DIAMINE COMPOUND, AND HEAT-RESISTANT RESIN OR HEAT-RESISTANT RESIN PRECURSOR USING SAME

Abstract

Provided are a photosensitive resin composition which has excellent pattern processabilities (high sensitivity and high resolution) and is excellent in chemical resistance and thermal resistance after thermally treated; a heat-resistant resin or heat-resistant resin precursor used for the composition; and a diamine compound which is a raw material of the resin and the precursor. The diamine compound is a diamine compound represented by a general formula (1).

##STR00001##

Claims

1-13. (canceled)

14. A heat-resistant resin or heat-resistant resin precursor, having a structure originating from the diamine represented by the general fonnula (1): ##STR00038## wherein each R.sup.1 represents an alkyl group having 1 to 5 carbon atoms; each p represents an integer of 0 to 2; q represents an integer of 0 to 100; each R.sup.2 represents any case of a bivalent aliphatic group, alicyclic group or aromatic group, any case of a bivalent organic group in which plural aromatic groups are bonded to each other through a single bond, or any case of a bivalent organic group in which plural aromatic groups are bonded to each other through —O—, —CO—, —SO.sub.2—, —CH.sub.2—, —C(CH.sub.3).sub.2—, or —C(CF.sub.3).sub.2 wherein each F is each fluorine; X represents —O—, —S—, —CO—, —SO.sub.2—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —C(CH.sub.3)(C.sub.2H.sub.5)—, or —C(CF.sub.3).sub.2— wherein each F is fluorine.

15. The heat-resistant resin or heat-resistant resin precursor according to claim 14, including at least one selected from polyimides, polybenzoxazoles, polybenzoimidazoles, and polybenzothiazoles; and respective precursors of these polymers, and copolymers of these polymers.

16. The heat-resistant resin or heat-resistant resin precursor according to claim 14, having at least one selected from respective structures represented by the general formulae (2), (3), and (5): ##STR00039## wherein R.sup.3 represents a bivalent to hexavalent organic group having 2 to 30 carbon atoms; E represents any one of OR.sup.4, SO.sub.3R.sup.4, CONR.sup.4R.sup.5, COOR.sup.4, and SO.sub.2NR.sup.4R.sup.5 wherein R.sup.4 and R.sup.5 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; i represents an integer of 0 to 4; and A represents a structure represented by a general formula (4); ##STR00040## wherein R.sup.6 represents a tetravalent to octavalent organic group having 2 to 30 carbon atoms; F represents any one of OR.sup.7, SO.sub.3R.sup.7, CONR.sup.7R.sup.8, COOR.sup.7, and SO.sub.2NR.sup.7R.sup.8 wherein R.sup.7 and R.sup.8 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms; j represents an integer of 0 to 4; and A represents a structure represented by the general formula (4): ##STR00041## wherein each R.sup.1 represents an alkyl group having 1 to 5 carbon atoms; each p is an integer of 0 to 2; q represents an integer of 0 to 100; each R.sup.2 represents any case of a bivalent aliphatic group, alicyclic group, or aromatic group, any case of a bivalent organic group in which plural aromatic group are bonded to each other through a single bond, or any case of a bivalent organic group in which plural aromatic groups are bonded to each other through —O—, —CO—, —SO.sub.2—, —CH.sub.2—, —C(CH.sub.3).sub.2—, or —C(CF.sub.3).sub.2 wherein each F is fluorine; and X represents —O—, —S—, —CO—, —SO.sub.2—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —C(CH.sub.3)(C.sub.2H.sub.5)—, or —C(CF.sub.3).sub.2 wherein each F is fluorine; and ##STR00042## wherein R.sup.9 represents a bivalent to hexavalent organic group having 2 to 30 carbon atoms; G represents any one of OR.sup.10, SO.sub.3R.sup.10, CONR.sup.10R.sup.11, COOR.sup.10, and SO.sub.2NR.sup.10R.sup.11 wherein R.sup.10 and R.sup.11 each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms; k represent an integer of 0 to 4; B represents a structure represented by a general formula (6), and each Y represents NH, O or S; ##STR00043## wherein each R.sup.1 represents an alkyl group having 1 to 5 carbon atoms; each p represents an integer of 0 to 2; q represents an integer of 0 to 100; each R.sup.12 represents any case of a trivalent aliphatic group, alicyclic group, or aromatic group, any case of a trivalent organic group in which plural aromatic groups are bonded to each other through a single bond, or any case of a trivalent organic group in which plural aromatic groups are bonded to each other through —O—, —CO—, —SO.sub.2—, —CH.sub.2—, —C(CH.sub.3).sub.2—, or —C(CF.sub.3).sub.2 wherein each F is fluorine; and X represents —O—, —S—, —CO—, —SO.sub.2—, —CH.sub.2—, —C(CH.sub.3).sub.2—, —C(CH.sub.3)(C.sub.2H.sub.5)—, or —C(CF.sub.3).sub.2.

17. A photosensitive resin composition, comprising the heat-resistant resin or heat-resistant resin precursor (a) recited in claim 14, and further comprising a photosensitive compound (b) and a solvent (c).

18. The photosensitive resin composition according to claim 17, wherein the photosensitive compound (b) is a quinonediazide compound (b1).

19. The photosensitive resin composition according to claim 17, wherein the photosensitive compound (b) is a photopolymerization initiator (b2).

20. The photosensitive resin composition according to claim 19, further comprising a radical polymerizable compound (d).

21. The photosensitive resin composition according to claim 17, further comprising an alkoxymethyl-group-containing compound, and/or a cyclic-polyether-structure-having compound (e).

22. A cured film, wherein the photosensitive resin composition recited in claim 17 is cured.

23. An element, comprising the cured film recited in claim 22.

24. An organic EL display device, wherein the cured film recited in claim 22 is located over at least one of a planarizing layer over a driving circuit, and an insulation layer over a first electrode.

25. A method for producing an organic EL display device, using the photosensitive resin composition recited in claim 17, comprising: the step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin film; and the step of subjecting the photosensitive resin film to drying, exposure to light, development, and heating treatment.

Description

EXAMPLES

[0233] Hereinafter, the present invention will be described in detail by way of working examples thereof. However, the invention is not limited by these examples. In each of the working examples, the production and evaluation of a cured film were performed by methods described below.

<Pattern Processability Evaluation>

[0234] (1) Production of Photosensitive Resin Film

[0235] A photosensitive resin composition (hereinafter referred to as a varnish) was applied onto a 6-inch silicon wafer. Next, a hot plate (application and development apparatus Mark-7, manufactured by Tokyo Electron Limited) was used to prebake the resultant workpiece at 120° C. for 3 minutes to yield a photosensitive resin film. [0236] (2) Method for Measuring Film Thickness

[0237] A product, Lambda ACE STM-602, manufactured by Dainippon Screen Mfg. Co., Ltd. was used to measure the thickness of the pre-baked film, and that of a film obtained by developing the pre-baked film at a refractive index of 1.629, and measure that of a cured film obtained by curing the developed film at a refractive index of 1.773. [0238] (3) Exposure to Light

[0239] A reticle cut into a pattern was set to an exposure apparatus (i-line stepper DSW-8570i, manufactured by GCA Corp.), and the photosensitive resin film was exposed to an i-line at an intensity of 365 nm while the period for the exposure was changed. [0240] (4) Development

[0241] A development apparatus, Mark-7, manufactured by Tokyo Electron Limited was used to develop the light-exposed film two times with a 2.38% solution of tetramethylammonium hydroxide in water for 45 seconds. Next, the workpiece was subjected to rinsing treatment with pure water. The workpiece was shaken to remove the water, and dried. [0242] (5) Sensitivity Calculation

[0243] The following was defined as the sensitivity of the film: the exposure value at which the light-exposed portions were dissolved to be completed lost (the value is referred to as the minimum exposure value Eth) after the exposure and the development. [0244] (6) Resolution Calculation

[0245] After the exposure and the development, the following was defined as the resolution of the film: at the Eth, a pattern width permitting a line-and-space pattern (1L/1S) to be formed with a one-to-one width. [0246] (7) Cured Film Production

[0247] An inert gas oven INH-21CD manufactured by Koyo Thermo Systems Co., Ltd. was used to heat the resin film produced by the above-mentioned method at 140° C. in a nitrogen gas flow (oxygen concentration: 20 ppm) for 30 minutes, and then the temperature of the film was raised to 230° C. in a period of 30 minutes. At 230° C., the film was thermally treated for 1 hour to produce a cured film (heat-resistant resin film).

<Chemical Resistance Evaluation>

[0248] The cured film produced by the above-mentioned method was subjected to immersing treatment in a peeling liquid 106 manufactured by Tokyo Ohka Kogyo Co., Ltd. at 70° C. for 10 minutes, About the treated cured film, the respective film thicknesses of the film before and after the treatment were measured and then the amount of the reduced film was gained.

<Thermal Resistance Evaluation>

[0249] The cured film produced by the above-mentioned method on the silicon wafer was peeled with hydrofluoric acid to yield a film. Into an aluminum clamp cell was filled 10 mg of this simple film, so as to produce a TGA measuring sample, and an apparatus TGA-50 (manufactured by SHIMADZU CORPORATION) was used to make a measurement. In a nitrogen atmosphere, the temperature at which the weight of the sample was reduced in a proportion of 5% was measured from 200° C. When the sample was a sample about which the temperature was lower than 320° C., the sample was judged not to be satisfactory (cross mark). Alternatively, when the sample was a sample about which the temperature was 320° C. or higher, the sample was judged to be good (circular mark).

Synthesis Example 1

Synthesis of Bisaminophenol Compound (a)

[0250] Into 250 mL of chloroform was dissolved 10.0 g (0.0598 mol) of 2,6-dihydroxymethyl-4-methylphenol. Thereto was added 36.0 g (0.414 mol) of manganese dioxide to cause the reactive components to react with each other at 60° C. for 20 hours. The reaction solution was filtrated, and the filtrate was dried under a reduced pressure. Thereafter, the precipitated yellow solid was caused to undergo reaction at 230° C. for 1 hour in the presence of 55.0 g (0.98 mol) of potassium hydroxide. The system was cooled to room temperature and the mixture was dissolved into 150 mL of pure water. The resultant was filtrated, and hydrochloric acid was added to the filtrate until the pH of the filtrate turned to 1. The precipitation was filtrated. The filtrate was washed with pure water, and dried at 110° C. all night to yield a yellowish brown solid. This solid was stirred at room temperature in 110 mL of thionyl chloride for 2 hours, and the resultant was subjected to filtration. The filtrate was dried under a reduced pressure to yield a brown solid.

[0251] 38.5 g (0.105 mol of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was dissolved into 200 mL of acetone and 17.4 g (0.3 mol) of propylene oxide. Thereto was dropwise added a solution in which 11.7 g (0.05 mol) of the brown solid yielded previously was dissolved in 100 mL of acetone. After the addition, the reactive components were caused to react with each other at room temperature for 4 hours, and then the precipitated white solid was collected by filtration. The solid was vacuum-dried at 50° C. to yield a bisaminophenol compound (a) represented by the following formula:

##STR00033##

Synthesis Example 2

Synthesis of Bisaminophenol Compound (b)

[0252] The same manner as in Synthesis Example 1 was carried out except the use of 17.2 g (0.0598 mol) of bis(2-hydroxy-3-hydroxymethyl-5-methylphenol)methane instead of 10.0 g (0.0598 mol) of 2,6-dihydroxymethyl-4-methylphenol. In this way, a bisaminophenol compound (b) was yielded.

##STR00034##

Synthesis Example 3

Synthesis of Polyimide Precursor (Polymer A)

[0253] In a dry nitrogen gas flow, 21.4 g (0.024 mol) of the bisaminophenol compound (a) yielded in Synthesis Example 1 and 0.37 g (0.002 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were dissolved into 80 g of N-methyl-2-pyrrolidone (NMP). Thereto was added 9.31 g (0.030 mol) of 3,3′, 4,4′-diphenyl ether tetracarboxylic acid anhydride (ODPA) together with 10 g of NMP to cause the reactive components to react with each other at 40° C. for 1 hour. Thereafter, thereto was added 0.65 g (0.006 mol) of 3-aminophenol as a terminal blocking agent, and further the reactive components were caused to react with each other at 40° C. for 1 hour. Thereafter, over 10 minutes, thereto was dropwise added a solution in which 7.14 g (0.06 mol) of N,N′-dimethylformamide dimethylacetal was diluted with 15 g of NMP. After the addition, the reaction system was stirred at 40° C. for 2 hours. After the end of the reaction, the solution was charged into 2 L of water, and the resultant polymer solid precipitation was collected by filtration. The polymer solid was dried in a vacuum drier of 50° C. for 72 hours to yield a polymer A as a polyimide precursor.

Synthesis Example 4

Synthesis of Polyimide Precursor (Polymer B)

[0254] The same manner as in Synthesis Example 1 was carried out except the use of 24.4 g (0.024 mol) of the bisaminophenol compound (b) yielded in Synthesis Example 2 instead of 21.4 g (0.024 mol) of the bisaminophenol compound (a) yielded in Synthesis Example 1. In this way, a polymer (B) as a polyimide precursor was yielded.

Synthesis Example 5

Synthesis of Polyimide (Polymer C)

[0255] In a dry nitrogen gas flow, 80.3 g (0.09 mol) of the bisaminophenol compound (a) yielded in Synthesis Example 1 was dissolved into 500 g of NMP. Thereto was added 31.0 g (0.1 mol) of ODPA together with 50 g of NMP, and the reaction solution was stirred at 30° C. for 2 hours. Thereafter, thereto was added 2.18 g (0.02 mol) of 3-aminophenol, and further the solution was continuously stirred at 40° C. for 2 hours. Furthermore, 5 g of pyridine was diluted with 30 g of toluene, and this liquid was added to the solution. A condenser was attached to the reaction system. While water was removed together with toluene to the outside of the system by azeotropy, the reactive components were caused to react with each other for 2 hours in the state of setting the temperature of the solution to 120° C., and further the reaction was conducted for 2 hours at 180° C. When the temperature of this solution was lowered to room temperature, the solution was charged into 3 L of water to yield a white powder. This powder was collected by filtration, and further washed 3 times with water. After the washing, the white powder was dried in a vacuum drier of 50° C. for 72 hours to yield a polyimide polymer C.

Synthesis Example 6

Synthesis of Polyhydroxyamide (Polymer D)

[0256] In a dry nitrogen gas flow, 26.8 g (0.03 mol) of the bisaminophenol compound (a) and 7.3 g (0.02 mol) of BAHF were dissolved into 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether. The temperature of the solution was cooled to −15° C. Thereto was dropwise added a solution in which 14.7 g (0.050 mol) of diphenyl ether dicarboxylic acid dichloride was dissolved in 25 g of GBL in such a manner that the internal temperature did not exceed 0° C. After the end of the addition, the stirring of the solution was continued at −15° C. for 6 hours. After the end of the reaction, the solution was charged into 3 L of water containing 10% by mass of methanol, and the resultant white precipitation was collected. This precipitation was collected by filtration, and washed 3 times with water. Thereafter, the white powder was dried in a vacuum drier of 50° C. for 72 hours to yield a polyhydroxyamide polymer D.

Comparative Synthesis Example 1

Synthesis of Polyimide Precursor (Polymer E)

[0257] In a dry nitrogen gas flow, 8.8 g (0.024 mol) of BAHF and 0.37 g (0.002 mol) of SiDA were dissolved into 80 g of NMP. Thereto was dropwise added 9.31 g (0.030 mol) of ODPA together with 10 g of NMP, and the reactive components were caused to react with each other at 40° C. for 1 hour. Thereafter, thereto was added 0.65 g (0.006 mol) of 3-aminophenol as a terminal blocking agent, and further reaction was conducted at 40° C. for 1hour. Thereafter, over 10minutes, thereto was dropwise added a solution in which 7.14 g (0.06 mol) of N,N-dimethylformamide dimethylacetal was diluted with 15 g of NMP. After the addition, the solution was stirred at 40° C. for 2 hours. After the end of the reaction, the solution was charged into 2 L of water, and the resultant polymer solid precipitation was collected by filtration. The polymer solid was dried in a vacuum drier of 50° C. for 72 hours to yield a polyimide precursor polymer E.

Comparative Synthesis Example 2

Synthesis of Polyimide (Polymer F)

[0258] In a dry nitrogen gas flow, 32.9 g (0.09 mol) of BAHF was dissolved into 500 g of NMP. Thereto was added 31.0 g (0.1 mol) of ODPA together with 50 g of NMP, and the reaction solution was stirred at 30° C. for 2 hours. Thereafter, thereto was added 2.18 g (0.02 mol) of 3-aminophenol, and further the solution was continuously stirred at 40° C. for 2 hours. Furthermore, 5 g of pyridine was diluted with 30 g of toluene (manufactured by Tokyo Chemical Industry Co., Ltd.), and this liquid was added to the solution. A condenser was attached to the reaction system. While water was removed together with toluene to the outside of the system by azeotropy, the reactive components were caused to react with each other for 2 hours in the state of setting the temperature of the solution to 120° C., and further the reaction was conducted for 2 hours at 180° C. When the temperature of this solution was lowered to room temperature, the solution was charged into 3 L of water to yield a white powder. This powder was collected by filtration, and further washed 3 times with water. Thereafter, the white powder was dried in a vacuum drier of 50° C. for 72 hours to yield a polyimide polymer F.

Synthesis Example 7

Synthesis of Quinonediazide Compound (c)

[0259] Ina dry nitrogen gas flow, 21.22 g (0.05 mol) of a product Tris P-PA ((trade name) manufactured by Honshu Chemical Industry Co., Ltd.), 26.86 g (0.10 mol) of 5-naphthoquinonediazidesulfonic acid chloride, and 13.43 g (0.05 mol) of 4-naphthoquinonediazidesulfonic acid chloride were dissolved into 450 g of 1,4-dioxane. The temperature of the solution was adjusted to room temperature. In this solution, 15.18 g of triethylamine was used which was mixed with 50 g of 1,4-dioxane. The same manner as in Synthesis Example 6 was carried out to yield a quinonediazide compound (c) represented by the following formula:

##STR00035##

Synthesis Example 8

Synthesis ofAlkoxymethyl-Group-Containing Thermally Crosslinking Agent (d)

[0260] (1) 103.2 g (0.4 mol) of the product Tris P-HAP was dissolved into the solution of 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After the product was completely dissolved, over 2 hours thereto was dropwise added 686 g of an aqueous formalin solution having a concentration of 36 to 38% by mass at 20 to 25° C. Thereafter, the solution was stirred at 20 to 25° C. for 17 hours. Thereto were added 98 g of sulfuric acid and 552 g of water to neutralize the solution. The solution was allowed to stand still as it was for 2 days. After the standing-still, a needle-form white crystal generated in the solution was collected by filtration, and washed with 100 mL of water. This white crystal was vacuum-dried at 50° C. for 48 hours. The dried white crystal was analyzed at 254 nm by a high performance liquid chromatography manufactured by SHIMADZU CORPORATION, using an ODS as a column, and acetonitrile and water (=70/30) as an eluent. As a result, it was understood that the starting materials were completely lost and the purity of the crystal was 92%. Furthermore, DMSO-d6 was used as a deuterated solvent to analyze the crystal by NMR (GX-270, manufactured by JEOL Ltd.). As a result, it was understood that the crystal was a hexa-methyloled Tris P-HAP. [0261] (2) Next, the thus yielded compound was dissolved into 300 mL of methanol. Thereto was added 2 g of sulfuric acid, and the solution was stirred at room temperature for 24 hours. To this solution was added 15 g of an anionic ion exchange resin (AMBERLYST IRA96SB, manufactured by the company Rohm and Haas), and the resultant was stirred for 1 hour. The ion exchange resin was removed by filtration. Thereafter, thereto was added 500 mL of ethyl lactate. A rotary evaporator was used to remove methanol to convert the solution to an ethyl lactate solution. This solution was allowed to stand still at room temperature for 2 days. As a result, a white crystal was generated. The resultant white crystal was analyzed by high performance liquid chromatography. As a result, it was understood that the compound of the crystal was a 99%-purity hexamethoxymethyl compound (alkoxymethyl-group-containing thermally crosslinking agent (d)) of the Tris P-HAP. This is represented by the following formula:

##STR00036##

[0262] Different thermally crosslinking agents and a different compound having a phenolic hydroxide group that were each used in the working examples are as follows:

##STR00037##

Example 1

[0263] The following were each weighed out: 10 g of the polymer A solid yielded in Synthesis Example 3; 1.9 g of the quinonediazide compound (c) yielded in Synthesis Example 8; 1.2 g of the alkoxymethyl-group-containing thermally crosslinking agent (d) yielded in Synthesis Example 9; and 0.6 g of the phenolic compound (g). These components were dissolved into 30 g of GBL to yield a varnish of a positive photosensitive resin composition. The resultant varnish was used to make the individual evaluations by the above-mentioned respective methods.

Example 2

[0264] A vanish of a positive photosensitive resin composition was yielded in the same way as in Example 1 except the use of 10 g of the polymer B solid yielded in Synthesis Example 4 instead of the polymer A, and 1.2 g of the NIKALAC MX-270 (e) instead of the alkoxymethyl-group-containing thermally crosslinking agent (d). The evaluations of the varnish were made by the respective methods.

Example 3

[0265] A vanish of a positive photosensitive resin composition was yielded in the same way as in Example 1 except the use of 10 g of the polymer C solid yielded in Synthesis Example 5 instead of the polymer A, and 1.2 g of the VG-3101L (f) instead of the alkoxymethyl-group-containing thermally crosslinking agent (d). The evaluations of the varnish were made by the respective methods.

Example 4

[0266] A vanish of a positive photosensitive resin composition was yielded in the same way as in Example 1 except the use of 10 g of the polymer D solid yielded in Synthesis Example 6 instead of the polymer A. The evaluations of the varnish were made by the respective methods.

Example 5

[0267] A vanish of a positive photosensitive resin composition was yielded in the same way as in Example 1 except the use of 1.2 g of the VG-3101L (f) instead of the alkoxymethyl-group-containing thermally crosslinking agent (d). The evaluations of the varnish were made by the respective methods.

Example 6

[0268] The following were each weighed out: 10 g of the polymer A solid yielded in Synthesis Example 3; 1.4 g of 1-(9-ethyl-6-nitro-9H-carbazole-3-yl)-1-[2-methyl-4-(1-meth oxypropane-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime) (NCI-831 “ADEKAARKLS” (registered trade name)) (manufactured by Adeka Corp.); 4.0 g of dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kayaku Co., Ltd.); and 1.2 g of the alkoxymethyl-group-containing thermally crosslinking agent (d) yielded in Synthesis Example 9. These components were dissolved into 30 g of GEL to yield a varnish of a negative photosensitive resin composition. The resultant varnish was used to make the individual evaluations by the above-mentioned respective methods.

Comparative Example 1

[0269] A vanish of a positive photosensitive resin composition was yielded in the same way as in Example 1 except the use of 10 g of the polymer E solid yielded in Comparative Synthesis Example 1 instead of the polymer A. The evaluations of the varnish were made by the respective methods.

Comparative Example 2

[0270] A vanish of a positive photosensitive resin composition was yielded in the same way as in Example 3 except the use of 10 g of the polymer F solid yielded in Comparative Synthesis Example 2 instead of the polymer C. The evaluations of the varnish were made by the respective methods.

Comparative Example 3

[0271] The following were each weighed out: 8 g of the polymer E solid yielded in Comparative Synthesis Example 1; 2 g of a Novolak resin G (trade name: PSF-2808, manufactured by Gunei Chemical Industry Co., Ltd.; m/p ratio: 100/0); 1.9 g of the quinonediazide compound (c) yielded in Synthesis Example 8; 1.2 g of the alkoxymethyl-group-containing thermally crosslinking agent (d) yielded in Synthesis Example 9; and 0.6 g of the phenolic compound (g). These components were dissolved into 30 g of GEL to yield a varnish of a positive photosensitive resin composition. The resultant varnish was used to make the individual evaluations by the above-mentioned respective methods.

Comparative Example 4

[0272] A vanish of a positive photosensitive resin composition was yielded in the same way as in Comparative Example 3 except the use of 2 g of a Novolak resin H (trade name: XPS-4958D, manufactured by Gunei Chemical Industry Co., Ltd.; m/p ratio: 45/55) instead of the Novolak resin G, and 1.2 g of the NIKALAC MX-270 (e) instead of the alkoxymethyl-group-containing thermally crosslinking agent (d). The evaluations of the varnish were made by the respective methods.

[0273] About each of Examples 1 to 5, and Comparative Examples 1 to 4, the composition thereof is shown in Table 1, and the individual evaluation results are shown in Table 2.

TABLE-US-00001 TABLE 1 Alkoxymethyl coumpond (e) or coumpomd (e) Photosensitive having a cyclic Different Polymer (a) compound (b) Solvent (c) polyether structure Novolak resin component Example 1 A: 10 g c: 1.9 g GBL: 30 g d: 1.2 g — g: 0.6 g Example 2 B: 10 g c: 1.9 g GBL: 30 g e: 1.2 g — g: 0.6 g Example 3 C: 10 g c: 1.9 g GBL: 30 g f: 1.2 g — g: 0.6 g Example 4 D: 10 g c: 1.9 g GBL: 30 g d: 1.2 g — g: 0.6 g Example 5 A: 10 g c: 1.9 g GBL: 30 g f: 1.2 g — g: 0.6 g Example 6 A: 10 g NCI-831: 1.4 g GBL: 30 g d: 1.2 g — DPHA: 4.0 g Comparative Example 1 E: 10 g c: 1.9 g GBL: 30 g d: 1.2 g — g: 0.6 g Comparative Example 2 F: 10 g c: 1.9 g GBL: 30 g f: 1.2 g — g: 0.6 g Comparative Example 3 E: 8 g c: 1.9 g GBL: 30 g d: 1.2 g Novolak G: 2 g g: 0.6 g Comparative Example 4 E: 8 g c: 1.9 g GBL: 30 g e: 1.2 g Novolak H: 2 g g: 0.6 g

TABLE-US-00002 TABLE 2 Pattern processibilities Chemical resistance Sensitivity Resolution Reduced film Heat [mJ/cm.sup.2] [μm] quantity [μm] resistance Example 1 160 3 0.15 ∘ Example 2 150 2 0.20 ∘ Example 3 200 4 0.12 ∘ Example 4 150 2 0.20 ∘ Example 5 150 2 0.20 ∘ Example 6 190 6 0.18 ∘ Comparative 250 5 0.20 ∘ Example 1 Comparative 350 6 0.18 ∘ Example 2 Comparative 160 3 1.20 x Example 3 Comparative 180 4 1.00 x Example 4