TW201007355A - Photosensitive resin composition, cured film, protection film and insulation film, and semiconductor device and display device therewith - Google Patents

Abstract

The present invention provides a photosensitive resin composition having excellent appearance after coating. The photosensitive resin composition is characterized by comprising an alkali-soluble resin (A), a sensitizer (B), one or more compounds (C) selected from the compounds represented by the formula (1) below, and a solvent (D). The present invention further provides a cured film composed of a cured product of the above photosensitive resin composition. The present invention further provides a protection film and an insulation film composed of the above cured film.

Description

[Technical Field] The present invention relates to a photosensitive resin composition, a cured film, a protective film, an insulating film, and a semiconductor device or display device using the same. [Prior Art] In the conventional surface protective film and interlayer insulating film of a semiconductor device, a polyimide resin having excellent heat resistance and excellent electrical properties and mechanical properties is used. However, recently, a polybenzoxazole resin which does not contain a carbonyl group derived from a highly polar quinone ring and which has good moisture resistance, has been developed, and by imparting photosensitivity to the resin itself, a part of the step of forming a relief pattern has been developed. A simplified photosensitive resin composition. At the present time, in order to further improve the safety surface, a positive photosensitive resin composition composed of a diazonium compound which can be used as a polybenzoxene precursor and a sensitizer for developing an aqueous alkaline solution has been developed (see Patent Document D). Here, the production of the relief pattern of the positive photosensitive resin composition is explained by a developing mechanism. The coating film on the wafer is irradiated (exposed) with a chemical ray by a photomask by a exposure apparatus such as Stepper, thereby generating a a part of the exposure (hereinafter referred to as an exposure portion) and an unexposed portion (hereinafter referred to as an unexposed portion). The diazonium compound present in the unexposed portion is insoluble in the aqueous solution and, in addition, interacts with the resin Further, it has a resistance H surface to the alkaline aqueous solution, and the diazo-containing brewing compound present in the exposed portion causes chemical change by the action of chemical rays to become soluble in the alkaline aqueous solution and promote dissolution of the resin. The solubility of the part and the unexposed part 098105610 4 201007355 The difference is that the exposure pattern is removed from the embossed pattern of the unexposed part of the financial production. Since the coating property is important, the coating property is important. When this positive photosensitive resin composition is applied to a wafer, unevenness may be observed on the coating film. In the case of a foundry that is sold in a round state, there is a case where it is considered to be problematic due to the cause of the makeup. Further, the edge portion of the wafer is usually removed by a solvent or the like in order to prevent contamination of the semiconductor manufacturing apparatus. The EBR (EdgeBeadRemGeai) of the resin at the edge portion is sometimes not removed by the device manufacturer. In this case, the unevenness at the edge portion of the wafer becomes remarkable. [Patent Document 1] Japanese Patent The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition, a cured film, a protective film, an insulating film, and the like which are excellent in appearance after application. The semiconductor device of the present invention is achieved by the present invention described in the following [1] to [13]. [1] A photosensitive resin composition characterized by comprising a soluble resin (A), Photosensitive agent (B), which is of general formula (1) One or more of the compounds (C) and the solvent (D) selected from the compounds shown in the formula. - [Chem. 1] 098105610 5 201007355

OH H3C—C=:CH-CH2'_CH2_*C a CH - ch2 CH3 CH3

OH (1) H3C—C=CH-CH2~*CH2—〇H2CH3 ch3 ch3

OH

The photosensitive resin composition as described in the above [1], wherein the content of the above chemical (C) is relative to the above alkali-soluble resin (A). 1 part by weight, the difference is 1 to 50 parts by weight. [3] The photosensitive resin composition according to [1] or [2] above wherein the solvent (D) is r-butyrolactone (D1). [4] The photosensitive resin composition as described in the above [3], wherein the combination of the above-mentioned fossil (C) and the above-mentioned τ-butane_(D1) is no" [] as described above [ The sense level composition according to any one of the above-mentioned items, wherein the above-mentioned test/complexity tree (A) is a polyamine-based resin containing a repeating unit represented by the general formula (2). [Chemical 2]

098105610 201007355 (wherein X and Y are organic groups. Ri is a thiol group, _0_R3, an alkyl group, a tyrosine group, a cycloalkyl group, and may be the same or different. r2 is a hydroxyl group, a carboxyl group, -o-r3, - Any one of C00-R3 may be the same or different. m is an integer of 0 to 8, and η is an integer of 0 to 8. R3 is an organic group having a carbon number of 1 to 15. Here, when 吣 is plural, They may be the same or different. When Ri is not a hydroxyl group, at least one of R2 must be a carboxyl group. Further, when R2 is not a carboxyl group, at least one of Ri must be a hydroxyl group.) [6] Photosensitivity as described in [5] above In the resin composition, X of the polyamid-based resin having a repeating unit represented by the general formula (2) of φ is one or more selected from the group consisting of the following formula (3). [Chemical 3] φ

(3) OH

HO

OH (wherein, * represents a bond to the NH group. D in the formula (3-7) is -CH2-098105610 7 201007355 -CH(CH3)-, -c(CH3)2-, -〇_, _s_ , _s〇2-, -c〇-, -NHCO-, C(CF3)2-, or a single bond. r4 is any of an alkyl group, an alkoxy group, a decyloxy group, or a cycloalkyl group, which may be the same (1) The photosensitive resin composition according to the above [5], wherein the polyamine compound having the repeating unit represented by the general formula (2) is the same. The γ of the resin includes one or more selected from the group consisting of the following formula (4). [Chemical 4]

(4-3)

(R5)v (4 — 2) (4)

(4-4) (here, * is a bond to a sulfhydryl group. Rs is a one selected from a base group, a burnt vine group, a burnt bond group, a (tetra) group, and a tooth atom, and may be the same or phase respectively. (8) An integer resin composition as described in the above π] or m, wherein the sensitizer (B) contains a diazo brewing compound. [9] A cured film comprising the cured product of the photosensitive resin composition according to (1) or (2) above. [10] A protective film comprising the cured film according to the above [9]. 098105610 8 201007355 [11] An insulating film comprising the cured film of the above [9]. [12] A semiconductor device comprising the cured film according to [9] above. [13] A kind of display device, film. [14] The photosensitive resin composition as described in the above [9], which is the same as the above-mentioned [6] and the above-mentioned photosensitive resin composition, which has the above-mentioned repeating unit of the formula (2) The Y of the resin includes those selected from the group consisting of the following formula (4). [Chemical 5]

(This is the table continued to c = thiol. To indicate that the selected from the yard base, the burnt vine base, the burnt base, the ether group, and the _ atom may be the same or different. v=0~4 In the case of this, it is possible to obtain a cured film, a protective film, an insulating film, and a semiconductor device using the same, which is excellent in appearance after application. [Embodiment] Hereinafter, preferred embodiments of the photosensitive resin composition, the cured film, the 098105610 9 201007355 protective film, the insulating film, the semiconductor device, and the display device of the present invention will be described in detail. The photosensitive resin composition of the present invention is characterized by comprising an alkali-soluble resin (A), a photosensitive agent (B), and one or more compounds selected from the compound (C) represented by the following general formula (1). [Chemical 6]

OH H3C——C: CH -CH2-CH2-f-CH=CH2 CHa ch3

OH h3c—c=ch-ch2-ch2-c—ch2ch3 (1) CH3 ch3 H3c—C—CH2CH2-CH2-C—ch=ch2

I I CH3 CH3 The cured film of the present invention is characterized by comprising a cured product of the photosensitive resin composition described above. Further, the protective film and the insulating film of the present invention are characterized by being formed of the cured film described above. Further, the semiconductor device and the display device of the present invention are characterized in that they have the cured film described above. First, a photosensitive resin composition (particularly a positive photosensitive resin composition) will be described. The photosensitive resin composition of the present invention contains an alkali-soluble resin (A). 098105610 10 201007355 Examples of the soluble resin (A) include a nail varnish resin, a styrene resin, a methyl acrylate resin, a methyl acid, and the like: an acrylic wax and a warp-containing resin. a cyclic olefin system such as a county, a poly-based resin, or the like. Among them, the polyamine-based resin is preferred in terms of excellent heat resistance and good mechanical properties, and (4), the county has at least the silk (four) and the polyamidene structure, and is in the main chain or a resin having a reduced, silk, ether or vine group in the side chain, a resin having a polyphenylene precursor structure, and having a polyfluorene

A linoleum precursor structure, a resin having a poly-structure, and the like. For the purpose of this type of poly(4), a polyamine-based resin having a repeating unit represented by the following formula (7) can be listed. [Chemistry 7]

(严1一Ϊ一丫一(2) Ο Ο (wherein X and Y are organic groups. Rl is a trans-group, -〇-R3, a pyridyl group, a methoxy group, a % alkyl group, which may be the same or different. I is a hydroxyl group, a carboxyl group, _〇_R3, _c〇〇_r3 'may be the same or different. m is an integer of 0 to 8, !! is an integer of 0 to 8. r3 is a carbon number The organic group of 15. Here, when & is plural, they may be the same or different. When Rl is not a radical, 'R2 must be at least one is a rebel. Also, when R2 is not a few, Ri must be at least One is a hydroxyl group.) In the polyamidamide resin represented by the general formula (2), 〇R? as a ruthenium substituent is used as the ο%, coo% of the Y substituent, and is adjusted in the basis of The base protected by the organic group R7 098105610 201007355 having a carbon number of 1 to 15 can also protect the hydroxyl group and the carboxyl group as needed. Examples of the r7 include mercapto group, mercapto group and ethyl group. a propyl group, a propyl group, a butyl group, a butyl group, a third butyloxycarbonyl group, a phenyl group, a benzyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, etc. A polyamine containing a structure represented by the general formula (2) Resin, system For example, a compound containing X diamine or bis(aminobenzene), 2,4-diaminobenzene, etc., and a tetracarboxylic dianhydride containing Y, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid a compound obtained by reacting a selected compound such as a dichloride or a dicarboxylic acid derivative.

In the case of citric acid, in order to improve the reaction yield and the like, a divalent acid derivative of an active vinegar type which is pre-reacted by a base benzoquinone or the like may be used. X of the polyamine-based resin represented by the general formula (2) may, for example, be an aromatic compound such as a phenylcyclophthalene ring, a bis-, a scaly, a (four) fresh heterocyclic compound, or (4) an integrated scale' The money is more expensive than the one shown in the following formula (5). By using the same, then (4) _ case can be obtained. Wei needs to be used alone or in combination of two or more. [化8]

098105610 12 201007355

* (5-1) (5-2) (5-3)

(5)

I R11 (5-4) (5-5)

*-R12TMSi—Ο—Si—Ri3—* R*)5 Rl5 (5-7) (here, * is a bond to the NH group. In the formula, A is -CH2-, -CH(CH3)- -C(CH3)2---Ο---S-, -S〇2-, -CO-, -NHCO-, -C(CF3)2-, or a single bond. R10 represents a burnt group, One of the flammable group and the halogen atom may be the same or different. Ru is an alkyl group, an alkoxy group, a decyloxy group or a cycloalkyl group, and may be the same or different. An integer of 0 to 4, and R12 to R15 are an organic group.) As shown in the general formula (2), 0 to 8 R5 are formed in the X bond (in the formula (5), R5 is omitted). - The preferred one of the formula (5) is the one shown by the following formula (6; . 6-1 to 6-18) which is excellent in heat resistance. [化9] 098105610 13 201007355

(6-6) (6-5)

(Rie)t (6-8) (6) (6-10) ch3 (6-11) ch3 (6-12)

(6-13)

Rr^ (wherein * represents a bond to a thiol group. In the formula, D is -CHr, -CH(CH3)-, -C(CH3)2---Ο-, -S-, -S02--- CO---NHCO-, -C(CF3)2-, or a single bond. R8 is any of an alkyl group, an alkoxy group, a decyloxy group, or a cycloalkyl group, and may be the same or different. R16 represents The one selected from the group consisting of an alkyl group, an alkyl ester group and a halogen atom may be the same or different. The integers of s=l~3 and t=0~4.) 098105610 14 201007355 [化ίο] ch3 ch3 *—( CH2)3—Si*—O—St—(CHA—* ch3 ch3

Ch3 ch3 -(CH2)2—S|—o—Si—(ch2)2——* ch3 ch3

(In the formula, (6) is a bond to the NH group.) Further, in the formula (6), it is particularly preferable to obtain good mechanical properties as shown by the following formula (3). ❿[化11] 098105610 15 (6-15) (6-16) (6) (6-17) (6-18) By using it, 201007355

(3) (wherein '* indicates that the bond to Νη Λ -ch(ch3)_, -c(ch3)2., η soil -) D is ·αί2·, •c(tetra)-, or a single bond. w 2: S〇2...C〇, c〇-, element base, alkoxy group, brewing oxy group, ring one, can be phased. An integer of 3 outside. In the case of the above-mentioned x-phase, the γ is an organic compound, and the aromatic compound such as a benzene ring, a ring, or the like, may be mentioned. Further, the heterocyclic compound such as the "Frequency" and the "Chuxi oxygen-sintering compound", and the like, more specifically, the following formula (7) can be preferably used. Good patterning can be obtained by using them or the like. They may be used alone or in combination of two or more. [化 12] 098105610 201007355

(7- υ (R17>u

(7-2)

(7) (7-8) R21 ^21 -Rtg-^i-O-f-R2〇-R22 R22 (7-9) (This '* is a bond to a thiol group. A is - CH2-, _c(CH3)r, -Ο-, -S-, -s〇2-, _c〇_, NHC〇_, _C(CF3)2_, or a single bond. ~ is represented by an alkyl group, an alkyl ester One of the selected ones of the halogen atoms and the halogen atoms may be the same and different from each other. ' R18 is an integer represented by a hydrogen atom, a burnt group, a ship base, or a _ atom. (4) An integer of 4 to 4, and Ri9 to R22 are an organic group. ), as read by the general formula (2), is omitted in the γ bond q~8 r-forms). 'By the formula (9), as the preferred one of the formula (7), the following formula (8, 8-1 〜 is shown. By (4), etc., good _ heat can be obtained. From the four_two_structure, the position of the c=o base is the position between the two to the I 彳 键 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , [Chemistry 13]

(8-3) (Rg)v (8-2)

(8-4)

(wherein * represents a bond to a C=0 group. R9 represents one selected from the group consisting of a burnt group, a burnt sulfonate group, a scaly group, an aryl ether group, and a halogen atom, and may be the same or different, respectively. To indicate 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 V = 0 to 4. (Chemical Formula 14) 098105610 18 201007355

(wherein * represents a bond to a C=0 group. R9 represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, and a halogen atom, and may be the same or different, respectively. To indicate one selected from an argon atom or an organic group having 1 to 15 carbon atoms, and a part thereof may be substituted. An integer of v = 0 to 4.) [Chemical 15] 098105610 19 201007355 ch3 ch3 (9-1) * —(CH2)3~* Dad i—〇—Si—{CH2)3—* CH3 ch3 CH3 ch3 CH3 Si—

(9-2) (9)

* (9-3) ch3 (CH2)2—S-0—Si—(CH2)2 ch3 ch3

(In the formula, * is a bond to a C=0 base.) Further, in the formulas (8) and (9), it is particularly preferable to be represented by the following formula (4). Good mechanical properties can be obtained by using them or the like. [Chemistry 16]

(4-4) (wherein, * represents a bond to a C=0 group. R5 represents a selected one of a burnt group, a burnt vine group, a hospital ether group, a benzyl ether group, and a halogen atom, and may be the same or In addition, the polyamine resin represented by the above general formula (2) is preferably an amine group of the terminal of the polyamine resin, and is used. An acid anhydride comprising an aliphatic group having at least one cation or alkynyl group or a cyclic compound group is added, and the amine group is capped as a hydrazine-amine. In this way, preservation can be improved. Examples of the group derived from the acid anhydride of the aliphatic group or the cyclic compound group containing at least one of the alkenyl group or the alkynyl group after the amino group reaction include a group represented by the formula (10) and the formula (1)). These may be used singly or in combination of two or more. [化17] Also caused by the case of the acid field, even if the cyclization is made into the structure of the imine

L

L η!

jjs〇H Ο

ο

H3C C —' H3c - S2 ~I -OH

ο

098105610 21 201007355 [化 18] cH〇>-c=ch

C=CH HO-C II Ο

Ο

C-〇-C=CH ¢11)

Ο it a c Η°-? ο Ο

o As a particularly good one, the base selected by equation (12) is preferred. In this way, the preservation can be particularly improved. [Chem. 19]

Further, the method is not limited to this method, and the terminal acid of 098105610 22 201007355 contained in the above polyamine resin may be an aliphatic group or a cyclic compound group containing a small alkenyl group or an alkynyl group. The amine derivative is capped to form decylamine. The mouth of the sensor of the present invention is a coated light agent (8). The sensitizer (b) may, for example, be an ester of an aged compound and a diazide-5-benzoic acid or a 1,2-naphthene-2-diazide-4-tetracarboxylic acid. Specifically, an ester compound represented by the formula (13) to the formula (I6) can be mentioned. These may be used alone or in combination of two or more.

[化 20] φ 098105610 23 201007355

Ch3 ch3 I I Λ

Q- NH- (CH2)3-Si - O - Si - (CH2)3 - NH- Q CH3 ch3 [Chem. 21] 098105610 24 201007355

[化22]

098105610 25 201007355

[化 23] 098105610 26 201007355

Q〇^〇tp^〇Q

In the formula, Q is selected from any one of a hydrogen atom and a formula (17) or a formula (18), and at least one of Qs of each compound is a formula (17) or a formula (18).

The content of the sensitizer (B) is not particularly limited, and is preferably from 1 to 50 parts by weight, more preferably from 10 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin (A). If the content is within the above range, the sensitivity is excellent. The photosensitive resin composition of the present invention contains one or more compounds selected from the group consisting of 098105610 27 201007355 ((:)) represented by the following general formula (1). Thus, the photosensitive resin composition is coated. Excellent appearance. [Chem. 25] Η Η2 c H= c — IH3 o—c·—c H2 CH H2· cl H c lif* c1c

c H2· c HiH3 o—cn«c I £ c H2-CH H- c11H3 c1c - 3C H2 c H= c HIH3 o——c—c 1 n2 CH H2- c H2· ciH3 HeIc I c H3 Although the reason why the photosensitive resin composition is excellent in the appearance after application of the above-mentioned compound (c) is not clear, it is presumed to be due to the influence of the composition on the dynamic viscosity and volatility of the substrate at the time of coating. The content of the compound (C) is not particularly limited, and is preferably (U to 50 parts by weight, and particularly preferably 5% by weight to the weight of the alkali-soluble resin (A). The content is within the above range. A photosensitive resin composition having an excellent appearance after coating can be obtained. The photosensitive resin composition of the present invention contains a solvent (D). Thus, the photosensitive resin composition can be made into a varnish state, and thus The coating property is improved. Examples of the solvent (D)' include, for example, N-fluorenylpyrrolidone, 7-butyrolactone, N,N-dimercaptoacetamide, dimethyl sulfoxide, and diethylene glycol. Alcohol dimethyl ether, two 098105610 28 201007355 Ethyl alcohol-B-mystery, diethylene glycol dibutyl sulfonate, propylene glycol monomethyl hydrazine, dipropylene glycol monoterpene squama, propylene glycol monoterpene ether acetate vinegar, lactic acid methyl vinegar, lactic acid ethyl vinegar, lactic acid Butane vinegar, methyl-1,3-butanediol acetate, butanediol _3 singular singular, propyl ketone, propyl acetate, methyl _3-methoxypropionic acid vinegar, etc. It may be used singly or in combination, and it is also preferable to use r-butane vinegar (di). Thus, the appearance after coating can be further improved. The content of the solvent (D) is not particularly limited, and is preferably from 1 to 4 parts by weight, and particularly preferably from 10 to 4 parts by weight, based on the weight of the above-mentioned soluble tree (A). When the content is within the above range, the practical viscosity which can be applied can be obtained even for various film thicknesses. Further, as the solvent (D), τ_butyrolactone is used (〇1) In the case of the above compound (c/m), the ratio of the combination of the above-mentioned compound (7-butane vinegar (4) is not particularly limited, and 0.01 0.5 is preferable. If the ratio is less than the above lower limit, the coating property may be improved. If the effect is less than the above upper limit, the storage stability of the wax composition may be lowered. Further, the above _ _ (c/m) is particularly preferably 〇 〇 。 2. In addition, in addition to the above effects, the storage property can be improved even when the sensitizer and the additive having poor disintegration are used together. Further, in the photosensitive resin composition of the present invention, the sensitivity is further improved. For the purpose of floating at the time of patterning, a compound having an aging base can be used in combination. Made 'include those shown in formula (19), and the like which may be used in combination of one or two or more kinds. [Formula 26] 098 105 610 29 201 007 355

The content of the compound having a heterogeneous radical is not particularly limited, and is preferably 4 parts by weight, more preferably (4) by weight of the alkali-soluble resin (Α), and the amount is within the above range. In the case of development, the occurrence of the collapse can be further suppressed, and the sensitivity can be improved by promoting the solubility of the exposed portion. The photosensitive resin composition may contain, if necessary, an additive such as a methacrylate, a polyoxazine, a fluorine-based or a fluorene-based compound, or an additive such as a sulphur coupling agent other than the compound (C). Examples of the above-mentioned decane coupling agent include, for example, 3-glycidoxypropyltrimethoxymethane, 3-glycidoxypropyl-decyldiethoxy sulphide, and 3-glycidoxypropyl group. Diethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxyxanthine, 3-methylpropionyloxypropyltrimethoxysulfate , 3-methylpropenyloxypropylmethyldiethoxylate, 3-methylpropenyloxypropyltriethoxylate, 3-propoxypropyltrimethoxy Strontium, Ν-2·(Aminoethyl)-3-aminopropyl decyl decyloxy sulphate, ν-2-(Aminoethyl)-3-aminopropyl dimethyl milylamide, N -2-(Aminoethyl)-3-aminopropyltriethoxylate, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-phenyl-3-amine Propyl trimethoxy decane, 3-mercaptopropylmethyl decyloxy decane, 3 mercaptopropyl 098105610 30 201007355 should be trimethoxy decane, bis(triethoxypropyl) tetrasulfide, 3_ Isocyanate propyl methoxy decane, and more amide compound with amine group and acid dianhydride or anhydride ^ Silane coupling agents obtained, but are not limited thereto. The above-mentioned anthracene compound having an amine group is not particularly limited, and may be 3-aminopropyltrimethoxywei, N-(2•amineethyl) phase-based group such as alkane or 3-aminopropylmethyldimethoxy Basestone Xixuan, N_(2-aminoethyl), tert-oxy-oxetane, 3-aminopropyltriethoxysulfonate, and the like. As the above-mentioned acid field, there should be no particular limitation, and examples can be cited.

Gas-based cis-butene _, cyano group cis-only _, rubbing L and so on. Further, it is also possible to use two kinds of the above-mentioned dimethyl lysine as the above-mentioned acid U, without the use of the phthalocyanine, the benzoic carboxylic acid, and the benzene, and the pyromellitic carboxylic acid, 2, 3, 3, respectively. ,,4,-diphenyl(tetra)(tetra)dianhydride, #微崎酸二肝, cut, 6, neo-dianhydride, naphthalene {2,4,5, tetralyl^tetra-acid dianhydride, naphthalic acid dianhydride, naphthalene -U,6,7- continued acid two Xuan, 4 8 2 \ Yi Xuan, strip cut, 8 make up, 7-tetra La dianhydride, dichloro-based extract; six gasification Cai dichloronaphthalene-1, 4,5,8-Si Lai Er Xuan, 2 3 6 , Ditetradecanoic acid dianhydride, 2: Anhydride, 1,4,5 8-tetraphthalene 2 3 6 7 ,...Tetrachlorin], 4,5, 8-tetracarboxylic acid II, "four gas #_2,3,6,7·tetraweidi-acid di-hepatic, 2,2,,3,3,-diphenyltetra-dianhydride, 2 m,,- Phenyl tetrasuccinic anhydride, 3,3,,,4,4,,H benzene, four _ two porch two: two stupid base, four linings, four wild, 2,3,3,,, 4,, _, ,3,3-p-terphenylene 098105610 - the present tetracarboxylic dianhydride, 2,2_double 31 201007355 phenyl)-propane dianhydride, 2 oxime, double, phenyl)-propane Xuan, Shuang (2,3_Dimethylhydrazine 2, double (3'4_二鲜基) shouted two livers, double (2,3_two rebellious phenyl) stupid) toluene dianhydride Double (2,3-two fiber) stone wind two =: two fresh _ two Xuan, u hungry 3 _ fresh base) Ethylene dianhydride, Π phenyl) M3,8,9_Silin Erxuan, Flower-,,,finely practice two Xuan ^(10) heart ship tetracarboxylic dianhydride, phenanthrene _; [ 2 7S . ^ ,, tetradecanoic acid anhydride, phenanthrene-1,2,6,7,8-tetracarboxylic acid Di-anhydride, bismuth (four) 'Caf four dianhydride, called 2,3,5,6 four rebel acid two needles" than the four hospitals of the four-year special batch 2,3 fine La H4, _ six gas iso-bens - tannic acid two Further, the above may be used alone or in combination. The certificate 2 is the above-mentioned 3, and a couple of the amine-cutting compound reacted with the acid dianhydride or the material. The preservation and imaging of the composition of the W-sensitive resin At the time, or after the treatment, the double-phase of the dense phase of the substrate such as Shixi wafer is established (34 two-base «two_3·Langyl tri-ethoxy Wei, 3,3,, 4,4, ·Diphenyl sulfonium tetraacetic acid - liver and -3 side group triethylene Wei Wei, bis (3,4 · di-fraction dianhydride #amine propyl-ethoxy wei, maleic acid needle and 3_ amine Preferably, a combination of propyltriethoxys. The method for producing a sensitive resin composition of the present invention is first applied to a suitable support (substrate), for example, a dream. Round, Taowan substrate, Ming substrate, etc. When the coating is applied to the semiconductor device, the final film thickness after curing is G.1~3G"m. If it is lower than the lower limit, _ Fully functioning as 098105610 32 201007355 is a function of protecting the surface film of a semiconductor element. If it exceeds the upper limit, it is difficult to obtain a fine processing pattern, and processing takes time and yield is lowered. As the coating method, there are a spin coating using a spinner, a spray coating using a spray applicator, dipping, printing, and a number of coatings. Gan a,, - Dun et al's '" person, to 60~13 (TC pre-baked after the film is dried, the chemical ray is irradiated on the desired figure Α #业Α(四). As a chemical ray, X can be used Ray, electron beam, ultraviolet ray, visible light, etc., but it is better to use a thief wavelength of 2 〇〇 to 5 。. Next, 'dissolve the illuminating part with a developing solution to obtain a relief pattern. As a developing solution, it can be used suitably. Adding an appropriate amount of sodium hydroxide, sodium hydroxide, sodium carbonate, sodium alginate, sodium sulphate, ammonia, etc., inorganic amines such as ethylamine and n-propylamine, monoethylamine, n-propylamine, etc. a secondary amine, triethylamine, methyldiethylamine, etc., one of the lysylethanolamines, an alcoholic surface of a triethanol material, and a tetragonal sulphuric acid tetraethylate An appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or an aqueous solution of a surfactant is added. As a method of the Xiandegu and the soil image, it can be a method such as Confucianism, (4), impregnation, or ultrasonic. The formed relief pattern is rinsed. For the _ lotion, use steam to wash the water. Heat treatment to form a loop, an imine ring, or a 4-salt ring and an yttrium ring to obtain a heat-resistant final pattern. The heat treatment temperature is preferably 380 ton, more preferably c. The heat treatment performed here is the heat treatment step described above. The cured film of the present invention is cured, and the cured film of the photosensitive resin composition 098105610 33 201007355 is used not only for a semiconductor device such as a semiconductor element but also It is also useful for a display device application such as a tft type liquid crystal or an organic EL, an interlayer insulating film for a multilayer circuit, a cover layer for a flexible copper plate, a solder resist film, and a liquid crystal alignment film. Examples of the use of the semiconductor device include a semiconductor. a passivation film formed by forming a cured film of the photosensitive resin composition on the element, a protective film such as a buffer coating film formed by forming a cured film of the photosensitive resin composition on the passivation film, or a semiconductor device An insulating film such as an interlayer insulating film formed by forming a cured film of the positive photosensitive resin composition on the formed circuit, or a "radiation blocking film, a flat film, or a protrusion (Resin column), partition, etc. · The wafer having such a cured film is excellent in coating properties around the wafer, so that the yield of the semiconductor device can be improved. As an example of the use of the display device, a protective film formed by forming a cured film of the photosensitive resin composition on a display element, an insulating or flat film for a TFT element and a color filter, or a protrusion for an MVA liquid crystal display device, etc. A partition wall or the like for a cathode or the like, which is formed by the above method by using a photosensitive resin composition layer which has been patterned on a substrate on which a money display element and a color county sheet are formed according to the use of a semiconductor device. The use of the display device is particularly high in insulation and flatness, and it is highly transparent. However, before the hardening of the composition of the lion composition, the resin layer having excellent transparency is also obtained through the post-introduction exposure step, which is practically preferable. Further, since the substrate for display having such a cured film is excellent in the periphery of the substrate, the yield of the display device can be improved. OUR OPERATION 098105610 34 201007355 [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto. «Example 1» [Synthesis of Alkali Soluble Resin (A-1)] Approximately 1.000 More of Diphenyl Ether 4,4,-Dicarboxylic Acid and 1.80 Moore Reaction _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ '彳Into a four-port split flask equipped with a thermometer, a drop machine, a raw material input port, and a dry nitrogen introduction tube, and added N-methyl-2-7 to slightly dissolve _ 3200 g to dissolve it. Thereafter, it was reacted at 75 ° C for 12 hours using an oil bath. Next, 32.8 g (0.200 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 1 gram of N-mercapto-2-pyrrolidone was added, and the mixture was stirred for further 12 hours to complete the reaction. After the reaction mixture is filtered, the reaction mixture is poured into a solution of water/isopropyl alcohol == 3/1 (volume ratio), the precipitate is collected by filtration, washed thoroughly with water, and dried under vacuum to obtain a desired alkali solubility. Resin (A-1). [Synthesis of photosensitive diazonium compound] '2,2-bis[4,4_bis(4-hydroxymethylmethylphenyl)cyclohexyl]-propane Μη克 (0·025 mol)' and three 8.60 g (0.085 mol) of ethylamine was placed in a four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube, and 135 g of tetrahydrofuran was added to dissolve it. After cooling the reaction solution to below 1 Torr, 1,2-naphthoquinone-2-diazide-4-sulfonium sulfonate 22.84 g 098105610 35 201007355 * (〇. 085 mol) and tetrahydrofuran 100 grams of common will not become 1 (TC above A, slowly drip, then 5 ° C below 5 ° C, after 5 hours at room temperature for the reaction, the end. After filtering the reaction mixture, will The reaction mixture was poured into a water/methanol-3/1 (volume ratio) solution, and the precipitate was collected by filtration and washed thoroughly with water; and dried under normal conditions to obtain a photosensitive diazonium of the formula (B-1). Compound. [Chem. 27]

[Preparation of a positive-type photosensitive resin composition] 10.000 g of a photosensitive diazonium compound having a structure of a base-soluble resin (A_1) and having a structure of the formula (d), having the structure of the following formula (d) 10.00 grams of material, dissolved in 7 ^ butyrolactone 150.00 grams, with a pore size of 〇 2

A filter paper of Tefulon (registered trademark) was filtered to obtain a positive photosensitive resin composition. [化28] 098105610 36 201007355 (C-1): [Evaluation of coating unevenness] H3C—C=CH-CH2-CH3 CH2~(j: One ch=ch2 CH3 was applied by spin coater to obtain film thickness About 7.0/am The positive-type photosensitive resin composition was pre-baked on a hot plate at 120 ° C for 4 minutes after the wafer was formed. Next, the following interference fringe inspection lamp (Nafutech) System, FNa_35 g

Irradiation of the dust-free oven and observation of the periphery of the wafer, no unevenness was observed, and it was good. [Evaluation of coating property] After the positive-type photosensitive resin composition was applied onto a tantalum wafer by a spin coater, The film was prebaked at 120 ° C for 4 minutes on a hot plate to obtain a coating film having a film thickness of about 7 Å. The coating film was measured by the optical interference type film thickness measuring device VM_8〇〇〇J (manufactured by Otsuka Screen Manufacturing Co., Ltd.) at a pitch of 1〇111111 in the X-axis direction, and as a result, the average film thickness was obtained. It is 148,784A. At this time, the range of the thickness (maximum value and minimum value) was 1,552 person's standard deviation was 496 A, and there was no problem with the coating film of the entire film. [Development evaluation] This positive photosensitive resin composition was applied on a 8 Å wafer using a spin coater, and then pre-baked at 12 (TC for 4 minutes) to obtain a film thickness. A coating film of about 7 um. The obtained coating film was passed through a embossed (manufactured) reticle (D (10) Chart No. 1: a residual pattern of 0.88 to 50/zm in width and a pattern removed), and Nikon was used. The ray stepper NSR-4425i exposes the exposure amount from 100mJ/cm2 to lOmJ/cm2 in stages, and then adjusts the development time between 098105610 37 201007355 to 2.38% of the aqueous tetramethylammonium hydroxide solution. The film edge was obtained by dissolving and removing the exposed portion, and then rinsing with pure water for 3 sec. The pattern was observed. As a result, it was confirmed that the exposure amount was 400 mJ/cm 2 , and no scum was formed, and the pattern opening was good. [Pull extension evaluation] The photosensitive resin composition was coated on a 8 吋矽 wafer in a manner of a thickness of about 1 〇 "m, and a Clean Oven (CLH-21CDL) manufactured by Koyo Thermo System (Nitrogen Co., Ltd.) in a nitrogen atmosphere. Next, it is hardened under a nitrogen atmosphere at 150/30 minutes + 32 CTC/30 minutes to obtain a cured film. The cured film is immersed in 2% hydrogen fluoride water, and the cured film is peeled off from the ruthenium wafer. Secondly, the obtained cured film is sufficiently washed with pure water, and dried in an oven at 6 ° C for 5 hours. The cured film was cut into a rectangular shape having a width of i〇mm to obtain a sample for the tensile test. Secondly, the tensile tester was used to measure the shape according to the shape of the sample: 10 mm width x 12 mm length and pull speed: 5 mm/min. The degree of elongation showed a good elongation of 36%. «Example 2» 15.00 g of the following formula (C-2) was used instead of C-1 used in Example 1, and the above formula (B-1) was added to 18.00 g, the same positive photosensitive resin composition as in Example 1 was produced, and the same evaluation was carried out. [OH29] OH H3C-c=ch~ch2-ch2-c-ch2ch3 ch3 CH3 (C-2) 098105610 38 201007355 «Example 3» & using the following formula CC_3) 8, () G gram instead of c] used in the example}, and reducing the above λ (Β_1) to 13·0 () gram ' The same positive evaluation of the positive photosensitive resin composition as in Example 1 was carried out. (C-3): «Example 4» H f H3c-c-CH2CH2-CH2-C--ch=ch2 ch3 ch3 [Synthesis of alkali-soluble resin (A-2)] In Example 1 In the synthesis of an alkali-soluble resin, 2,2-bis(3-amino-4-hydroxyphenyl)propane 258.33 g (i.ooo mol) is used instead of 2,2_bis (3_amino-4-hydroxy) Phenyl) hexafluoropropane 366.26 g (1._mole), and the synthesis of the alkali-soluble resin (A 2) was carried out in the same manner as in Example 1, and the same was carried out in the same manner as in the preparation of the positive photosensitive resin composition. Evaluation. «Example 5» [Synthesis of alkali-soluble resin (A-3)] 4,4'-oxydiphthalic anhydride 17.06 g (0.055 mol) and ethanol 5 〇 7 g (0.110 mol) and ratio 1 〇 92 g (0.138 mol) force σ into a four-port flask with a wound thermometer, a mixer, a raw material inlet, a dry nitrogen inlet tube, and 150 g of Ν-methyl-2-pyrrolidone Let it dissolve. In this reaction solution, 14.86 g (0.110 mol) of hexyl-1,2,3-benzotriazole and Ν-mercapto-2-pyrrol bite 098105610 39 201007355 30 g were dropped together. Cyclohexylcarbodiimide 22 7 g (〇11〇 mol) was added together with N-methyl-2-pyrrolidone 5 g, and reacted at room temperature overnight. Thereafter, a dicarboxylic acid derivative obtained by reacting diphenyl ether_4,4,-dicarboxylic acid i oxime and hydroxy-1,2,3-benzobisazole 2 in the reaction solution (active ester) 27 〇9 g (〇.055 mol for hexafluoro·2,2·bis(3·amino-4)-phenyl)propane 44.68 g (0.122 mol) and Nf-based_2_ 70 g of hydral ketone was added in common, and stirred at room temperature for 2 hours, and then reacted at 75 ° C for 12 hours using an oil bath. Next, cis was dissolved in 40 g of N-methyl-2-pyrrolidone 4.80 g (0.049 mol) of butenedic anhydride, stirring for another 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 3 / 1 (volume ratio), and the precipitate was collected by filtration. After thoroughly washing with water, it is dried under vacuum to obtain a target of the soluble resin (A-3). [Synthesis of a photosensitive diazonium compound] 1,1,1-para (4-Mphenyl) Ethane (Benzhou Chemical Co., Ltd.) 18 38 g (〇_莫耳), and Erqi private 13.66 g (0.135 m) are placed in a four-port split type equipped with a thermometer, a mixer, a raw material inlet, and a dry nitrogen introduction tube. Flask and add 135 g of tetrahydrofuran Dissolve. After cooling the reaction solution to below 1 Torr, the 1,2-naphthoquinone-2-diazide-5-continuous gasification 36.27 g (0.135 mol) together with 100 g of tetrahydrofuran will not The mixture was slowly dropped to a temperature of 10 ° C or higher, and then stirred at 10 ° C or lower for 5 minutes, and then stirred at room temperature for 5 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was poured into water / methanol = 3 In the solution of /1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum, 098105610 40 201007355 to obtain a photosensitive diazonium compound represented by the formula (B-2). ] φ 〇Q ο

(B-2): C-^)-〇Q <Preparation of positive photosensitive resin composition> Synthetic test soluble resin (A-3) l〇〇.〇〇g, having the above formula (β_2 20.00 g of the photosensitive diazonium compound of the structure and 20.00 g of the compound having the structure of the above formula (c_i) were dissolved in 14 gram of butyrolactone, and were made of Tefulon (registered trademark) having a pore diameter of 2 μm. The filter paper was filtered to obtain a positive photosensitive resin composition. [Evaluation of Coating Property] The above positive photosensitive resin composition was evaluated in the same manner as in Example 。. «Comparative Example 1» In the preparation of the positive photosensitive resin composition of Example 1, a synthetic alkali-soluble resin (Α·1) 10_1, a photosensitive diazonium compound having the structure of the above formula) 15.00 g, r _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The same results are shown in Table 1. Here, the numbers of the soluble resin, the sensitizer, and the compound in Table 1 indicate the added parts by weight. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Solubility of the tree (A) Al Al Al A-2 A-3 Al 100 100 100 100 100 100 Sensitizer (B) Bl~ Bl Bl Bl B-2 Bl 15 18 13 15 20 15 Compound (C) C4 C-2 C-3 Cl Cl - 10 1 15 8 10 20 - Harmony of the Ministry of Violence ^ No" No film thickness uniformity Average film thickness (A) 148784 148352 148591 148724 148912 148212 #ε»ί£ΐνΛ/ standard deviation (A) 1552 496 1541 ^QQ 1559 1563 cni 1535 1571 Sensitivity (mJ/cm2) ------ 499 482 5U7 400 Γ 390 410 430 450 430 Pulling bow 1 ( (%) Γ 36 40 卜 36 32 34 29 As shown in Table 1, it can be seen that the embodiment 丨2, 3, 4, and 5 are excellent in coating unevenness in the case where the edge portion is not observed. Further, it is understood that the sensitivity and the tensile elongation are also better than those of the comparative example. (Industrial Applicability) The present invention is It is suitable for use in a photosensitive resin composition excellent in appearance after application, a cured resin, a protective film, an insulating film, and a semiconductor device using the same. 098105610 42

Claims (1)

201007355 VII. Patent application scope 1. A photosensitive resin composition characterized in that A 3 is an I 3 alkali soluble resin (A), a sensitizer (B), and a compound represented by the general formula (1). Selected solvent (D); [Chemical 1] The above compound (c), and H3C-C-CH-CH2~CH2*~C-~CH=CH-CH3 CH. OH H3C-C=CH-CH2 -CH2~C - ch2ch2 ch3 ch3 (1) OH H H3C--C-CH2CH2-CH2-C-CH=CH^CH5CH3 2. The photosensitive resin composition of claim 1, wherein the compound The content of the (C) is a photosensitive resin composition of the first or second aspect of the invention, wherein the solvent is in the range of 0.1 to 5 parts by weight. (0) is a butyrolactone (D1). The photosensitive resin composition of the third aspect of the invention, wherein the above-mentioned 098105610 43 201007355 compound (C) and the above 7-butyrolactone (D1) The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (A) contains a general formula (2). ) The repeating unit of the polyamine resin, [Chemical 2] (wherein, X and Y are organic groups; hydrazine is hydroxy, -o-r3, alkyl, decyloxy, cycloalkyl, which may be the same or different; R2 is a transradical, rebel, -〇-R3 And any one of -C00-R3 may be the same or different; m is an integer of 0 to 8, and η is an integer of 0 to 8; 吣 is an organic group having a carbon number of 1 to 15; When they are not hydroxyl groups, at least one of r2 must be a carboxyl group; and when R2 is not a carboxyl group, h must be at least one hydroxyl group). 6. The photosensitive resin composition of the fifth aspect of the invention, wherein the X of the polyamid-based resin having the repeating unit represented by the general formula (2) is composed of the following formula (3) One or more selected from the group, [Chem. 3] 098105610 44 (3) 201007355 OH (wherein, * represents a bond to an NH group; and D in the formula (3-7) is -CH2-, -CH(CH3)-, -C(CH3)2-, -0-, -S- , -S〇2-, -CO-, -NHC0-, -C(CF3)2-, or a single bond; R4 is any one of an alkyl group, an alkoxy group, a decyloxy group, or a cycloalkyl group, which may be The same or different; s = l~3 integer). In the photosensitive resin composition of the fifth aspect of the invention, the Y of the polyamine resin having the repeating unit represented by the general formula (2) is contained in the following formula (4). One or more selected from the group, [Chem. 4] 098105610 45 201007355 (4) (4-3) (4-4) (here, the silk is bonded to the (10) base; _ means the one selected from the silk, the silk base, the burnt ether base, and the _ sub, which may be the same or different ; v = 0 to 4 integer). 8. If you apply for a patent scope! Or a photosensitive resin composition of two items, wherein the photosensitive agent (B) is a diazonium containing compound. 9. - A type of cured film is formed by a cured product of a photosensitive resin composition of the second or the second. 10. - A protective film' is characterized by a hardened film of the ninth item in the hometown. The U-type insulating film ' is characterized by a cured film of the ninth application of the patent application. A semiconductor device characterized by having a cured film of claim 9th. 13. A display device characterized by having a hardened crucible of claim 9th. 14. The photosensitive resin composition of the sixth aspect of the patent application, wherein the oxime of the polyamine resin having the repeating unit represented by the general formula (2) is contained in the following formula ( 4) One or more selected from the group, [Chem. 4] (wherein, * is a bond to a c=o group; r5 is a one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group, or a halogen atom, and may be the same or different; respectively; =0 to 4 integer). 098105610 47 201007355 IV. Designation of representative drawings: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: OH :ch-ch2-ch2-c-ch=ch2 h3c-ch3 ch3 OH I H3C-〇=CH~CH2—CH2-C-CH2CH3 ch3 ch3 (1) OH H H3C 〇CH2CH2—CH2—C CH=CH2 ch3 ch3 098105610 3