

201232182 SUMMARY OF THE INVENTION Technical Field The present invention relates to a positive photosensitive resin composition containing a specific epoxy siloxane compound, and a permanent resist using the positive photosensitive resin composition. Agent. [Prior Art] In electronic components such as a thin film transistor (hereinafter referred to as a "TFT") liquid crystal display device, a magnetic head device, an integrated circuit device, and a solid-state imaging device, in order to insulate the wirings arranged in layers, An interlayer insulating film is provided. As a material for forming the interlayer insulating film, it is preferable to use a radiation-sensitive resin composition (see Patent Document) for the purpose of obtaining a desired pattern shape with a small number of steps and having sufficient flatness. In the above-mentioned electronic component, for example, a TFT-type liquid crystal display element is manufactured by forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon. Therefore, in the step of forming a transparent electrode film, interlayer insulation is performed. The film is exposed to high temperature conditions or to the stripping solution of the anti-knocking agent used for pattern formation of the electrode, and thus sufficient resistance to such is required. Further, according to the manufacturing steps, the interlayer insulating film formed is also exposed to the dry type, and therefore sufficient resistance to dry etching is required (refer to Patent Document 2). In addition, the TFT-type liquid crystal display device has a large screen, high luminance, high definition, high-speed response, and thinning, and the composition for forming an interlayer insulating film used has high sensitivity. For the interlayer insulating film formed, a higher performance than the previous one of 159809.doc 201232182 is required in terms of low dielectric constant, high transmittance, and the like. An interlayer insulating film material which is excellent in insulating properties, heat, solvent, dryness, dryness, and the like, and which can form a fine pattern, has been developed to contain a polysulfide compound having a slow base and a photosensitive diazonium. The positive photosensitive composition of the compound (refer to Patent Document 3) 'also known as a composition containing an epoxy group-containing cyclic siloxane compound, but due to the development margin in the development step (development time) The length of the time to be optimal is small. Therefore, if the development time is slightly excessive, the developer is permeated between the formed pattern and the substrate, and peeling easily occurs. Therefore, the development time must be strictly controlled, and the yield of the product is good. There are problems in the aspect. On the other hand, a compound in which a cyclic siloxane compound having an epoxy group is bonded (see Patent Document 4) is known, but a positive photosensitive resin composition containing such a compound is not known. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Laid-Open No. 2001-354822 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. 2005-345757 Patent Document 3: Patent Application No. 2〇1 〇 _ 1 〇丨 〇丨 〇丨 专利 〇丨 〇丨 〇丨 〇丨 〇丨 〇丨 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The formation of an interlayer insulating film having heat resistance, high solvent resistance, high transmittance, and low dielectric constant 'has a large development margin which can form a good pattern shape even if the optimum development time is exceeded in the development step. 159809.doc 201232182 [Means for Solving the Problems] The present inventors conducted intensive studies in view of the above problems, and as a result, completed the present invention. In other words, the present invention provides a positive-type photosensitive resin composition containing a polybasic compound having a hydroxy group and/or a silky substance as a base resin, a photosensitive diazonium compound as a photosensitive component, and an organic solvent. The residue represented by the following formula (1) is linked to a residue represented by the following formula (1) in a compound having 2 to 4 vinyl groups in the i molecule, or is bonded to the following formula (1) An epoxy siloxane compound having a group represented by the following formula (7),

It is synonymous with the above formula (1)). [Effects of the Invention] The effects of the present invention are to provide a positive photosensitive resin composition suitable for high heat resistance and high solvent resistance, which is high. The transmittance and the low dielectric constant layer 159809.doc 201232182 are formed between the insulating films, and have a large development margin which forms a good pattern shape even if the optimum development time is exceeded in the developing step. [Embodiment] Hereinafter, a positive photosensitive resin composition and a permanent resist of the present invention will be described in detail based on preferred embodiments. The present invention contains a polyoxyalkylene compound having a carboxyl group and/or a phenolic hydroxyl group as a matrix resin (hereinafter also referred to as a base resin of the present invention), a photosensitive linear compound as a photosensitive component, and an organic solvent. A photosensitive resin composition containing a residue having a vinyl group removed from a compound having 2 to 4 vinyl groups in a ruthenium molecule, and linking the groups represented by the above formula (1) to each other or to the above formula (1) The base of the material is the same as the base represented by the above formula (7), and the epoxy compound compound (hereinafter also referred to as the present invention) is described as 'the epoxidized compound of the present invention. In the above formula (1) Indicates an aryl group which may be the same or different carbon number or carbon number 6 to H). Examples of the carbon group of the carbon number 4 include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, an isobutyl group, a t-butyl group, etc. as a carbon number of 6 to 1. The aryl group of () may, for example, be phenyl, ethylphenyl, toluene, isopropyl, xylyl, pSeUd〇cumyl, decyl, tert-butyl, stupid Base. The term "r] is preferably a methyl group, an ethyl group and a phenyl group in terms of improving heat resistance, more preferably a methyl group and a phenyl group, and most preferably a methyl group. In the above formula (1), E represents a group having an epoxy group. Examples of the group having an epoxy group include an aliphatic epoxy group such as the following formula (5) or (6), and an alicyclic epoxy group such as the following formula (7) to (9); The aromatic epoxy group or the like of the formula (10) or (11) is preferably 'the following formula (5) or (from the viewpoint of storage stability of the positive photosensitive resin composition of the present invention). The aliphatic epoxy group of 6) is a group of a partial structure, more preferably 1,2-epoxypropyl group of the following formula (5), and further preferably a group having a glycidyl ether group, most preferably 3 Glycidoxypropyl. A 〇 —CH2-CH-CH2 (5) A CHr?’—, CH2 (6) ch3 CH3 (?) ~〇^°(8) ~〇^°(9)

4(10) ^^yc-CH2 (11) ch3 In the above formula (1), a represents a number of 2 to 5, and since a commercially available raw material is more easily obtained, a is preferably 2 to 4 The number is preferably 2 to 3, and the best is 3. In the above formula (2), b represents a number of 2 to 6 in which a-b+Ι is 〇~4, and R1, E and a are synonymous with the above formula (1). In the epoxy oxime compound of the present invention, it is difficult for the anti-knocking agent to remain on the substrate of the alkaline developing & t, and the above compound having 2 to 4 ethylene groups in the plant molecule The number of vinyl groups is preferably 2. Examples of the compound having 2 to 4 vinyl groups in one molecule include compounds represented by the following formulas (12) to (18), and from the viewpoint of heat recovery, preferably the following formula ( 12) The compound shown in ~(14) is easy to obtain industrially. 159809.doc

From the viewpoint of S 201232182, it is preferably a compound represented by the following formula (16).

(In the formula, R4 to R6 represent an alkyl group having a carbon number of 1 to 4 or an aryl group having a carbon number of 6 to 10, c is a number of 1 to 3, and d and e are each independently represented by 0 to 6; number). CH, CH=CH2 =CH-Si-〇- R7 ch=ch2 ij-〇4-Si-CH=CH2 r9 /fR7 (13> (wherein, R7 to R9 represent the same or different carbon number 1~ 4 alkyl or carbon 6 to 10 aryl, f represents 0 to the number).

(wherein R10 represents an alkyl group having 1 to 4 carbon atoms or a carbon number of 6 to 10 which may be the same or different, and represents a number of 3 to 4).

(wherein R11 and R12 represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different). 159809.doc •9- 201232182 CH2=CH^0(—, 16) (where h is the number from 1 to 2). CH2=ch_^ Meaning 2) 』(17) (where j is the number from 1 to 3) 〇, , /CH2CH=GH2 /C—N, CH=CHCH Factory N, .,0=0 (1 8 X-N7 0/ R13 (wherein R13 represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 1 carbon atoms, a glycidyl group or an allyl group). The compound represented by the above formula (12) is attached to! A compound having 2 to 4 ethylene groups in the molecule. In the above formula (12), R4 to R6 represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different. Examples of the alkyl group having a carbon number of 44 and the aryl group having a carbon number of 6 to 10 include the groups exemplified in the description of the above formula (", and the like, as R4 to R6, the heat resistance is good. Preferably, it is a methyl group, an ethyl 'propyl group and a phenyl group, more preferably a methyl group, an ethyl group and a stupid group. The most preferred group is a fluorenyl group. C represents a number of 1 to 3, and d and e respectively represent 〇~ In the compound represented by the above formula (12) wherein c is 1, the preferred compound may, for example, be dimethyldivinylnonane, diethyldivinylnonane or diphenyldiene. Vinyl decane, tetramethyl hydrazine, 3_divinyldioxane, 1,1,3,3-tetraethyl-u-divinyldioxane, 159809.doc -10- 201232182 1, 1,3,3 -tetrabenyl-1,3 --diyl--a decomposing oxygenator, etc., preferably a dimethicone, a vinyl sulphate, a diethyldithiocarbazite, and a diphenyl bis The vinyl pulverization is more preferably 1,1,3,3-tetradecyl·1,3-divinyl bismuth oxide. The above formula (12) is represented by 2 Among the compounds, preferred examples of the compound include mercaptotrivinylguanidine. Alkane, ethyltrivinyl decane, stupid trivinyl decane, 1,1,3,5,5-pentamethyl-^, trivinyltrioxane, 1,1,5,5-tetra Methyl-3-phenyl-1,3,5-trivinylsandicarb, tris(dimethylvinyldecyloxy)methyldecane, tris(didecylvinyldecyloxy)phenyl The compound represented by the above formula (12) wherein c is 3, and preferred examples of the compound include tetravinylnonane, tetrakis(dimethylvinyldecyloxy)decane, and the like. The compound represented by the formula (13) is a compound having four vinyl groups in the fluorene molecule. In the above formula (9), 'r7 to r9' represent an alkyl group having a carbon number of 1 to 4 or a carbon number 6 which may be the same or different. The aryl group having a carbon number of 丨~々 and the aryl group having a carbon number of 6 to 10, and the bases exemplified in the description of the above formula (1) iR can be cited as 'R7 to R9'. In terms of good heat resistance, it is preferably a methyl group, an ethyl group, a propyl group and a phenyl group. More preferably, it is a fluorenyl group, an ethyl group and a stylyl group are preferably a methyl group. f represents a number of 〇~1〇 In the above formula Preferred examples of the compound include: dimethyl-tetraethylene-dithiocarbazone, coffee tetramethyl hydrazine, vinylene, etc. ... base-MW·tetraethylene-based three-AS two-form ( 14) The compound shown has 3 to 4 vinyl groups in one molecule. In the above formula (14), R1 represents the same or different 159809.doc 201232182 carbon number 1 to 4 The alkyl group or the aryl group having 6 to 10 carbon atoms. The alkyl group having a carbon number of 4 and the aryl group having a carbon number of 6 to 10 may be exemplified by the above formula (" Preferably, the mercapto group, the ethyl group, the propyl group and the phenyl group are more preferably a methyl group, an ethyl group or a phenyl group, and most preferably a methyl group β g represents a number of 3 to 4. In terms of the ease of industrial access, g is preferably a number of four. In the compound represented by the above formula (14) wherein 8 is 3, 'as a preferred compound, 2,4,6-tridecyl 2,4,6-trivinylcyclotrioxane is exemplified. Alkane ' 2,4,6•triethyl 2,4,6•trivinylhdoxane, 2,4,6-triphenyl-2,4,6-trivinylcyclotrioxane Alkane, 2'4·dimercaptophenyl-2,4,6-trivinylcyclotrioxane, and the like. Among the compounds represented by the above formula (14) wherein g is 4, preferred examples of the compound include 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl. Cyclotrioxane, 2,4,6,8-tetraethyl-2,4,6,8-tetravinylcyclotrioxane, 2,4,6,8-tetraphenyl-2,4, 6,8-tetravinylcyclotrioxane, 2,4,6-trimethyl-8-phenyl-2,4,6,8-tetraethylene ring trihydrogen, 2,4- Dimethyl-6,8-diphenyl-2,4,6,8-tetravinylcyclotrioxane, and the like. The compound represented by the above formula (15) is a compound having two vinyl groups in a ruthenium molecule. In the above formula (15), Rii&Rl2 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 1 carbon atoms which may be the same or different. Examples of the alkyl group having a carbon number and the aryl group having a carbon number of 6 to 10 include the above-described formula (the group exemplified in the description of OiRi, etc., and Rii and Ri2 are preferably 曱 in terms of heat resistance. The group, the ethyl group, the propyl group and the phenyl group, more preferably a methyl 'ethyl group and a phenyl group' are preferably a methyl group. Among the compounds represented by the above formula (15), 'as a preferred compound, a丨, 2·bis(dimethylvinyl decyl) 159809.doc

S •12- 201232182 Benzene, 1,3-bis(dimercaptovinyl fluorenyl)benzene, hydrazine "bis(dimethylvinyl decyl) benzene, 1,2-bis(diethylvinyl fluorenyl) Benzene, i, 3_bis(diethylethenylalkyl)benzene, anthracene, 4_bis(diethylvinylfluorenyl), etc., preferably 1,2-bis(dimethylethylene) The quinone alkyl)benzene and 1>4 bis (dithioglycolyl) benzene, more preferably 1,4-bis(dimercaptovinyl fluorenyl) benzene. The compound represented by the above formula (16) is a compound having 2 to 3 vinyl groups in one molecule. In the above formula (16), h represents the number of 1 to 2. The compound represented by the above formula (16) wherein h is 1 may, for example, be fluorene, 2-divinylbenzene, 1,3-divinylbenzene, anthracene or 4-divinylbenzene. The compound represented by the above formula (16) wherein h is 2 may be exemplified by trivinylbenzene or 1,3,5-triethylenebenzene. The compound represented by the above formula (17) is a compound having 2 to 4 vinyl groups in one molecule. It is expressed in the above formula (17)! ~3 number. Examples of the compound represented by the above formula (17) wherein j is 1 may include anthracene, 2-divinylcyclohexane, 1,3-diethylenecyclohexane, anthracene, and a 'divinyl ring. Hexane. The compound represented by the above formula (17) wherein h is 2 may, for example, be 1,2,4-trivinylcyclohexane or 1,3,5-divinylcyclohexane. The compound represented by the above formula (17) which is a number of 匕 is exemplified by tetravinylcyclohexane. The compound represented by the above formula (18) is attached to! A compound having 2 to 3 vinyl groups in the molecule. In the above formula (18), R13 represents a carbon group of i to 4, an aryl group having a carbon number of 6 to 10, a glycidyl group or an allyl group. As the rU, from the viewpoint of heat resistance, a mercapto group, an ethyl group, a glycidyl group, and an allyl group of 159809.doc -13·201232182 are preferable. Among the compounds represented by the above formula (10), preferred compounds 'are exemplified by 1'3-diallyl-5-methylisocyanuric acid, D•diallyl·5·ethyl isocyanide. Uric acid vinegar 'diallyl_5_glycidyl isocyanurate, 1,3,5- triallyl isocyanurate, and the like. In the case where the proportion of the epoxy group in the epoxy oxime compound of the present invention is too small, the mechanical properties of the obtained cured product are lowered, so the ratio is preferably 1000 or less in terms of epoxy equivalent, more preferably 7〇〇 below W. Further, the term "epoxy equivalent" means a value obtained by dividing the molecular weight by the number of epoxy groups, that is, the molecular weight of each epoxy group. When the molecular weight of the epoxy oxirane compound of the present invention is too small, the effect of improving the development margin is small, and if it is too large, the resist remains on the substrate after the alkaline development. Therefore, the molecular weight is preferably 1000 to 1 Torr, more preferably 15 Å to 7 _, and most preferably 2,000 to 500 Å in terms of weight average molecular weight. In the present invention, the so-called weight average molecular weight means The weight average molecular weight in terms of polystyrene when the tetrahydrofuran was subjected to Pemeation Chn > matography 'gel permeation chromatography> as a solvent. In the positive photosensitive resin composition of the present invention, when the content of the epoxy oxymethane compound of the present invention is too small, the effect of improving the development margin is small, and in the case of excessive sensation, there is a checkability. The developability and the physical properties of the resist have an adverse effect, and the residue of the (4) residue remains on the substrate after development. Therefore, the content is preferably 1 to 3 parts by weight based on 1 part by weight of the base resin of the present invention. More preferably, it is 2 to 25 parts by weight, and most preferably 3 to 2 parts by weight. 159809.doc

• 14-201232182 The cyclodecoxy hydride compound of the present invention can be obtained by subjecting a SiH group of a cyclic siloxane compound represented by the following formula (la) to 2 to 4 molecules per molecule. The vinyl group of the vinyl compound is subjected to a hydrazine hydrogenation reaction to further carry out a hydrazine hydrogenation reaction of an epoxy compound containing a carbon-carbon double bond reactive with an SiH group.

The hydrogenation reaction of the cyclic oxirane compound represented by the above formula (la) with a compound having four vinyl groups in one molecule is preferably carried out using a catalyst as a catalyst, for example, a fluorene catalyst. Catalyst, system catalyst, = catalyst, etc. Examples of # platinum-based catalyst include chloroplatinic acid, a complex of chloroplatinum oxime with an alcohol, a ketone, a ketone, etc., a turn-olefin complex, and a quinolyl vinylmethyloxane. Compound (〇ssk〇 catalyst), platinum-divinyltetradecyldioxane complex (KaRstedt catalyst), platinum-cyclovinylmethyloxane complex, platinum-octanal Compound, platinum-phosphine complex (eg Pt[P(C6H5)3]4, Ptcl[P(C6H5)3]3, pt[p(C4H9) sylvestre acid vinegar complex (eg Pt[P (〇C6H5)3]4), 叩(10) is called mountain), two groups of two gas and aunt. As the catalyst or the lanthanide catalyst, for example, a compound containing an atom of an atom or a recording atom in place of the above-mentioned ruthenium catalyst can be cited. These may be used in one type or two or more types may be used in combination. (4) Hydrogenation catalyst, from the viewpoint of reactivity, preferably platinum (four), more preferably platinum·divinyltetramethyl 159809.doc • 15-201232182 bis-dioxane complex and platinum-carbonyl The vinyl methyl oxime complex is preferably a platinum carbonyl vinyl methyl oxime complex. Further, from the viewpoint of reactivity, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001% by weight of the total amount of each raw material. ·〇% by mass, the best is 〇1~〇 lf %. The reaction conditions for the hydrogenation of hydrazine are not particularly limited, and may be carried out under previously known conditions using the above-mentioned catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 to 130130 t). A previously known solvent such as toluene, hexane, methyl isobutyl ketone or cyclopentanone 'propylene glycol monomethyl ether acetate can also be used. The cyclic oxirane compound represented by the above formula (la) and a hydrogenation reaction of a reactant having a compound of 2 to 4 vinyl groups in a ruthenium molecule with an epoxy compound containing a carbon-carbon double bond reactive with a siH group, as long as it is in the above formula (la) The cyclic oxoxane compound may be carried out under the same conditions as the hydrazine hydrogenation reaction of a compound having 2 to 4 vinyl groups in the fluorene molecule, preferably after the hydrogenation reaction of the hydrazine, without allowing the reactant to be separated The reaction is continued with purification. As an epoxy compound containing a carbon-carbon double bond reactive with the above SiH group, 5,6-epoxyhexene, 7,8-epoxyoctene, allyl group is used. Glycidyl ether, glycidyl methacrylate, etc. The aliphatic epoxy group of the above formula (5); if 3,4-epoxymethylbutene or the like is used, the aliphatic epoxy group of the above formula (6) can be introduced; if i, 2 ring is used The alicyclic group may be introduced into the alicyclic epoxy group of the above formula (7) by using oxy_4_vinylcyclohexene or (3,4-epoxycyclohexyl)decyl decyl acrylate; if i, 2_ is used; Epoxy limonene or the like can be introduced into the alicyclic epoxy group of the above formula (8); if 3-vinyl-5 is used, 6_ring I59809.doc 201232182 Oxygen-reduced (3-vinyl-5,6) -ep〇xy_norpinane) or the like, the alicyclic epoxy group of the above formula (9) can be introduced; if 4-epoxyethyl styrene or the like is used, the aromatic epoxy group of the above formula (10) can be introduced; When 4_(didecyl epoxyethyl)styrene or the like is used, the aromatic epoxy group of the above formula (11) can be introduced. The base resin of the present invention will be described. The matrix resin of the present invention has m. a base-and/or sh-based group of agglomerated compounds. In a positive-type photosensitive resin composition containing a photosensitive diazonium-containing compound as a photosensitive component, the matrix resin is originally soluble in the developer, However, in the unexposed portion, the photosensitive resin is insoluble or poorly soluble in the developer, and the matrix resin is prevented from being dissolved in the developer. For this, the exposed portion is made photosensitive by ultraviolet irradiation or the like. The storage compound is decomposed to form a pattern in which the matrix resin is soluble in the developer. The polysiloxane compound having a carboxyl group and/or a phenolic hydroxyl group is used as a positive photosensitive resin composition having a matrix θ. The (4) oxygen-containing compound having a carboxyl group and/or an aging base has a good readability or astigmatism, but has a problem that the development margin becomes small, and the photosensitive resin composition of the present invention can contain the present invention. The epoxy (iv) burns the compound to increase the development margin. In the case where the content of the carboxyl group and the phenolic hydroxyl group is too small in the matrix resin of the present invention, the 'developability of the testability is poor, and when the amount is too large, the film is reduced. Therefore, the total amount of the content is preferably agglomerated. It is 1~5 mmol/g, more preferably 〜5~4 mm〇1/g, and the best is (a) coffee.丨^. Further, in the case where the molecular weight of the matrix resin of the present invention is too small, when the reduction/largeness is too large, the substrate residue of the substrate after the development of the surface is inferior to the surname residue of the surface of the substrate I59809.doc -17-201232182 Therefore, the weight average molecular weight is preferably 1_~2_〇1 preferably 2_~16〇〇〇, most preferably 4_~13〇〇〇. The base resin of the present invention preferably contains a (tetra)-form alcohol group because the thermal crosslinkability of the positive photosensitive resin composition is improved and the mechanical strength or chemical resistance of the obtained compound is improved. The amount of the octanol group in the base resin of the present invention is preferably 丨 to "% by mass, more preferably 5% by mass", more preferably 5 to 20% by mass, based on the OH content. As the matrix resin of the present invention, Since the effect of improving the development margin obtained by using the additive of the present invention is large, it is particularly preferably a cyclic siloxane compound represented by the following formula (i 9) and a formula represented by the following formula (20). A hydrolysis condensate of a siloxane compound (refer to Patent Document 3 above).

(式辛' R" represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and 15 8 represents a hydrocarbon linking group having a carbon number of 2 to 10, and R16 and R17 are the same or a saturated aliphatic hydrocarbon group having a carbon number of 2 to 10, which is different in carbon number, and R18 and the same or different alkyl groups having a carbon number of 1 to 4, wherein k represents a number of 1 to 3, and m represents a number of 〇$, η represents the number of 0~5, and p represents the number of 1~5. Among them, m, n&p becomes m+n= 1 ~5, m+n+p=3~6)° 201232182 R2〇_ Si>-R21)q H (2〇) (wherein R20 represents an aryl group having 6 to 10 carbon atoms, and R2i& R22 represents an alkyl group which may be the same or different and has a carbon number of 1 to 4, and q represents 2 to 3; Number). In the above formula (19), rM represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 1 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of the above formula (1). As the rH, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a phenyl group are preferred from the viewpoint of heat resistance and ease of industrial availability, and more preferably a methyl group. And stupid base, the best is methyl. In the above formula (19), R > 5 represents a divalent hydrocarbon linking group having 2 to 1 carbon atoms. Examples of the hydrocarbon linking group having a carbon number of 2 to 1 Å include an exoethyl group, a propyl group, a 1-methyl-ethyl group, a methyl group, a tetramethylene group, and a tetramethylene group. , 3-methyl-amyl, hexamethylene, octamethylene, decamethylene, ring M-i'4-dimercapto, 2-phenylene-M'-diyl, diyl, etc.丄 as R15, from the viewpoint of ease of industrial availability and heat resistance, it is preferably "extended ethyl, 2-methyl extended ethyl and 2-phenylethane_M, -diyl" is more preferably 2-methyl-extended ethyl and 2-phenylethane", dibasic, most preferably 2. In the above formula (IV), Rrn represents a saturated aliphatic group which may be the same or different in carbon number of 2 to 10 Hydrocarbyl group. The divalent aliphatic hydrocarbon group having a carbon number of 2 to 1 Å may, for example, be an ethyl group, a propylene group, a methyl group, a methyl group, a methyl group, or a tetramine. Its ... tetramethylene, hydrazino, 3-methyl pentyl, hexamethylene octamethylene, ^ 16 decamethylene, etc., as Rl6 and R, 7, on the industrial 159809.doc 201232182 From the viewpoint of the availability of the cereal and heat resistance, it is preferably an ethyl group, a methyl group and a propyl group, and more preferably an ethyl group. In the above formula (19), Ris and r19 represent an alkyl group having 1 to 4 carbon atoms which may be the same or different. The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group or a tert-butyl group. As R18 and R, since the reactivity by the hydrolysis condensation reaction is good and the heat resistance of the matrix resin of the present invention is improved, a methyl group and an ethyl group are preferable, and a mercapto group is more preferable. In the above formula (19), 'k' represents the number of b, and m represents. ～5, η represents the number of 〇~5, and p represents... wherein m, η, and p are the numbers of m+n=1~5, m+n+p=3~6. In terms of the availability of industrial raw materials, it is preferable that Am + n + p is 3 to 5, more preferably 3 to 4 'best. Since the adhesion to the substrate is good, the ratio of the claw to n is preferably G.5 to 2, more preferably G.8 to 1.8, and most preferably i.o to u. In the above formula (20), r2〇 represents an aryl group having 6 to 1 carbon atoms. Examples of the aryl group or the like exemplified in the description of the above formula (1) are as R2. (4) The concept of the easiness of heat and the fourth (four). The point 5' is preferably a phenyl group and a tolylylene group, more preferably a phenyl group. R21 and π represent the carbon number which may be the same or different, and the carbon number is 4, and the alkyl group is exemplified by the alkyl group exemplified in the description of R丨 of the above formula (1), and R" and R22. Since the reactivity of the hydrolysis condensation reaction is good and the heat resistance of the matrix resin of the present invention is improved, it is preferred that the methyl group and the ethyl group have a too small molecular weight in the matrix resin of the present invention, and the present invention is present.

S -20-201232182 When the positive photosensitive resin composition of the invention is applied to an object, the film formation property is poor. In the case of excessively large, there is an anti-substrate surface resistance after the development of the substrate. The amount of the etchant residue is preferably from 600 to 50,000, more preferably from 800 to 2 Torr, most preferably from 1,000 to 10,000, based on the weight average molecular weight, in the base resin of the present invention, in the carboxyl group and the phenolic property. When the content of the hydroxyl group is too small, the alkali developability is deteriorated, and when there are too many cases, the film reduction at the time of development becomes large, so the content of the carboxyl group is set to A (unit: mmol/g). The content of the phenolic hydroxyl group is set to B (unit: mm〇i/phantom case] The value of A+O.lxB is preferably 0 〇1~3 mm〇i/g, more preferably 〇~2 mmol/g. Preferably, it is ο"-!"mm〇1/g. The hydrolysis condensation reaction of the cyclic oxirane compound represented by the above formula (19) with the oxirane compound represented by the above formula (2〇) is only required The so-called sol-gel reaction can be carried out, and as such a trans (four) reaction, it is reported to be hydrolyzed by using an acid or a test substance in a solvent. The solvent to be used at this time is not particularly limited, and specific examples thereof include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, propylene glycol, methyl ethyl _, The second broth, the tetrahydrofuran, the bromo-2-propanol acetic acid, the U2-dimethoxy ethoxylate, the toluene, etc., one of these may be used, and # may be used in combination of two or more. The reaction of the oxo-based compounds with each other, that is, the above-described hydrolytic condensation reaction, is carried out by: using the silk base of the compound towel as a base; using the hydrolysis to produce a (tetra)yl group (8), and the formation The Shixiyuan alcohol group is condensed with each other, the cut alcohol group and the alkoxy group. The 吏X Jc decondensation reaction proceeds rapidly, preferably by adding an appropriate amount of 159809.doc 201232182 water' to dissolve the catalyst in water. Further, the hydrolysis condensation reaction can be carried out even by using water in the air or a trace amount of water contained in a solvent other than water. The catalyst such as an acid or a base used in the hydrolysis condensation reaction may be one which promotes the hydrolysis condensation reaction, and specific examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid; formic acid, acetic acid, oxalic acid, citric acid, and mercaptosulfonate. Organic acids such as acid, stupid sulfonic acid, p-toluenesulfonic acid, monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia; tridecylamine, triethylamine, monoethanolamine, and An amine compound (organic base) such as ethanolamine or the like may be used, and one type thereof may be used, 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, and is preferably 0 to 80 ° C ', more preferably 5 to 50. (:, preferably 8 to 30 t. The stanol group formed by hydrolysis of the oxoalkyl group is not all subjected to a condensation reaction, but a part remains unreacted, and chemical resistance and adhesion to the substrate are obtained. The base resin of the present invention preferably contains a stellite alcohol group. The content of the stanol group in the matrix resin of the present invention is preferably 丨 to Mn by mass, more preferably 3 〜. 25% by mass 'best is 5 to 20 masses. / (^ As a method for quantifying stanol groups, alkylation of decyl alcohol trimethyl hydrazine by trimethyl gas oxime or the like is used and the mass is increased according to the before and after the reaction. Quantitative and quantitative method (TMS (Trimethylsilyl) method), by using a near-infrared spectrophotometer (refer to Japanese Patent Laid-Open Publication No. 2001-208683A) Or a method of quantitative analysis by machine analysis of 29Si-NMR (NUClear Magnetic Resinance) (refer to Japanese Patent Laid-Open Publication No. 2007-21 7249, etc.) 159809.doc

S 201232182 The human alkanol group has a situation in which I easily causes a condensation reaction and reduces the amount of the stanol group by treatment. Especially after the hydrolysis condensation reaction, the product is detached and the stanol groups are easily caused by each other. Since the dehydration condensation reaction is carried out, it is preferred to prepare the base resin of the present invention, and after performing the hydrolysis condensation reaction in a solvent, the solvent is concentrated or replaced with another solvent as needed without being separated, and formulated into a positive photosensitive film. Resin composition. Next, the photosensitive diazonium compound of a photosensitive component is demonstrated. The photosensitive diazonium compound which can be used in the present invention is not particularly limited as long as it is a diazonium compound which is known to be used in a photosensitive material, and since it has good photosensitivity and can form a fine pattern, A compound (4-diazonaphthoquinone sulfonate) in which a hydrogen atom of a compound having a phenolic hydroxyl group is substituted with a group represented by the following formula (21), or is represented by the following formula (22) A compound substituted with a group (5-diazonium naphthalene acid).

Preferred examples of the photosensitive diazonium-containing compound include, for example, the compounds represented by the following formulas (23) to (28), and the positional isomers thereof.

159809.doc •23· 201232182

(In the above formulas (23) to (28), Q is a group represented by the above formula (21) or the above formula (22) or a hydrogen atom. wherein 'in each of the formulas, q is not all hydrogen atoms). Since the group represented by the above formula (21) absorbs in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Further, since the group represented by the above formula (22) absorbs in a wide wavelength region, it is suitable for exposure at a wide range of wavelengths. Therefore, it is preferred to select one of the groups represented by the above formula (2) or the group represented by the above formula (22) in accordance with the wavelength to be exposed. The positive photosensitive resin composition of the present invention The content of the photosensitive diazonium compound is 〇丨~(7) parts by weight, preferably 15 parts by weight, based on the total amount of the epoxy oxirane compound of the present invention and the matrix resin of the present invention. The damage is preferable from the viewpoint of developability and fine workability of the permanent anti-contact agent of the present invention. Next, the organic solvent will be described. The organic solvent which can be used in the present invention is not particularly limited as long as it can be used. The epoxy 7 oxyalkylating compound of U, the base resin of the present invention, the photosensitive diazomethane compound, and the compound base compound of the formula (3) described later, and the compound of the following formula (4) Hydrolysis of aryl-based compounds 159809.doc •24· 201232182 The substance may be dissolved or dispersed, and may be any organic solvent. Examples of such an organic solvent include decyloxy-ethanol, hydrazine-ethoxy-ethanol.丨_propoxyethanol isopropoxy- Alcohol, 1-butoxy-ethanol, methoxy-2-propanol, 3-methoxybutanol, 3-methoxybutenyl butanol, ether alcohols, 1-methoxyethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2-propionic acid acetate, 3-decyloxy-1-butyl acetate, 3-methoxy-3-indolyl- Acetate of ether alcohol such as 1-butyl acetate; ketones such as acetone and methyl ethyl ketone; 4-hydroxy-2-butanone, 3-hydroxy-3-indolyl-2-butanone, base Ketone alcohols such as 2-mercapto-2-pentanone (diacetone alcohol); ethers such as hydrazine, furan, 1,2-dimethoxy ethane; 丫-butyrolactone, hydrazine a cyclic ester such as 4-hydroxytetrahydrolactone lactone; a carbonic acid excipient such as ethyl carbonate, propylene carbonate or diacetic acid carbonate; and among these, due to solubility A good and moderately volatile volatilization is preferably an acetic acid vinegar, preferably 1. methoxy·2-propyl acetate, 3-methoxy-丨-butyl acetate And 3-methoxy-3-methylbutyl acetate, preferably 1-methoxy-2-propyl acetate. In the positive photosensitive resin composition of the present invention, operability Or coated film ^ From the viewpoint of the nature, the total weight f/j of the content of the above organic solvent relative to the content of the % oxygen oxytoxin compound of the present invention and the matrix resin of the present invention is 1 〇 1 1 〇 重量 重量 ' Just as the weight part is 0, the positive type (four) resin of the present invention is used, and the mouth material is preferably a wire 7-burning compound represented by the formula T (3) and the lower layer. () a hydrolysis condensate of the aryl cerium compound of ητ (hereinafter also referred to as a hydrolysis condensate of the present invention). 159809.doc •25· 201232182 R-Si-fx% (3) (R represents no carbon number 1 ~ 4 炫 base, χ 1 represents carbon number b 4 alkoxy or south atom). R-Si-fx2)3 (4) (indicates an aryl group having a carbon number of 6 10 and χ2 represents an alkoxy group having a carbon number of 44 or a halogen atom). In the above formula (3) towel, R2 table * carbon number b 4 yard base. Examples of the alkyl group having 1 to 4 carbon atoms include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a monobutyl group, an isobutyl group, a t-butyl group and the like, and R2 is used as a development margin. It is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. More preferably, it is preferably an anthracene group and an ethyl group. To show the alkoxy or _ atom of carbon number 4. Examples of the alkoxy group of the carbon number 4 include a methoxyethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group; and examples of the halogen atom include a fluorine atom and a gas atom. The atomic atom, the atomic atom and the like are X, and since the reactivity is good, a methoxy group, an ethoxy group and a gas atom are preferred, and a decyloxy group and an ethoxy group are more preferred. Among the alkyl decane compounds represented by the above formula (3), preferred examples of the compound include methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, and methyltriazole. Isopropoxydecane 'ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tripropoxy decane, ethyl triisopropoxy decane, propyl trimethoxy decane, propyl triethoxy Base decane, isopropyl trimethoxy decane 'isopropyl triethoxy decane' butyl trimethoxy carbaryl, T-based triethoxy 7 炫, isobutyl trimethoxy shirite, 598 〇 9d 〇C -26-

S 201232182 isobutyl triethoxy decane, decyl trichloro decane, ethyl trichloro decane, propyl dioxane, isopropyl trioxane, butyl trichloro decane, isobutyl three gas dream, etc. . In the above formula (4), R3 represents an aryl group having 6 to 10 carbon atoms. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, an ethylphenyl group, an anthranilyl group, a cumyl group, a dimethylphenyl group, a decyl group, a decyl group, a tert-butylphenyl group, and a benzoquinone. As the R3, as the R3, from the viewpoint of heat resistance, a phenyl group and an indolinyl group are preferred, and a phenyl group is more preferred. Χ2 represents an alkoxy group or a hydroxyl atom of carbon number. Examples of the alkoxy group having a carbon number of 丨4 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and an isobutoxy group; and examples of the dentate atom 2 include a fluorine atom. , chlorine atoms, desert atoms, helium atoms, etc. X2 is preferably a methoxy group, an ethoxy group or a chlorine atom because of its good reactivity, and more preferably a methoxy group. In the aryl stone compound compound represented by the above formula (4), preferred compounds 'are exemplified by phenyl trimethoxy sinter, phenyl triethoxy oxalate, and phenyl tripropoxy sulphur And phenyl triisopropoxy zebra, tolyldimethoxy decane, toluene decyl triethoxy fluorene, phenyl trioxane, tolyltriyl trioxane, and the like. In the hydrolysis condensate of the present invention, the base resin of the present invention is used in the case where the aryl A ishixiyuan compound represented by the above formula (4) is relatively small in comparison with the domain formula (the amount of the money compound) is too small. When the compatibility is excessive (4), there is a case where the hardening property of the hardened material (such as crack resistance) is adversely affected, so the molar content is 0.1 to 1 G, more preferably 〇. 2 to 4, most Good for 〇 4~2. I59809.doc -27·201232182 The hydrolyzed condensate of the present invention may be a compound of the above-mentioned formula (3) or a compound of the following formula (4) as long as it does not degrade its function. One of the aryl sulfonium compounds is partially substituted with a tetraalkoxy decane compound, a group having R (alkyl group having a carbon number of 4 4), and/or a group represented by R 3 (an aryl group having a carbon number of 6 to 10). A dialkoxy decane compound or a bidentane compound, a decane diol compound having a group represented by R (an aryl group having 6 to 1 carbon atoms), and a reaction is carried out. Examples of the compound include a tetraalkoxydecane compound such as tetramethoxynonane or tetraethoxysilane; dimethyl dimethoxy decane, dimercapto diethoxy decane, and diethyl ruthenium. Oxal oxide, monoethyldiethoxy oxime, dipropyl dimethoxy oxalate, dipropyl diethoxy decane, dibutyl dimethoxy decane, dibutyl diethoxy矽, methyl ethyl dimethoxy decane, decyl ethyl diethoxy sulphur, sulphur-based gas, sulphur, sulphur, sulphur, dipropyl, sulphur, a bis-oxo-oxygen compound or a di-decane compound having a group represented by R2, such as a butyl dioxane; a benzyloxy group, a diphenyldiethoxy group, a diphenyl group a di-n-oxyxanthene compound or a di-decane compound having a group represented by R3, such as a second gas stone court, a base gas, and a diphenyl decane compound; methylphenyldimethoxydecane, methylphenyl Ethoxylated oxime, ethyl carbyl monomethoxy sulphate, ethyl phenyl diethoxy sylvestre, methyl phenyl monooxane, ethyl phenyl di a dialkoxy decane compound or a di il decane compound having a group represented by R 2 and a group represented by R 3 such as decane; -28 having a group represented by R 3 such as diphenylnonanediol or diphenyldecanediol; · 159809.doc

S 201232182 decanediol compound. When the molecular weight of the hydrolysis condensate of the present invention is too small, the improvement effect of the development margin is not observed, and in the case of excessive material, the solubility in the test developer is decreased and the residual agent after the development is developed (4) The increase is, therefore, preferably from 6 〇〇 to 2 以, more preferably from 800 to 10,000 Å, most preferably from 1 〇〇〇 to 5 以, in terms of weight average molecular weight. The hydrolysis condensation reaction of the alkyl decane compound represented by the above formula (3) with the aryl decane compound represented by the above formula (4) may be carried out under the same conditions as in the case of the base resin of the present invention. In the hydrolytic condensation reaction, any one of an alkoxy decane compound and a dentate compound may be used, or the two may be mixed to make it easy to remove the control or by-product removal, so it is preferably used. An alkoxy decane compound, that is, an alkyltrialkoxy decane having a carbon number of 丨4 (a compound in which the oxime of the above formula (3) is alkoxy group of carbon number 4) and an alkoxylated compound, that is, a carbon number 6 to 1 芳 of the aryl-based compound of the oxylates (the compound of the above formula (4) is a compound having an alkoxy group having a carbon number of 丨4 to 4). Since the development margin of the positive photosensitive resin composition of the present invention can be enlarged, the hydrolysis condensate of the present invention preferably contains a stanol group, and the content of the base of the Shixiayuan in the hydrolysis condensate of the present invention is (10) The content is preferably (4)% by mass, more preferably 3 to 25% by mass, most preferably 5 to 2% by mass. The phenolic alcohol group formed by hydrolysis of a compound having a tris-oxy (tetra) or tri(tetra) fluorene has a tendency to undergo a condensation reaction and to reduce the content of the sylvestre base by treatment, especially in water (4). After the reaction, the product is isolated to cause dehydration condensation reaction of the phenolic groups with each other. Therefore, it is preferred to carry out the hydrolysis condensation reaction in the solvent 159809.doc •29·201232182 when the additive of the present invention is produced. The solvent is concentrated without being isolated, or if necessary, replaced with another solvent, and formulated into a positive photosensitive resin composition. In the case of the positive-type photosensitive resin composition of the present invention, when the content of the hydrolysis-condensation product of the present invention is too small, the development margin is not improved, and when it is too large, residue tends to be generated during development. Further, the physical properties of the obtained cured product are lowered, so that it is preferably 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, even more preferably 15 to 50 parts by weight, per part by weight of the base resin of the present invention. In the positive photosensitive resin composition of the present invention, a plasticizer, a thixotropic imparting agent, a photoacid generator 'thermal acid generator', a knife, a coating, a pigment, and a pigment may be blended as needed. Any component such as a dye. The blending of the optional components is not particularly limited, and it is preferably 5 parts by weight or less based on the weight of the base resin 100 of the present invention. Next, the permanent anti-caries agent of the present invention will be described. Q The permanent agent of the present invention is produced by using the positive-type photosensitive resin composition of the present invention. The procedure for producing the permanent anti-button agent of the present invention will be described. (1st step) Coating film forming step The coating film forming step is a step of forming a coating film by pre-bake and baking the prepared positive photosensitive resin composition of the present invention onto a target material. The material of the film is as long as it is for a positive photosensitive tree. The organic solvent or the like in the material has chemical resistance, and is not particularly limited as long as it has heat resistance for the fourth step and the development of the test solution or the treatment in the sixth step, and the glass and the golden eyebrow can be used. , semiconductors, etc. as target materials. In particular, the surface of the TFT 159809.doc 201232182, which is required to form an insulating layer, may be exemplified as the coating method, and is not particularly limited. For example, 1st Division - ^ .. ^ . Using a spin coating method, a dip coating method. Various prebaking methods, such as a ruthenium method and a slit coating method, are performed to remove an organic solvent from a positive-type pressure-sensitive adhesive composition layer coated on the target material. The pre-compound layer is insoluble for the test solution, and the portion irradiated by the light in the two-light step (the following is called the case) is determined to be soluble, and the temperature of the baking is different depending on the type of the organic solvent. When the temperature is too low, there is a case where the residual amount of the organic refrigerant is large and the exposure sensitivity or the resolution is lowered. 'X. If the temperature is too high, the entire coating film is hardened by prebaking. Further, since the solubility of the portion irradiated with light is lowered for the solubility of the alkaline developing solution, the exposure sensitivity or the resolution is lowered, and therefore it is preferably (9) to just. c, more preferably 70~120t:. The pre-baking time varies depending on the type of the organic solvent to be used and the pre-baking temperature, and is preferably from μ second to ι min, more preferably from 1 to 5 minutes. The prebaking can be carried out directly after applying the positive photosensitive resin composition of the present invention to the target material, and the permanent resistance of the present invention is improved after physical properties and chemical resistance after a high heat history. It is preferred that the concentration of the organic solvent in the positive photosensitive resin composition layer is 5% by mass or less at room temperature to less than 60 C and at normal temperature or reduced pressure before the pre-bake. The organic solvent is volatilized and then prebaked. The thickness of the positive photosensitive resin composition layer after prebaking differs depending on the use of the permanent resist 159S09.doc 31 201232182 agent of the present invention, and is not particularly limited as long as it is 〇i pm~i〇〇μηι, It is preferably 〇· 3 μιη~ 1 〇μιη. (Second Step) Exposure Step The exposure step is a step of irradiating the pre-baked positive-type photosensitive resin composition layer with the patterned light to increase the alkali solubility of the exposed portion. Although the pre-baked positive-type photosensitive resin composition layer is insoluble in an alkaline solution, the photosensitive diazonium compound in the exposed portion is decomposed by light irradiation to become a carboxylic acid compound, and becomes soluble. Disperse in an alkaline solution. The irradiation light is not particularly limited, and may be any light that can increase the alkali solubility of the light-irradiated portion of the pre-baked positive photosensitive resin composition layer, for example, an energy of 10 to 1000 mJ/cm 2 . The range of light is particularly preferably in the range of 40 to 300 mj/cm2. Further, the wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited. When 4—diazonaphtidine acid vinegar is used as the photosensitive diazonium compound, a high pressure mercury lamp is used. An ultra-high pressure mercury lamp or the like may be irradiated with light having a narrow wavelength mainly composed of a krypton line (365 nm); when a 5-diazonaphthoquinone sulfonate is used as the photosensitive diazonium compound, it is used as long as it is used. High-pressure mercury lamps, ultra-high pressure mercury lamps, etc., can be irradiated with a wide wavelength of light including 丨 line (365 nm), ^ line (1) "nm", and g line (436 nm). The method of patterning the above-mentioned illumination light is not particularly The method may be a previously known method, such as a light irradiation method via a photomask or the like, or a selective light irradiation method using laser light. (Step 3) Development step The development step is performed by using a developer to remove the second Step exposure step 159809.doc

S •32- 201232182 The step of illuminating the alkali and dissolving the pattern. Yuli: sub-extraction (exposure portion), whereby a specific flow water or water sprayer is formed to remove the exposed portion with water, and it is preferable to carry out dehydration drying using the inside. Washing can also be carried out in the range of 50 to 12 generations. • As a developing method, gamma-type spray method, smog method, etc., development method, dipping method, and 'basic tree 浐 且 。 。 。 method. The optimum development time differs depending on whether there are several bases and/or condensed radicals, oxo compounds, temperature of the developer, etc., but usually 3 〇 18 〇 / mile. A positive photosensitive resin composition containing a carboxyl group and/or a phenolic hydroxyi-oxygen compound as a base resin and a photosensitive heavy gas awakening material and an organic agent as a photosensitive component is present in a developing step. The development margin is small, but the development margin is made larger by containing the additive of the present invention, and it is difficult to cause the developer to penetrate between the pattern and the substrate even if the development time becomes slightly longer than the optimum development time. The resulting peeling can increase the yield of the product. The developer to be used in the development step is not particularly limited as long as it can dissolve or disperse the exposed portion in the solution, and for example, sodium hydroxide, hydroxide, sodium carbonate, or carbonic acid can be used. ; ethylamine, n-propylamine, etc. - amines; two: 4: secondary amines such as n-propylamine; trimethylamine, methyldiethylamine, dimethylethylamine, two a tertiary amine such as ethylamine; a tertiary alkanolamine such as dimercaptoethanolamine, mercaptodiethanolamine or diethanolamine; pyrrole, piperidine, n-decylpiperidine, n-methylpyrrolidine, M-diazo Heterobicyclo[5.4.〇]_7_undecene, 1,5-azabicyclo[4 3 〇]_5_pinene and other cyclic tertiary amines; pyridine, three 159809.doc -33- 201232182 An aromatic tertiary amine such as pyridine, lutidine or quinoline; an aqueous solution of an aqueous solution such as tetramethylphosphonium oxide or tetraethylammonium hydroxide; and the concentration is the previous positive type The alkali concentration of the developer used for the removal of the photosensitive resin composition layer may be used. These alkali aqueous solutions may further contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant. (Step 4) Bleaching and Exposure Step The bleaching and exposing step is an overall irradiation of the positive photosensitive resin composition layer (hereinafter also referred to as a resist layer) remaining in the alkaline solution treatment in the developing step of the third step. The step of improving visible light transmission (bleaching exposure). The anti-surname layer contains a photosensitive diazonium compound and is therefore colored yellowish or light brown. When the resist layer is irradiated with light, the remaining unreacted photosensitive diazonium compound is photodecomposed to become a ruthenium carboxylic acid compound which does not absorb in the visible light region, thereby improving visible light transmittance, and thus the permanent resistance of the present invention is used. The contact agent is particularly preferable in the case of a permanent resist for an active matrix substrate used in a liquid crystal display device or an organic EL (Electr® Lu Luminescence) display device. The irradiation light in the bleaching exposure step is not particularly limited as long as it is irradiated with light having a wavelength in the range of 10 to 1000 mJ/cm 2 , preferably 40 to 600 mJ/cm 2 . Further, the wavelength of the irradiation light is not particularly limited, and may be visible light or ultraviolet light. However, it is preferable to select the irradiation light depending on the type of the photosensitive diazonium compound to be used, similarly to the exposure step of the second step. The wavelength. (Step 5) Post-baking step 159809.doc

S -34- 201232182 In the fourth step, the visible light transmittance of the bleach-exposed resist layer is improved, but the alkali solubility is also improved. The post-baking step is performed by heat-treating the bleach-exposed anti-stoconstant layer on the 12 〇U to thermally crosslink the polyoxyxene resin in the anti-money layer to impart the requirement as a permanent resist. The step of making the permanent anti-money agent of the present invention by heat resistance, chemical resistance and chronological resistance. The post-baking is preferably carried out in an inert gas atmosphere such as nitrogen, helium or argon, preferably at a temperature of 12 Torr to 40 °C for 15 minutes to 2 hours, more preferably at a temperature of 2 Torr to 350 °C. In the coating film forming step as the first step, the positive photosensitive resin composition of the present invention can be directly applied to a target material such as a semiconductor substrate, but it can also be applied. The coating film is formed on the support film to be used as a dry film resist. After the coating film is formed, the dry film resist is prebaked to remove the solvent in the coating film and protect the film on the surface layer of the coating film. In the case of using the dry film resist obtained from the positive photosensitive resin composition of the present invention, the dry film resist is thermocompression bonded and attached after peeling off the protective film from the dry film resist. On the target material, if necessary, the support film is peeled off, and then exposed, developed, bleached, and post-baked under the above conditions. As the support film, for example, polyethylene terephthalate may be used. Vinegar (PET, Polyethylene terephthalate), poly Alkene, polypropylene, etc., but excellent in thermal properties and mechanical properties as a support film, it is preferred that the film thickness of the PET film support film is usually 1 μηι to 5 mm, preferably 1 〇μηι 100 μηΐβ The thickness of the coating film formed on the body film varies depending on the use, and is not particularly limited, and is preferably 1591 pm to l 00, preferably 159809.doc -35 to 201232182, which is 0.3 μηι to 10 μηι. The permanent anti-knocking agent obtained by the positive photosensitive resin composition of the invention is excellent not only in transparency, insulation, heat resistance and chemical resistance but also in a heat history at a high temperature of about 300 to 3 50 ° C (high heat history) In addition, the interlayer insulating film for an active matrix substrate used in a liquid crystal display device, an organic EL display device, or the like has a polycrystalline germanium film as an active layer, and is excellent in transparency, insulating properties, and chemical resistance. The interlayer insulating film for the active matrix substrate of the TFT is extremely useful. Further, the permanent anti-contact agent obtained from the positive photosensitive resin composition of the present invention can also be used for the interlayer insulating film of a semiconductor element, and a half. Wafer coating material for conductor components (surface protection film, bump protection film, MCM (multi-chip module) interlayer protection film, junction coating), encapsulation material (sealing material, die bonding material) Further, the permanent k-contact agent obtained from the positive photosensitive resin composition of the present invention is also useful as an insulating film for a semiconductor element, such as a multilayer wiring board. Examples of the semiconductor element include a diode, a transistor, and a compound. Individual semiconductor components such as semiconductors, thermistors, varistors, and thyristors, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), EPR〇M (Erasable Programmable read-only memory), Mask R〇M (Mask read-only memory), eeprom (Electrically-Erasable Programmable Read-Only Memory » Electronic erasable rewritable read-only memory), flash memory (Flash J59809.doc

S -36· 201232182

Memory components such as Memory, microprocessor, DSP (digital signal processor), ASIC (Application-specific

Integrated circuit components such as integrated circuits, such as integrated circuits, and integrated circuit components such as compound semiconductors represented by MMIC (MonoIithic Microwave Integrated Circuit), hybrid integrated circuits (hybrid 1C 'hybrid Integrated Circuit), a light-emitting diode, a photoelectric conversion element such as a charge-bonding element, and the like. Further, examples of the multilayer wiring board include a high-density wiring board such as MCM. [Examples] Hereinafter, the present invention will be further described by way of examples and comparative examples, but the present invention is not limited thereto. Further, the content of the stanol group is such that the sample is reacted with trimethyl chlorodecane in a pyridine solution to change the stanol group to a trimethyl decyl ether group, and then treated with a tetramethylammonium hydroxide aqueous solution to cause C- The 0_Si bond is hydrolyzed and calculated by inverse calculation based on the weight increase rate after the reaction. Furthermore, "%" is a unit of mass unless otherwise specified. [Production Example 1: Production of the epoxy decane compound A-1 of the present invention] 250 g of toluene was added to the glass reaction volume H equipped with a thermometer and a device, and the cyclic oxime represented by the above formula (la) was used. M,6,8-tetramethylcyclotetraoxane 144 g (〇6 mol) of the alkane compound, i as a compound having 2 to 4 vinyl groups in the i molecule, divinylbenzene 52 mol ), allyl glycidolation m94 g (17 moles) as a compound containing a carbon-carbon double bond reactive with a SiH group, and a dimethoxyl-tetramethyldioxime complex (Kamedt touch) Medium) 9 mg, face-to-face mixing - noodle to ~6〇. (: the next reaction is 15 hours. Under the solvent (10), the solvent is dehydrated from the reaction liquid by 159809.doc • 37·201232182 to obtain a glycidyl ether group-containing oxane compound, that is, the epoxy decane compound A_ of the present invention. The epoxy decane compound A-oxime of the present invention obtained by the present invention, wherein in the above formula (I), ... is a methyl group, and E is a group having an epoxy group of the above formula (5), a is equivalent The compound having 2 to 4 ethylene groups in one molecule is M-diethyl benzene (the compound of the above formula (16) wherein h is 1). Further, the present invention The weight average molecular weight of the epoxy decane compound A-1 measured by GPC analysis was 1500', and the analysis value of the epoxy equivalent was 244. [Production Example 2: Production of the epoxy decane compound A_2 of the present invention] The glass reaction vessel of the stirring device was prepared by adding 250 g of toluene as a cyclic oxirane compound represented by the above formula (la), 2,4,6,8-tetramethylcyclotetraoxane 24 〇g ( 1 〇莫耳), as a compound having 2 to 4 vinyl groups in a ruthenium molecule, 5-triallyl isocyanuric acid brewing 24 .9 g (0.1 mol) and platinum-divinyltetramethyldioxane complex (Karstedt catalyst) 9 mg, reacted for 5 hours at 5 Torr to 6 〇〇c while stirring. After the solvent and the unreacted 2,4,6,8-tetramethylcyclotetrazepine were distilled off under reduced pressure at ° C, a solution of 25 〇g was added as the inclusion and SiH group. The reactive carbon-carbon double bond compound of the propyl glycidyl ether 114 g (l. 〇 耳 — — 面 一面 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂The reaction mixture is distilled off under reduced pressure to obtain a glycidyl ether compound having a glycidyl ether group, that is, the epoxy decane compound A-2 of the present invention. The obtained epoxy decane compound A 2 of the present invention is the following compound, wherein In the formula (1), Ri is a fluorenyl group, E is a group having an epoxy group of the above formula (5), and a corresponds to a number of 3, and has 2 to 4 ethylene in the molecule. J59809.doc

S -38· 201232182 The compound is 1'3'5·trisylpropyl isocyanuric acid _ (the compound of the above formula (i8) wherein R is an allyl group). Further, the weight average molecular weight measured by GPC analysis of the epoxy decane compound of the present invention is 267 ». [Production Example 3 · Manufacturing of the base resin B_i of the present invention] The base resin Li of the present invention is produced by the production example of the polyfluorene oxide resin (a) described in the paragraphs [G152] to [G155] of the above Patent Document 3. That is, in a glass reaction vessel equipped with a thermometer and a stirring device, 3 〇〇g, 2,4,6,8-tetramethylcyclotetracycline 12 〇g (〇5 mol), heart Ethyl benzoic acid-t-butyl ester 102 g (〇5 mol), 4_t-butoxystyrene 132 g (〇.75 mol), tridecyloxy vinyl decane 111 g (0.75 Mohr), and platinum·tetraethyltetradecyldioxane complex (Karstedt catalyst) i, decompressed at 6 (rc) after stirring for 15 hours at 6 (TC) Distillation is carried out to obtain a carboxyl group of the cyclic oxirane compound represented by the above formula (19) and a compound obtained by subjecting a phenolic hydroxyl group to a third butyl group, that is, an intermediate b-oxime. The weight average molecular weight measured by GPC analysis was 900 (theoretical molecular weight was 933.1). The above intermediate b-oxime was added as 9 〇g (0.1 mol) as the above formula (20). The oxyalkylene compound phenyl trimethoxy decane 91 g (〇46 mol) and toluene 200 g were added dropwise as an organic acid catalyst for 1 hour while stirring in an ice bath at 1 ° C. Oxalic acid 5 〇g of the solution, and further stirring at 10 ° C for 15 hours. After rinsing twice with water 1 〇〇 g, reflux dehydration and de-fermentation were carried out at 50 ° C under reduced pressure, and at 5 ° C, The solvent of benzene and 1-methoxy-2-propanol acetate (hereinafter referred to as 159809.doc • 39-201232182 PGMEA (Propylene Glycol Mono-methyl Ether Acetate, propylene glycol monoterpene ether acetate) )) solvent exchange to obtain a 25% PGMEA solution of the intermediate b_2. In order to detach the second butyl group, boron trifluoride diethyl ether was added to 400 g of the 25% PGMEA solution of the above intermediate b-2. 3 g of the complex, after 8 hours of stirring at TC, 1 〇〇g of solvent treatment under reduced pressure. For the addition of an acidic adsorbent (Kyowa Chemical Industry Co., Ltd., trade name: Kyoword 500SH) after 10 g, at 80 ° (:: a slurry solution which is mixed for 1 hour, and the solid matter is removed by filtration to obtain a cyclic oxirane compound represented by the above formula (19) and the above formula (2〇) The hydrolysis condensate of the oxalate compound shown in Fig. 2 is the base resin of the present invention. The PGMEA solution obtained. The obtained base resin of the present invention is a compound in which the group in the above formula (19) is rm: mercapto 'R15: exoethyl, R16 · · ethyl, Ri7: ex Ethyl group, Rl8: methyl group, m·l'n: i.S'P: number; the base knife in the above formula (2〇) is R. Phenyl group, R21: methyl group, q:3 number. Further, the weight average molecular weight of the base resin B-1 of the present invention measured by GPC analysis is 6,900, and the content of the stanol group is $, the carboxyl group (a) and/or the divalent base group (content of 〇H). The content of B) (Α+0·1χΒ) is 1.17 mmoi/g. [Production Example 4: Production of Hydrolysis Condensate C-1 of the Present Invention] Methyltriethoxygen as an alkyl decane compound represented by the above formula (3) is added to a glass reaction vessel equipped with a thermometer and a stirring device. 178 178 g (i mole), phenyl dimethoxy decane 198 g (i mole) as an aryl decane compound represented by the above formula (4), 1-methoxy-2 as a solvent - 159809.doc 201232182 Propanol = acid hydrate (hereinafter referred to as PGMEA) 1 〇〇 g, while immersing in an ice bath for 1 hour, adding 5% aqueous solution of oxalic acid as an organic acid catalyst _ g, Continue to spoil for 10 hours. 250 g of toluene was added to the reaction volume, and the mixture was dehydrated under reduced dust and under a boot, and further concentrated under reduced pressure to remove the alcohol and toluene formed in the reaction, and filtered to obtain the hydrolysis condensate c_lgp3 ()f of the present invention. Amount % pgmea solution. The weight average molecular weight measured by the coffee analysis of the obtained hydrolysis condensate (2) of the present invention is 2000, and the content of the hair alcohol base is 7.8% of the content of 〇h. [Example 5: Manufacture of Hydrolyzed Condensate c_2 of the Invention] In Production Example 3, ethyltriethoxyxanthine 250 g (1.3 mol) was used instead of methyltriethoxyl 178 g (1 mol), and phenyl group was used. The hydrolysis condensate of the present invention was obtained by the same operation as in Production Example 1 except that the amount of the trimethoxycarb was changed from 198 g (l mole) to 125 g (〇7 mole). 〇PGMEA solution. The weight average molecular weight measured by GPC analysis of the obtained hydrolysis condensate of the present invention is a touch, and the content of the sulphate base is 75% based on the content of OH. Manufacture of epoxy oxime compound for comparison] According to paragraph 3 of the above Patent Document 3 In the production example of the oxygen-containing compound (j) having a shrinkage t oil base (4) as described in [164], a comparative epoxy epoxide element is produced, and the mouth material D·1 is produced. Adding toluene in the glass reactor, adding toluene 150 S, 2,4,6,8-tetradecylcyclotetrazepine 6〇g (0.25 mol), propyl propyl glycidyl ii4 g (i Moer), and _ 二 二 四 甲基 甲基 ( ( ( ( ( ( ( ( ( ( ( ( ( ( K K 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 159 The solvent was distilled off from the reaction liquid under reduced pressure at 60 ° C to obtain a decyloxy group compound having a glycidyl ether group, that is, a comparative epoxy siloxane compound D-1. [Examples 1 to 6 And Comparative Examples 1 to 3: Preparation and Evaluation of the Positive Photosensitive Resin Composition of the Present Invention and Comparative Example] The epoxy decane compound of the present invention obtained in the above Production Example, the comparative epoxy decane compound, and the present invention a PGMEA solution of a base resin, a PGMEA solution of the hydrolysis condensate of the present invention, and a photosensitive diazonium compound (diazobenzene) as a photosensitive component The hydrazines (DNQ) were blended in the proportions shown in Table 1, and then filtered to prepare positive-type photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3. Further, the values in the table were used. In the above formula (23), the compound of the formula (22) is a compound represented by the above formula (22) (manufactured by Daitochemix Co., Ltd., trade name: PA-). 6) [Table 1] Base resin epoxy oxirane compound hydrolysis condensate photosensitive component organic solvent Example 1 Bl (100) Al (10) - DNQ (7) PGMEA (240) Example 2 Bl (lOO) Al (10) DNQ(7) PGMEA(240) Example 3 B-1(100) Al(10) C-2(30) DNQ(7) PGMEA(240) Example 4 Bl(lOO) A-2(10) DNQ(7) PGMEA (240) Example 5 Bl(lOO) A-2(10) DNQ(7) PGMEA(240) Example 6 Bl(lOO) A-2(10) C-2(30) DNQ(7) PGMEA(240 Comparative Example 1 B-1(100) - DNQ(7) PGMEA(240) Comparative Example 2 Bl(100) Dl(10) - DNQ(7) PGMEA(240) Comparative Example 3 Bl(100) Dl(15) - DNQ(7) PGMEA (240) The positive photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to -42-159809.doc

S 201232182 The following evaluation. The results are shown in Table 2. [Preparation method of test piece] The positive photosensitive resin composition is applied onto a glass substrate so that the film thickness of the coating film becomes 2 to 3 μm by a spin coating method, and then the solvent is volatilized. Audition. Further, the patterning exposure is performed by heating the four sheets at 9 〇t for 2 minutes, and then providing a mask having a line width of 5 μΐ at the upper portion of the glass substrate, and Ultraviolet light was irradiated with an ultrahigh pressure mercury lamp at 9 〇mJ/cm2 (converted by a wavelength of 365 nm). [Evaluation of Optimal Development Time and Development Margin] The development time was changed from 30 seconds to every 5 seconds, and the optimum development time and development margin were evaluated. Specifically, for each of the positive photosensitive resin compositions, 15 test pieces were prepared, and after pattern exposure, the test pieces were immersed in a tetramethyl chlorohydroxide aqueous solution of 2.38 mass% at a liquid temperature of 25 ° C. In the middle, after 30 seconds from the start of the repair, it is taken out every 5 seconds. Immediately after taking out the test piece, it was washed with ultrapure water for 1 minute, and the air was cleaned. The air-dried test piece was observed. The time necessary for the line width to be 5 μm was set as the optimum development time, and the time from the optimum development time to the line of 5 μη. The time until the pattern was peeled off was set as the development margin. * [Alkaline resistance test] • After the test piece developed at the optimum development time is air-dried, it is irradiated as an bleaching exposure with an ultrahigh pressure mercury lamp at 200 mJ/cm2 (wavelength (10) exposure), and then exposed to the atmosphere. The heat treatment was carried out at 23 Torr for (9) minutes or under a nitrogen atmosphere at a pressure of 35 Torr for 3 minutes to form a permanent resist film by heat treatment of 159809.doc -43·201232182. The wavelength was 4 〇〇nm before and after 30 minutes of immersion in an alkaline solution of rc (monoethanolamine··n-methyl 垸 : : diethylene glycol butyl ether: 3 〇: 6 〇 mass ratio) The light transmittance was measured, and the film thickness of the resist was measured using a stylus type surface shape measuring device, and the testability was evaluated according to the rate of change of the light transmittance and the film thickness according to the following criteria. The rate of change of the light transmittance of the test piece heated under 〇C is less than 1%, the rate of change of the film thickness is less than 10%, and the alkali resistance and the high alkali resistance after the heat history are excellent. △: at 230° The rate of change of the light transmittance of the test piece heated under c is less than 1%, the rate of change of the film thickness is less than 1%, and the rate of change of the light transmittance of the test piece heated under 3 muscles is 1% or more. The change rate of the film thickness is ι〇% or more, and the alkali resistance is excellent, but the alkali resistance after the high heat history is poor. The rate of change of the light transmittance of the test piece heated at 230 C is 1 /〇 or more. The change rate of the film thickness is 1% or more, and the alkali resistance is inferior. [Table 2] Development time (section λ development margin (seconds) Financial Example 1 60 30 Example 2 60 35 〇 Example 3 60 35 〇 Example 4 60 30 〇 Example 5 ibSir . Comparative Example 2 -^_ A 60 35 35 〇~~0~ _ 50 10 Δ 45 10 〇t匕 Comparative Example 3 -1 10 〇 According to the above results, it is clear that a polyoxyalkylene compound having a carboxyl group or a phenolic hydroxyl group as a matrix resin, and a photosensitive component are contained in 159809.doc

S • 44· 201232182 The positive photosensitive resin composition of the photosensitive diazonium compound has a problem that the development margin in the development step is small, but it can be increased by containing the epoxidized alkyl ester of the present invention. A large development margin, and even if the development time exceeds the optimum development time, it is difficult to cause peeling caused by the developer to penetrate between the pattern and the substrate, and a good pattern shape can be formed. 159809.doc 45-

Claims (1)

201232182 VII. Patent application scope: 1 . A positive photosensitive resin composition containing a polyoxyalkylene compound having a carboxyl group and/or a phenolic hydroxyl group as a matrix resin, and a photosensitive diazonium hydride as a photosensitive component The compound and the organic solvent are characterized in that: a residue having a vinyl group removed from a compound having 2 to 4 vinyl groups in one molecule is bonded to each other or to a group represented by the following formula (1). An epoxy siloxane compound having a group represented by the formula (1) and a group represented by the following formula (2), (1) (wherein RI represents an alkyl group having 4 or 10 carbon atoms or a carbon number of 6 to 10 which may be the same or different, and a group having an epoxy group, and & represents a number of 2 to 5) It is synonymous with the above formula (1)). The positive photosensitive resin composition of the first aspect of the invention, further comprising a hydrocarbyl condensate compound represented by the following formula (3) and a hydrolyzed condensate of the aryl sulfonium compound represented by the following formula (sentence) 159809.doc 201232182 R2—Si—^X% (3) (R2 represents an alkyl group having 1 to 4 carbon atoms, and X1 represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom) R3—Si—fx2)3 (4) (R3 represents an aryl group having 6 to 10 carbon atoms, and X2 represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom). 3. A permanent resist obtained from a positive photosensitive resin composition according to claim 1 or 2" 159809.doc S 201232182 IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 159809.doc