TW201111414A - Alkali-soluble resin, positive photosensitive resin composition, cured film, and protective film, insulating film, semiconductor device and display device using the cured film - Google Patents

Abstract

The alkali-soluble resin of the present invention contains a polybenzoxazole precursor structure composed of a bis(aminophenol) and a structure derived from a dicarboxylic acid, and when the two aromatic rings of said bis(aminophenol) are rotated, the energy barrier of rotation of the dihedral angle calculated according to computational chemistry is less than 3 [kcal/mol].

Description

[Technical Field] The present invention relates to an alkali-soluble resin, a positive-mold photosensitive resin composition, a hardened film, a protective film, an insulating film, and a semiconductor device or a display device using the same. [Prior Art] A protective film or an insulating film of a semiconductor element is used, for example, a polyimide resin having excellent heat resistance and excellent electrical properties, mechanical properties, and the like, and moisture resistance in addition to the above characteristics. ; #好佳的聚苯和十坐树脂等. And 'there has been developed to impart sensitivity to the precursor resin such as polyimine resin, polybenzoxazole resin, etc., and the embossing pattern can be made into a part of the step simplification' and has high sensitivity Further, in the case of L-type, a photosensitive resin composition having high heat resistance, excellent electrical properties, mechanical properties, and a step-up and yield (productivity)-improving effect is not only used as a semiconductor film. It also has the possibility of being used as a resin composition for insulation. Furthermore, it has been developed from the safety layer, and a positive-type sensible resin composition capable of developing an aqueous solution has been developed. For example, Patent Document i discloses a positive photosensitive resin composition comprising a polystyrene-based polystyrene and a sensitizer-based compound. The developing mechanism of the positive photosensitive 2 lipid composition is as follows. If the positive 2-light resin composition coated on the substrate is irradiated with actinic rays through a mask of the desired pattern, the exposure (4) (exposure portion) (4)_ compound will produce 099122459 201111414 chemical change. 'Become soluble in the aqueous solution, and promote the dissolution of the soluble resin. The diazo awakening compound which is not exposed (the secret part) is insoluble in the aqueous alkali solution, and by interaction with the alkali-soluble resin, it is It is resistant. By using the difference in solubility between the exposed portion and the unexposed portion, the exposed portion is dissolved and removed, whereby a relief pattern having only an unexposed portion can be obtained. The photosensitive imide resin of the photosensitive pattern forming the embossed pattern, the polybenzazole precursor resin, and finally the dehydrated ring by 3003⁄4~35 (hard near rc) Polyurethane resin, polystyrene, and resin. In recent years, due to the miniaturization, high concentration, and thinning of semiconductor components, it is required to have a small internal stress and can harden at low temperatures. Resin, polyphenylene g σ sitting on the resin. When it is hardened at a low temperature, it is important. For example, in a reliability test such as a temperature cycle test of a semiconductor device, the properties of the cured product are almost unchanged, and the heat resistance of the semiconductor device is hard. [Provisional Technical Documents] [Patent Literature] Patent Document 1. Japanese Patent Laid-Open Publication No. SHO 56-27140 (Summary of the Invention) The object of the present invention is to provide In the case of a positive photosensitive resin composition, the internal stress is small and the alkali-soluble resin having excellent heat resistance and soilability even at low temperature is cured. ' # 099122459 4 201111414 The purpose of this seven is to provide: the internal stress is small, and even in the low = row hardening (four) excellent (four) thermal and can be red (four) New resin group frequency - two T, protective enamel, insulating film, and semiconductor devices using the same, (Improvement of the problem) (1) The species 1 is achieved according to the invention described in the following (1) to (9). (1) An alkali-soluble resin, which is composed of a structure in which an acid is bitten Two pairs (amine groups), and derived from the second retardation, Α Ύ precursor structure, wherein, according to the calculation of chemical calculations, the above-mentioned double (amine filament) opening energy energy barrier system is less than 3 [k secret. w (2) The alkali oxime described in the above (1) is represented by the following formula (1): _ knowing 'the above bis (amino group 1)

(1) (wherein Rl is derived from _0-, -S-, or a carbon number of 3 or less;

Earth's organic base. Κ·2 is a hydrogen atom, γ is §, U ^ ^ , in any of an alkyl group, an alkoxy group, a decyloxy group, or an alkyl group, and may be the same or different, respectively. A polyphenylene precursor structure composed of a bis(amine silk) and a structure derived from two or more oximes, wherein the two sides of the above double (amine secret) are not caused by the following formula (2) Angle AB-R3-D, (180 degrees to (10) 099122459 201111414 degrees rotation every 5 degrees, when using molecular orbital method to obtain the heat of formation in each configuration, the difference between the highest generated heat and the lowest heat of formation The system is less than 3 [kcal/mol].

(wherein R3 is an organic group selected from -〇-, -S-, an alkylene group having 3 or less carbon atoms, or a substituted alkyl group. R4 is a hydrogen atom, an alkyl group, or an alkoxy group, respectively (4) A positive photosensitive resin composition containing the soluble resin described in any one of the above (1) to (3), and a sensitizer. (5) A cured film comprising a cured product of the positive photosensitive resin composition described in the above (4). (6) A protective film comprising the cured film described in the above (5). (7) An insulating film comprising the cured film described in the above (5). (8) A semiconductor device comprising the cured film according to (5) above. (9) A display device comprising the cured film described in the above (5). (Effect of the Invention) According to the present invention, it is possible to provide an alkali-soluble resin which is excellent in heat resistance and reliability even when it is used as a positive photosensitive resin composition, and which has a small internal stress and is hardened at a low temperature and has a heat resistance and reliability of 099122459 6 201111414. Further, according to the present invention, it is possible to provide a positive photosensitive resin, a cured film, a protective film, an insulating film, and the like which have a small internal stress and are excellent in heat and reliability even at a low temperature. A semiconductor device or a display device. [Embodiment] Hereinafter, preferred embodiments of the soluble resin, the positive photosensitive resin composition, the cured film, the protective m, the insulating film, the semiconductor device, and the display device of the present invention will be described in detail. The soluble resin used in the present invention contains a polyphenyl benzopyrene structure composed of bis(amine) and a structure derived from Erlin, and is characterized in that: the above bis (amino group) is used as When the two aromatic rings are rotated, the energy barrier of the dihedral rotation is less than 3 [kcal/mol] calculated according to the different chemistry. The positive photosensitive wax composition is characterized by containing the above-mentioned soluble resin, Further, the protective film or the insulating film of the present invention is characterized in that it is composed of a cured film of a cured product of the positive photosensitive resin composition. Further, the semiconductor device and the display device of the present invention are characterized. The above-mentioned cured film is provided. First, the soluble resin of the present invention will be described in detail. The soluble resin of the present invention contains a polybenzoic acid composed of a bis(amine group) and a structure derived from a dicarboxylic acid. The precursor structure is characterized in that when the two aromatic rings contained in the bis(aminophenol) of the above 099122459 201111414 are rotated, the energy barrier of the dihedral rotation calculated by the calculation chemistry is less than 3 [kcal/mol] The bis(aminophenol) is preferably represented by the following formula (1): [Chemical 3]

(wherein, Ri is an organic group selected from -〇-, -S-, an alkylene group having a carbon number of 3 or less, or a substituted alkyl group. R2 is a hydrogen atom, an alkyl group, an alkoxy group, a decyloxy group, Any of the cycloalkyl groups may be the same or different.) The energy barrier of the dihedral rotation of the bis(aminophenol) is, for example, the Scigress Explorer manufactured by Fujitsu Co., Ltd., according to the PM5 method of MOPAC2006. Can be calculated. Specifically, the structure of the bis(aminophenol) represented by the formula (2) is drawn such that the dihedral angle AB-R3-D is rotated every 5 degrees in the range of -180 to 180 degrees, and heat of formation is calculated. You can find the value of the energy barrier. [Chemical 4]

(wherein R3 is an organic group selected from the group consisting of -0-, -S-, an alkylene group having a carbon number of 3 or less, or a substituted alkyl group. The FU-based hydrogen atom, an alkyl group, or an alkoxy group may be respectively The same can be different.) 099122459 8 201111414, number finding method. On the other hand, in the present invention, the technique of stress is easily relaxed by making the rotational motion of the molecule easier. The easiness of the movement of the molecular filaments is regarded as the amount of the intramolecular rotation barrier. The calculation of the difference between the highest and lowest values of the generated heat when using the above-mentioned dihedral rotation is performed by using computational chemistry, and it is found that the value is less than 3_. When 双1] is a double (amine wire), it can be obtained. c When the internal stress at the time of hardening is less than 3 GMPa, it is a low-stress positive photosensitive resin composition. The lower the energy barrier is, the better it is. It is particularly difficult to have a substituent on the (iv) ring, and the linkage is an ether-bonded 3,3'-diamino-4 4,4,-dihydroxydiphenyl ether. The methylene-bonded 4,4,-methylene bis (2-aminol age) and the like. The energy barrier system is preferably as low as possible from the viewpoint of internal stress relaxation, but the energy barrier is preferably 0.50 or more in consideration of other physical properties and disposal requirements for the positive photosensitive resin composition. Further, if the hardening is performed at a low temperature because the glass transition temperature of the cured film is also lowered, there is generally a problem of reliability. However, it has been found that the aromatic ring designed to reduce the rotational energy barrier has fewer substituents on the linker, and the smaller monomer 'has reflow resistance despite the lower hardening temperature of 200 ° C. Excellent heat and reliability. This phenomenon is considered to be due to the fact that the structure having a small number of substituents and a small volume is associated with dense packing of molecular chains, which causes the flux used in the reflow test to be less likely to penetrate into the film. R1 of the formula (1) and R3 of the formula (2) are each an alkyl group selected from the group consisting of -0-, -S-, a carbon number of 3 or less, 099122459 9 201111414 alkyl group, a substituted alkyl group, and an alkyl group. Specific examples of the substituted alkylene group may be, for example, -CH2-, _ch(ch3)-, -C(Ch3)2_

Under the condition that the recordable material is maintained, the core liquid has sufficient impurities to obtain a more balanced and excellent solubility resin. Specific examples of the alkyl group include, for example, a small knife, even if the hard-CH3 > -CH2CH3'-CH2CH2CH3'-CH(CH3)2'-ch2ch2ch2ch3'-CH2CH(CH3)2'-CH(CH3) is applied at a low temperature. ) (CH2CH3) '-CH2CH2CH2CH2CH3, -CH2CH2CH2CH2CH2CH3. Specific examples of the alkoxy group include -OCH3, -OCH2CH3, -OCH2CH2CH3, -〇CH(CH3)2, -OCH2CH2CH2CH3, and the like. The alkali-soluble resin used in the present invention has a polybenzoxazole precursor structure, but is not limited thereto, and may have other structures. Other structures may, for example, have a structure in which at least one of a poly- and a carbazole structure and a polyimine structure has a hydroxyl group, a carboxyl group, an ether group or an ester group; and a polyimine precursor Construction, polyphthalate structure. For example, from the viewpoint of heat resistance and reliability after final heating, a polyamide resin having a structure of the formula (3-1) is preferred. More preferred polyphenylene β-azole precursor resin represented by formula (3-2): [Chemical 5] 099122459 10 201111414

(In the formula (3), the X and Y organic groups. a, b, c, and d represent the percentage of moles, a+b=100, c+d=100, and a and c are 70 or more and 1〇, respectively. 〇 Hereinafter, b and d are respectively 〇 or more and 30 or less. &, hydroxy, or sine, and may be the same or different. Rs is a hydroxyl group, a carboxyl group, _〇_&, _c〇〇_h One can be the same or different. The integer of the claw system 〇~2, the integer η of the η system 〇4 is an integer of 0 to 2. The & is an organic group having a carbon number of 〜15. In the case where R? is not a hydroxyl group, Rs must have at least i carboxyl groups. Further, when Rg is not a carboxyl group, R*7 must have at least one mesogenic group. The organic group selected from the group consisting of -Ο-, -S-, an alkyl group having a carbon number of 3 or less, and a substituted alkyl group. Re Ru is a hydrogen atom, an alkyl group, an alkoxy group, a decyloxy group or a cycloalkyl group, and may be the same or different. Specific examples of the alkylene group and the substituted alkylene group of '&, R1() in the formula (3) include, for example, -CH2-, -CH(CH3)-, -C(CH3)2- and the like. Specific examples of the alkyl group of 'R_6 and Ru in the formula (3) include, for example, _ch3, -CH2CH3, -CH2CH2CH3, -ch(ch3)2, -ch2ch2ch2ch3, -CH2CH(CH3)2 > -CH(CH3) (CH2CH3) > -ch2ch2ch2ch2ch3 > -CH2CH2CH2CH2CH2CH3 and the like. Specific examples of the methoxy group include, for example, -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, 09912245911 201111414-〇CH2CH2CH2CH3. The polyamine resin having a structure represented by the formula (3-1) is, for example, a bis(aminophenol) represented by the formula (1), a diamine or a bis(aminophenol) optionally containing X, and 2 a compound selected from the group consisting of 4-diaminophenol and the like, and a tetracarboxylic dianhydride containing from Y, trimellitic anhydride, a dicarboxylic acid or a dicarboxylic acid dicarboxylic acid, a dicarboxylic acid derivative, a transbasic acid A compound obtained by reacting a compound selected from the group consisting of a base dicarboxylic acid derivative, and obtained by a reaction. The polybenzazole-based precursor resin represented by the formula (3-2) is, for example, a bis (amine group) represented by the formula (1), a bis (amino group) containing X as necessary, and 2,4- A compound selected from the group consisting of a compound selected from the group consisting of a Y-containing dicarboxylic acid or a di-vaporized diterpene, a dicarboxylic acid derivative, and the like is obtained by a reaction. Further, in the case of the dicarboxylic acid, in order to increase the reaction yield and the like, an active ester type dicarboxylic acid street material which is previously reacted with 1-hydroxy-1,2,3-bromotriazole or the like may be used. When a and c are 70% by mole or more, the internal stress is less than 3 MPa MPa, and the soluble resin is excellent in heat resistance and reliability even at 2 〇 (TC is hardened). In the alkali-soluble tree fat, -O-R9 which is an X substituent, and -O-R9 and -COO-R9 which are Y substituents are carbon-reducing for the purpose of adjusting the solubility of a hydroxyl group and a carboxyl group in an aqueous alkali solution. The group of 1 to 15 organic groups protected by I, if necessary, can also protect the hydroxyl group, carboxyl group. Examples of R9 are: formazan, fluorenyl, ethyl, propyl, isopropyl, tert-butyl , the third butyl gas several 099122459 12 201111414 base, phenyl, fluorenyl, tetrachloro butyl group, tetraaza d-butyl group, etc. When the alkali-soluble resin is heated at a low temperature of 150 ° C or more and not The treatment is carried out at 280 ° C, and the treatment is carried out at 280 ° C or higher and 380 ° C or lower at the high temperature, and the dehydration ring closure is carried out, and the polybenzoxazole resin or polybenzoxazole resin can be used. And a heat-resistant resin obtained by copolymerization with a polyimide resin. If heat treatment is performed at a low temperature, The internal stress is small, and the yield is improved in the production of the semiconductor element, and the effect is excellent in reliability. The X-based organic group of the formula (3), for example, an aromatic compound such as a benzene ring or a naphthalene ring; Further, a heterocyclic compound such as a phenol, a pyrrole or a furan; and a oxoxane compound are more preferably those represented by the following formula (4). These may be used alone or in combination as needed. More than one species. [Chem. 6]

(4-3)

One°—, one R16—3 Ria ^18 (4-7) (4) 099122459 13 201111414 (wherein * indicates that the bond is bonded to the NH group. A is -CH2-, -CH(CH3)-, -C(CH3 ) 2-, -Ο-, -S-, -S〇2-, -CO-, -NHCO-, -C(CF3)2-, or a single bond. R13 is derived from a base, a base, and a burn The one selected from the group consisting of a sulfhydryl group and a tooth atom may be the same or different. Rl4 is one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom. An integer of R = 0 to 2. R15 to R18 It is an organic group.) In the formula (4), the alkyl group of Rl3 and R14 is specifically exemplified by -CH3, -CH2CH3, -ch2ch2ch3, -CH(CH3)2, -CH2CH2CH2CH3, -CH2CH(CH3)2 , -CH(CH3)(CH2CH3), -C(CH3)3, -CH2CH2CH2CH2CH3, -CH2CH2CH(CH3)2, -ch2ch(ch3)(ch2ch3), -ch(ch2ch3)(ch2ch3), -CH(CH3) (CH2CH2CH3), -CH(CH3)(CH(CH3)2), -CH2CH2CH2CH2CH2CH3, -CH(CH3)(CH2CH2CH2CH3), _ch(ch3)(ch2ch(ch3)2), -CH2CH2CH2CH2CH2CH2CH3, -CH2CH2CH2CH2CH2CH2CH2CH3, and the like. As shown in the formula (3), 在~2 R7 or R12 are bonded on X. (In the formula (4), R7 and Rl2 are omitted). In the formula (3), the molar percentages b and d containing the repeating unit of X may also be 0 (zero). Further, the γ-based organic group of the formula (3) has the same substance as the above X, for example: the 裒T ring special-purpose fragrant compound; the double-seeking class, the e-ratio 17 type, and the “7 class, the coward A heterocyclic compound such as a southern type; and a Wei compound, etc., more specifically preferably 099122459 14 201111414 as shown in the following formula (5). These may be used alone or in combination of two or more. [Chemistry 7]

(5-7) — R23 R23

(wherein * indicates that the bond is bonded to the 〇0 group. The A system is -CH2-, -CH(CH3)-, -C(CH3)2_, _〇_, -S-, -S〇2_, -CO- -NHCO-, -C(CF3)2_, or a single bond. The one selected from the group consisting of an alkyl group, an alkyl ester group, an alkyl ether group and a halogen atom may be the same or different. One selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. An integer of t = 0 to 2. R21 to R24 are an organic group.) In the formula (5), a specific example of an alkyl group of R19 and R20, For example, -CH3, -CH2CH3 > -CH2CH2CH3' -CH(CH3)2' -CH2CH2CH2CH3' -CH2CH(CH3)2, -ch(ch3)(ch2ch3), _c(ch3)3, _ch2ch2ch2ch2ch3, - CH2CH2CH(CH3)2'-CH2CH(CH3)(CH2CH3) > -CH(CH2CH3)(CH2CH3) -ch(ch3)(ch2ch2ch3) -CH(CH3)(CH(CH3)2) 099122459 15 201111414 -ch2ch2ch2ch2ch2ch3, -ch(ch3)(ch2ch2ch2ch3), -CH(CH3)(CH2CH(CH3)2), -ch2ch2ch2ch2ch2ch2ch3, -CH2CH2CH2CH2CH2CH2CH2CH3, and the like. As shown in the formula (3), 0 to 4 R8 are bonded to Y (in the formula (5), R8 is omitted). Among these, those who are particularly good are those shown by the following formula (6). The structure derived from the tetracarboxylic dianhydride in the following formula (6) is, for example, a position at which a bond is bonded to a c=o group, or both of them are in a para position, and may also contain a meta position and a pair. The construction of the bit. [化8]

099122459 16 201111414 (wherein * means a bond to a C=0 group. R25 is one selected from the group consisting of an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, and each may be the same or R26 is one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and a part thereof may be substituted. An integer of u = 0 to 2. In the formula (6), a specific example of the alkyl group of R25 For example, -CH3, -CH2CH3, -ch2ch2ch3, -ch(ch3)2, -ch2ch2ch2ch3, -ch2ch(ch3)2, -ch(ch3)(ch2ch3), -c(ch3)3, -ch2ch2ch2ch2ch3 -CH2CH2CH(CH3)2 ' -CH2CH(CH3)(CH2CH3)' -CH(CH2CH3)(CH2CH3)' -CH(CH3)(CH2CH2CH3)' -CH(CH3)(CH(CH3)2)' -CH2CH2CH2CH2CH2CH3 -ch(ch3)(ch2ch2ch2ch3), -CH(CH3)(CH2CH(CH3)2), -CH2CH2CH2ai2CH2CH2CH3, -CH2CH2CH2CH2CH2CH2CH2CH3, and the like. In order to be able to form a positive photosensitive resin composition composed of the above-mentioned alkali-soluble resin, it has excellent heat resistance at low temperature, and is preferably an X- and Y-based cyclic compound in the formula (3), particularly preferably an aromatic compound. . Further, the alkali-soluble resin represented by the above formula (3) is preferably an acid group at the terminal of the alkali-soluble resin, using an acid anhydride containing an aliphatic group or a cyclic compound group having at least one of a gyro group or a fast group or The acid derivative is capped to form a guanamine. This will improve the preservation. Such an anhydride of a (tetra) group or a cyclic compound group containing at least one of a filament or a silk which reacts with an amine group at the end of the soluble resin may be, for example, maleic acid or bicyclo [221] a -5-ene-2,3-dicarbamic anhydride, 4-ethynylphthalic acid-, 4-(phenylethyl fast) ortho-dicarboxylic acid material, for example, formula (7). The acid property system can be exemplified by the formula: 099122459 17 201111414 (8). These systems may be used singly or in combination of two or more. [化9] Ο Ο

099122459 18 201111414 [化 ίο]

Among these, the most preferable one is selected from the group in the following formula (9). This can be used to improve retention. [化11]

Further, 'and not limited to the present method' may also be used as the terminal carboxylic acid contained in the alkali-soluble resin, using an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. Blocking to form guanamine. (Positive photosensitive resin composition) Next, the positive photosensitive resin composition will be described in detail. The positive or optical resin composition is characterized by containing the above alkali-soluble resin and a sensitizer. The sensitizer used in the present invention may be a sensitizer capable of performing positive patterning, and specifically, a photosensitive diazonium compound or a phosphonium salt or the like which generates an acid using light 099122459 19 201111414 or dihydrogen may be used. A pyridine compound or the like. The photosensitive diazonium compound may, for example, be a phenol compound or an ester with 1,2-naphthoquinone-2-diazo-5-sulfonic acid or 1,2-naphthoquinone-2-diazo-4-sulfonic acid. . Specifically, for example, an ester compound represented by the formula (10) to the formula (13) can be used. These systems may be used singly or in combination of two or more. [化 12]

099122459 20 201111414 [Chem. 13]

OQ QO

OQ

OQ H3C CH3

-ch3

OQ

OQ, ch3

CH3 h3c OQ

Ch3 h3c

(11) 099122459 21 00 201111414 [Chem. 14]

Ch3 ch3 ch3 (12) 099122459 22 201111414 [Chem. 15]

QO OQ QO CH3 H3C OQ (13) In the formula, Q is selected from a hydrogen atom, a formula (14), or a formula (15). Here, at least one of the Qs of each compound is a formula (14) or a formula (15). [Chemistry 16]

[Π化]

Further, in the present invention, in order to further perform the development according to the high sensitivity, the patterning of the resin residue (residue) is carried out in the line of 099122459 23 201111414, and a phenolic compound can be added. The resin composition and the photosensitive resin composition of the present invention may further contain an additive such as a leveling agent or a decane coupling agent as needed. In the present invention, the components are dissolved in a solvent and used in the form of a varnish. The solvent may, for example, be N-methyl-2-β-pyrrolidone, lactone, ν,ν-dimercaptoacetamide, diterpene hard, diethylene glycol dioxime, diethylene glycol diethyl Test, diethylene glycol dibutyl hydrazine, propylene glycol monomethine, dipropylene glycol monomethyl bond, propylene glycol monomethyl (tetra) _, lactic acid, lactic acid, lactic acid, methyl 1,3-butanediol Acetate, 1,3-butanediol monoterpene (tetra), propyl warm methyl ester, propyl S is the same as the acid, and 3-methoxypropionic acid is used alone or in combination. The method of using the photosensitive resin composition of the present invention is first applied to a suitable support (for example, a stone substrate, a ceramic substrate, a substrate, or the like). The coating amount is applied when applied to a semiconductor element, and the final film thickness after hardening is 0.1 to 30/rni. If the film thickness is less than the lower limit, it will be difficult to fully utilize the protection of the semiconductor element. If the function exceeds the upper limit, it is difficult to obtain a fine relief pattern. Processing takes less time and leads to lower productivity. The coating method is, for example, spin coating using a spin coater, spray coating using a spray coater', or such as dipping, printing, coating, and the like. Next, pre-baking is carried out at 6 〇 to 13 〇t to dry the coating film, and then the actinic ray is irradiated to have a desired pattern shape. The actinic ray system can be used, for example, X-ray, electron beam, ultraviolet light, and can be seen as a wavelength of 200 to 500 nm. By dissolving and removing the illuminating portion by the developing solution, (4) the developing solution can be suitably used, for example, sodium hydroxide, sodium hydride, sodium sulphate, sodium sulphate, ammonia, and the like; a secondary amine such as n-propylamine or an amine, diethylamine or di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; an alcohol amine such as dimercaptoethanolamine or triethanolamine; An aqueous solution of a quaternary ammonium salt such as tetramethyl sulphate or tetraethylammonium hydroxide, and a water-soluble organic or surfactant prepared by adding an appropriate amount of an alcohol such as f-alcohol or ethanol (IV) or a surfactant in the towel. Aqueous solution. Development methods can be used: spray, paddle method, impregnation, ultrasonic, and the like. Next, the relief pattern formed by development is subjected to cleaning. The cleaning solution uses distilled water. Next, heat treatment (hardening) is performed to form a sirolimus ring. The anthracene ring and the brewed imine ring give a heat-resistant hardened material. The heat treatment can be carried out at a high temperature or at a low temperature, and the heat treatment temperature at a high temperature is preferably, more preferably, 29 〇 &lt; t 〜 35 (the heat treatment temperature at a temperature of rc ^ m is preferably l5 〇〇 c to 28 (rc, more preferably 180 ° C to 260 ° C. Next, the cured film of the photosensitive resin composition formed according to the present invention will be described. The cured film of the cured product of the photosensitive resin composition is not only It can be used for semiconductor devices such as semiconductor devices, and can also be effectively used for display devices such as TFT-type liquid crystals or organic ELs, or for example, interlayer insulating films of multilayer circuits or surface coatings of exchangeable copper plates. A solder film and a liquid crystal are provided in a film. The semiconductor device is used as a passivation film in which a cured film of the photosensitive resin composition is formed on a semiconductor element, and the photosensitive resin composition is formed on the passivation film. The protective film such as a buffer coating film made of a cured film, and an insulating film such as an interlayer insulating film formed by forming a cured film of the photosensitive resin composition on a circuit formed on a semiconductor element And an alpha line barrier film, a flat film, a protrusion (resin column), a partition wall, etc. The display device use example is a protective film formed by forming a cured film of the photosensitive resin composition on a display element. An insulating film or a planarizing film for a TFT element or a color filter, a protrusion for an MVA liquid crystal display device, a spacer for an organic EL element cathode, and the like. The method of use is according to the use of the semiconductor device, according to the above method. Forming a patterned photosensitive resin composition layer on a substrate on which a display element or a color filter has been formed. Display device use (especially for insulating film or planarizing film use) requires high transparency Before the photosensitive resin composition layer is cured, a resin layer having excellent transparency can be obtained by introducing a post-exposure step, which is practically preferable. <Examples> Hereinafter, the present invention is carried out according to Examples and Comparative Examples. In detail, the present invention is not limited thereto. <Example 1> (Synthesis of alkali-soluble resin) 0.18 mol of isophthalic acid and 4,4,-dicarboxylic acid of diphenyl ether 0.72 Mo 099122459 26 201111414 The dicarboxylic acid derivative (active ester) obtained by the reaction of the ear and 1-hydroxy-1,2,3-benzotriazole 1.8 mol was 426.62 g (0.9 mol), and 4, 4'-methylenebis(2-aminophenol) 230.26 g (l mole), which was placed in a four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube, and added N 2628 g of methyl-2-pyrrolidone was dissolved, and then reacted for 16 hours at 803⁄4 using an oil bath. Next, 4-ethynyl group dissolved in N-mercapto-2-pyridinium oxime and 172 g was added. 43.04 g (0.25 mol) of phthalic anhydride was added, and the reaction was terminated by stirring for 3 hours. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water/isopropyl alcohol = 7/4 (volume ratio), and the sediment was collected by filtration and thoroughly washed with water, and then dried under vacuum. Thus, a target alkali-soluble resin composed of the compound represented by the formula (3-2), c = 100, d = 〇' and the compound shown in Table 1, was obtained. Energy barrier for dihedral rotation: The calculation system uses a personal computer MY18A/E-1 manufactured by Nippon Electric Co., Ltd. equipped with 504 MB of memory. 4,4·-indenyl bis(2-aminophenol) was depicted using Scigress Explorer Workspace manufactured by Shishitong Co., Ltd. The dihedral angle ABR^-D represented by the formula (2) is rotated every 5 degrees in the range of -180 to 180 degrees, and the heat of formation of each configuration is obtained by the molecular orbital method (PM5 method), and Make an energy map. The highest generated heat and the lowest generated heat are read from the energy map, and the nose difference is calculated. In Example 1, the energy barrier system of the dihedral angle is 10 [kcal/mol]. 099122459 27 201111414 (Synthesis of sensitizer) A phenol type (Al) 12.74 g (0.03 mol) and a triethylamine 7.59 g (0.075 mol) were placed in a thermometer, a stirrer, a raw material input port, and dried. In a four-necked flask equipped with a gas introduction tube, 3 g of acetone was added to dissolve. After the reaction solution is cooled to below 10 ° C, 丨, 2-naphthoquinone-2_diazo-5-sulfonated sulfonium 20.15 g (0.075 mol) together with acetone i〇〇g, depending on It will drip slowly over 10 °C. Then, at 1〇. (: After stirring for 5 minutes, the reaction was completed by stirring for 5 hours at room temperature. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water/sterol = 3/1 (volume ratio), and filtered. The precipitate was collected and thoroughly washed with water, and then dried under vacuum to obtain a sensitizer of the formula (Q-1).

099122459 2S 201111414

OQ (In the formula, 'Q is an IL atom, or 〇^Ν·, and Q is a total of 83% 〇^Ν·.) IS〇s (Production of photosensitive resin composition) The alkali-soluble resin to be synthesized 100 g, 13.5 g of a sensitizer having a structure of the formula (Q-i), and 2,2··methylene double-presence, dissolved in a thiol group of 200 g in a thiol group, using 0.2/mi Teflon (registered trademark) The filter is applied through a crucible to obtain a positive photosensitive resin composition. Evaluation of the workability: The positive photosensitive resin composition was applied on a Shihwa wafer by a spin coater, and then pre-baked at 120 ° C for 4 minutes using a hot plate to obtain a coating having a film thickness of about 8. Ομπι. membrane. The coating film was passed through a mask made by the letterpress printing company (test pattern No. 1 : drawing width 0.88 to 50/xm residual pattern and removal pattern) using an i-line stepping machine (manufactured by Nikon Co., Ltd., 4425i) , the exposure amount is changed and irradiated. Then, using 2.38% aqueous solution of tetramethylammonium hydroxide, the difference in film thickness between the unexposed portions after pre-baking and the visible 099122459 29 201111414 is Ιμηι, and the paddle development is adjusted during development. . Then, it was cleaned with pure &amp; 10 seconds and observed. The case where the pattern was formed was rated as "仃", and the case where the pattern was not formed was evaluated as "X", and the evaluation was performed. As a result, it was confirmed that patterning was carried out in Example 1. Internal Stress Evaluation: Further, the above-mentioned positive photosensitive resin composition was applied in the same manner. The next day, after the pre-baking, the dust-free oven in the oven is hardened at an oxygen concentration of 1000 ppm or less and at 200 c for 90 minutes. The coating film obtained on the enamel wafer was measured by a surface roughness measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 1400D) to measure the 爪 wafer diameter of 2〇〇mm (5) (except for the end) When the center of the Shixi wafer is set to zero, the difference between the core and the 19〇_ two-end part (floating part) is regarded as the “warpage amount”. FIG. 1 is a schematic diagram showing the method of measuring the amount of warpage of the wafer S. Fig. 1(a) shows the surface curvature (8), the measured distance (4), and the curvature half control (8) of the Shixi wafer s on which the coating film m has been formed. Figure j (8) is a plan view of Figure j (8), the figure does not tie the x, y direction of the sand wafer S. But, figure! Attached, painted claws are omitted. The enchantment amount (X) is the average value of the warpage of the Shixi wafer s in the χ and y directions. The internal stress a (MPa) was calculated from the obtained tortuosity (X)' using the following (Formula 1) and (Formula 2). (Number υ

R=(a2+4X2)/8X 099122459 201111414 a=D2E/{6Rt(l_v)} (Expression 2) R: radius of curvature [mm] . a: measurement distance (nine) called X: surface curvature [mm] D :矽 Wafer thickness [mm] E : elastic modulus of [ [kgf / mm2] t : cured film (coating film) thickness [mm] v : Poisin ratio In addition, in this embodiment, {E / (lv)} =180500kgf/mm2. In the first embodiment, the internal stress (7 series 25.7 MPa. Evaluation of the reflow resistance: a wafer subjected to pattern processing according to the above-described workability evaluation, in a dust-free oven, an oxygen concentration of 1000 ppm or less, and 200 ° C, 90 The hardening was performed in a minute. Then, the flux and BF-30 of Tamura Kasei Co., Ltd. were applied on the wafer by a spin coater at 500 rpm/5 sec + 1 〇〇〇 ppm / 30 sec. It was continuously applied twice in a reflow oven at 140 to 160 ° C / 100 seconds (preheating) and 350 ° C / 30 seconds. Then, it was washed with xylene heated to 40 ° C for 10 minutes. 'Using isopropyl alcohol for cleaning and drying. - The surface of the film from which the flux has been removed is observed with a metal microscope. No large cracks and wrinkles are evaluated as "〇", and large cracks will occur. The wrinkle was evaluated as "X" and evaluated. The first example did not cause large cracks, enemies, etc., and was good. 099122459 31 201111414 &lt;Example 2&gt; The monophenyl ether _4, 4'_ Dicarboxylic acid obtained by reacting 0.9 mol of dicarboxylic acid with 丨_hydroxy-丨, 2,3·benzotriazole 1·8 mol Derivative (active ester) 443.2g (〇. 9 mole), and 3,3'-diamino-4,4'-dihydroxydiphenyl ether 162 57§ (07 mole), and 4,4' - Methylene bis(2-amino-3,6-dimethylphenol) 85.918 (0_3 mole) was placed in a four-port split type equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. 2767 g of N-methyl-2-pyrrolidone was added to the flask to dissolve it. Then, the reaction was carried out at 8 (TC for 16 hours) using an oil bath. Next, the solution was added to N-methyl-2. 4_B-butyl phthalate in the ketone Mg (0·25 mol), and then carried out for 3 hours. After the reaction was filtered, the reaction mixture was poured into the water/isopropanol to collect the precipitate. After thoroughly washing with water, the mixture was subjected to "under vacuum" to obtain a target alkali-soluble resin composed of the compound shown in Table 1 with the heart = 7G, (4) 〇, P = 2, and the others are as in the examples. The photosensitive resin composition was produced in the same manner, and the same evaluation as in Example 1 was carried out. The obtained results are shown in Table 。. In Example 2, 3,3,-diamino-4,4'-dihydroxy group Diphenyl ether, 4,4'-Asia The energy barrier of the dihedral rotation of methyl bis(2-amino-3,6-dimercaptophenol) was calculated in the same manner as in Example 1, and was 〇.7 [kcal/mol], 4.7 [ Kcal/mol]. The alkali-soluble resin is 70% of 3,3,-diamino-4,4,-dihydroxydiphenyl ether, and 3% of 4,4,-fluorenylene bis(2- Amino-3,6-dimercapto) is used after mixing, so the energy barrier of its rotation will be 3,3,_2 099122459 32 201111414 Amino-4,4'-di-diphenyl bond 〇.7[kcal/mol] multiplied by a value of 0.7 times, multiplied by 4.7 [kcal/mol] of 4,4'-fluorenylene bis(2-amino-3,6-dimethylhydrazine) • The total of the multiples is 1.9 [kcal/mol]. '&lt;Comparative Example 1&gt; A dicarboxylic acid obtained by reacting 0.87 mol of diphenyl ether-4,4'-dicarboxylic acid with 1-hydroxy-1,2,3-benzotrisyl 1.566 mol Derivative (active ester) 428.42g (0.87 mole), and hexafluoro-2,2,-bis(3-amino-4-hydroxyphenyl)propane 366.26g (l mole), In a four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube, 3179 g of N-decyl-2-pyrrolidone was added to dissolve. Then, the reaction was carried out at 80 ° C for 16 hours using an oil bath. Next, 55.95 g (0.325 mol) of 4-ethynyl phthalic anhydride dissolved in 224 g of N_mercapto-2-pyrrolidinone was added, and the reaction was terminated by stirring for 3 hours. After the reaction mixture was filtered, the reaction mixture was poured into a solution of water/isopropyl alcohol = 7/4 (volume ratio), and the sediment was collected by filtration and thoroughly washed with water, and then dried under vacuum. The target alkali-soluble resin composed of the compound shown in Table 1 and having c=0, d=100, and p=2 represented by the formula (3-2) was obtained. The photosensitive resin composition was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was carried out. Results obtained • As shown in Table 1. In Comparative Example 1, the energy barrier of the dihedral angle rotation was 5.3 [kcal/mol]. 099122459 33 201111414 [s Characteristic processability 〇〇〇 reflow property 〇〇 X internal stress (MPa) 25.7 29.7 33.2 1 + dihedral rotation energy barrier 1 (kcal / mol) 〇〇 \ CO &gt; τ sensitizer (Q-1) (g) I 13.5 13.5 13.5 Preparation of soluble resin (100g) Acid (mole ratio) Isophthalic acid (0.18), diphenyl ether-4,4'-dicarboxylic acid (0_72 Diphenyl ether-4,4'-dicarboxylic acid (0.9) diphenyl ether-4,4'-dicarboxylic acid (0.87) amine (mole ratio) 4,4'-arylene di(2-amine) (1) 3,3'-diamino-4,4'-dihydroxydiphenyl ether (0.7), 4,4'-fluorenylene bis(2-amino-30000-didecyl) (0.3) Hexafluoro-2,2·-bis(3-amino-4-hydroxyphenyl)propane (1) Private province: π inch £---660 201111414 as shown in Table 1 In the first and second embodiments, the internal stress is small, and even when the temperature is 2 〇〇〇c, the reflow resistance is excellent, and the heat resistance and reliability are excellent. (Industrial Applicability) According to the present invention, it is possible to provide an alkali-soluble resin which is excellent in heat resistance and reliability even when it is used as a positive-type photosensitive resin composition, and has low internal stress and is cured at a low temperature. According to the present invention, it is possible to provide a positive photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor device using the same, which exhibits low internal stress and is excellent in heat resistance and reliability even at low temperature. Body device. This application is based on the Japanese Patent Application No. 2〇09-161652 filed on July 8th, 2009 and claims priority, and the disclosure of this article is cited in this case. [Simple description of the drawing] Fig. 1 is a schematic illustration of the method for measuring the amount of interesting music used in the calculation of the internal stress. Fig. 1(a) is a front view, and Fig. 1(b) is a plan view of Fig. 8(8). [Main component symbol description] a Measuring distance m Coating film R Curvature radius S 矽 Wafer X Charm volume 099122459 35

Claims (1)

201111414 VII. Patent application scope: 1. An alkali-soluble resin containing a polybenzoxazole precursor structure composed of a bis(aminophenol) and a structure derived from a dicarboxylic acid, which is characterized by calculation Chemically calculated that the energy barrier of the dihedral rotation between the two aromatic rings of the above bis(aminophenol) is less than 3 [kcal/mol]. 2. For the determination of soluble resin in the first paragraph of the patent application, wherein the above bis(aminophenol) is represented by the following formula (1): [Chemical 1] R9 Η H R2 (wherein R1 is independent of each other from - Ο-, -S-, an alkyl group having a carbon number of 3 or less, an organic group selected from a substituted alkyl group; a hydrogen atom of R2, an alkyl group, an alkoxy group, an anthracene Any of an oxy group and a cycloalkyl group, and may be the same or different). 3. An alkali-soluble resin comprising a polybenzoxazole precursor structure composed of a bis(aminophenol) and a structure derived from a dicarboxylic acid, which is characterized by the following formula (2) The dihedral angle AB-R3-D of the above bis(aminophenol) is shown to be rotated every 5 degrees in the range of -180 to 180 degrees, and when the heat of formation in each configuration is obtained by the molecular orbit method The difference between the highest heat of formation and the lowest heat of formation is less than 3 [kcal/mol]; [Chemical 2] 099122459 36 201111414 (wherein R3 is an organic group selected from -ο-, -s-, an alkylene group having 3 or less carbon atoms, or a substituted alkyl group; and R4 is a hydrogen atom, an alkyl group, or an alkoxy group, respectively The same or different). 4. A positive photosensitive resin composition comprising a soluble resin and a sensitizer according to the first or third aspect of the patent application. A cured film comprising a cured product of a positive photosensitive resin composition of claim 4 of the patent application. A protective film comprising a cured film of the fifth aspect of the patent application. An insulating film comprising a cured film of the fifth aspect of the patent application. A semiconductor device characterized by comprising a cured film of claim 5 of the patent application. A display device comprising a cured film of claim 5 of the patent application. 099122459 37