TW201001066A - Photosensitive resin composition, and photosensitive resin laminate comprising the same - Google Patents

Abstract

Disclosed is a photosensitive resin composition which enables the formation of a pattern thereon, and can be formed into a flexible dry film that produces a sufficiently reduced quantity of cutting dusts when the film is cut. Specifically disclosed are: a photosensitive resin composition comprising (A) an alkali-soluble phenolic resin, (B) a photosensitizing agent having a 1,2-naphthoquinonediazide group, and (C) an alkali-soluble resin having a group derived from an aromatic hydroxy compound in a side chain; and/or a photosensitive resin composition comprising (A) an alkali-soluble phenolic resin, (B) a photosensitizing agent having a 1,2-naphthoquinonediazide group, and (D) a compound which is induced from at least one compound selected from the group consisting of Bisphenol A, Bisphenol E, Bisphenol F, Bisphenol S and a compound produced by hydrogenating any one of the above-mentioned compounds and which has at least one hydroxy group at the terminal.

Description

201001066 VI. The invention relates to a photosensitive tree laminate composition which can be developed by using an aqueous solution, and a photosensitive resin laminate using the same, and the use thereof. The photosensitive resin composition is suitable for the production of a printed circuit board, and is redundantly used for manufacturing a lead frame for mounting (hereinafter referred to as a lead frame), a metal mask for metal precision processing, and a thin film transistor such as a liquid crystal display element. Manufacture of semiconductor packages such as BGA (BaU Gnd Array), CSP (Chip Size - a 'wafer size package), IT 〇 (Indium Tin/xide) electrodes, address electrodes, or The manufacture of components such as electromagnetic wave masks and the manufacture of photoresist patterns suitable for use as protective cover members when processed by a spray substrate. [Prior Art] As an image forming method used for a semi-conductive body circuit, a liquid crystal display device, a printed circuit diagram, or the like, a positive type using a photosensitive resin composition containing her or a compound of a hamster compound as a raw material is known. The photoresist composition forms a positive type. == When the photosensitive resin is coated with a h-shape, the coating thickness is generally 0 5~=, if the positive photoresist is used, a wide size range can be achieved. Image. Eight-size dry circumference, for example, from the range of 半·3 _ around the sub-micron (sub_ 秘丽刚) is widely spread to the size range of tens to hundreds of divisions. Thereby, At ^ micromachining. (4) This is sufficient for the surface of a variety of substrates in the field of liquid crystal displays, etc. 139313.doc 201001066, also with TFT (Thin Flim Transistor), STN (SUper Twisted Nematic 'super twisted nematic) As technology such as liquid crystal progresses, the line width of an image becomes thinner, and the tendency to be finer is enhanced. For example, in the previous TN (Twisted Nematic) and STN liquid crystal, the image size was designed from 200 μηι to hundreds of μηι, and the image was recently developed due to the development of new technologies. The minimum design size is less than 100 μηη. Further, in a TFT display element having good responsiveness or imageability, the image design size is increased to a level of several μm. The characteristics expected as a photoresist material are as follows: the above-mentioned fine processing force is maintained and the area is increased. In other words, the liquid crystal display in which the substrate has been increasing in size in recent years, and the PDP (Pla_ Display Panel, plasma display) which has been initially applied to the large surface. For these substrates, it is an important technology to make the film thickness in the plane more uniform. Further, as a common problem of the large-area display, it is possible to further reduce the cost and the liquefaction of the photoresist used in the production. In the above-mentioned problem, in order to further improve the film thickness in the surface of the photoresist, and to achieve the liquefaction of the photoresist material, the company has continuously researched and applied the coating method. As a result, a new slit coating method is being developed to replace the conventional spin coating method. It is predicted that these techniques (4) can cope with substrates with dimensions of 550 mm x 68 〇 _. However, in the case of facing larger substrates, the application of technologies such as (4) Dragon is more difficult. Further, in the field of printed circuit boards, so-called negative dry film photoresists are widely used at present. The negative dry film photoresist refers to the use of the polyester film as a support (4), and the negative photosensitive resin composition of the 139313.doc 201001066 10~100 μχ is coated on the support and the layer 4 to 40 is laminated thereon. The μιη thick polyolefin film is used as a protective film. The negative dry film photoresist technology is also applied to printed circuit boards having a width of about 600 mm. However, when used in the field of printed circuit boards, the resolution required for negative dry film photoresist is at most about 30 to 300 μηι. . Hereinafter, the fabrication of a printed circuit board using a negative dry film photoresist will be briefly described. First, when a protective film is present in a negative dry film resist, the protective film is removed by a method in which the negative electrode type photosensitive resin composition is brought into contact with a substrate for producing a printed circuit board. The support is exposed to active light to cure the photosensitive resin composition. Second, the concentration is usually used as the mass of i. /. (IV) Aqueous solution represented by the aqueous solution of sodium carbonate The unexposed photosensitive resin composition is dispersed and removed for development. Thereafter, the copper on the substrate is immersed in copper (4). Then, the hardened photosensitive resin composition was completely peeled off by using a sodium hydroxide (tetra) solution or a potassium hydroxide aqueous solution having a concentration of 2 to 3%. ί However, when you need to manufacture TFTs for LCDs, you can scare the image processing technology of the South as above, and the resolution is, for example, 2~Π), which is significantly higher than that of printed circuit boards. In addition to this, the following technologies are also required: no metal ion development, stripping using an organic stripping solution, or Ta' Α丨箄 鸰 鸰 鸰 鸰 溥 溥 溥 溥 溥 及 及 及 及 及 及 及 及 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 For the 5 荨 荨 technology, and the following requirements for the photoresist · The film thickness is a number, for the long-term silk, into the μ of the metal film of various fields, or the inorganic "sexual improvement" For the TFT with a bump of about 1 μηι, the right-handed electric >+ 1 existing pattern is improved, for

The layering of the Mm-wide substrate is accelerated, and thus completely exceeds the limit of the dry film photoresist of the conventional type 1393l3.doc 201001066. In summary, in order to meet the requirements of the LCD and PDP industries, there has been a limit to the method of directly applying a positive liquid photoresist to a substrate or transferring a negative dry film photoresist to a substrate. In order to solve the above problems, the industry is considering the use of positive dry film photoresist, but it has not been put into practical use. For example, in the materials of the positive-type resists of the fifth aspect, for example, Patent Literatures 1 and 2 disclose that a phenol novolak resin is used as a main component, and a 2-naphthoquinonediazide acid S is used as a photosensitive component. However, when it is directly applied to the case of a tantalum photoresist, it cannot be applied to the support thickly due to poor coatability. 'By even if it can be applied thinly, the film is brittle and lacks flexibility. It is difficult to make it into a roll-shaped product. X, Patent Document 3 also discloses a compound obtained by softening a film to induce a reaction of a dry oil (tetra) resin. However, the positive dry film photoresist that currently uses these materials has not yet reached practical use. The details are described below. A rolled product having a desired film width is obtained in the following manner. First, the positive photosensitive resin composition is usually applied to a support or the like to form a wider roll. Next, the roll is cut by the slit "having a film width of 2, and in order to laminate the photosensitive resin composition on the substrate on which the image is formed", the dry film photoresist is usually taken out from the roll-shaped article. A 2 is bonded to the substrate by a bonding machine for thermal transfer. If the lamination is excessive or difficult, the dry film photoresist is cut into the length direction of the substrate longer than when the film is more brittle. There is a problem of dry film light of the following positive photosensitive resin composition: the chips of the photosensitive resin composition of the positive 139313.doc 201001066 type (hereinafter referred to as chips) are generated at the time of the above cutting. The dry film photoresist is cut into a predetermined length in the longitudinal direction of the substrate, and the chips are easily cut from the α-face. The chips become dust and contaminate the operating environment of the substrate or the laminating machine and adhere to the substrate. As a result, the image pattern is likely to be defective. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 06 No. 27657 [Patent Document 2] Patent Publication No. 2〇〇〇_1〇 Bulletin No. 5466 [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei 2 No. 3 3 16577 [Disclosed] The present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern capable of forming a film in a dry film manner. In the present invention, the photosensitive resin composition is soft, and the photosensitive resin composition which can sufficiently suppress the generation of chips and the photosensitive resin laminate using the same can be used. In order to solve the above problems, it has been found that the above problems can be solved by using a sensory resin composition having the following constitution. The present invention is as follows. Π] A photosensitive resin composition, The invention comprises a (Α) alkali-soluble phenol resin, (8) a sensory resin containing (2) a naphthyl group, and (c) a solvent-soluble resin having a group derived from an aromatic radical compound in a side chain. [2] The photosensitive resin composition according to the above [1], wherein the component (c) is a test resin containing (tetra) styrene as a copolymerization component. 139313.doc 201001066 [3] as above [1] The photosensitive resin composition of the above-mentioned (2) is contained in the above-mentioned (A) component, and 75 mass% of the above-mentioned (A). (b) The photosensitive resin composition as described in any one of the above-mentioned items [1] to [3], further comprising (D). [5] The photosensitive resin composition according to any one of the above-mentioned items (1), which contains a compound represented by the following formula (1) A sulfonate as the above component (B): [Chemical 1]

In the formula, 1 to 116 are independently hydrogen, halogen, ci~c4 alkyl, alkenyl or hydroxy, and R7 and R8 are each independently hydrogen, i or C1 to C4 alkyl, and R9 to R" The photosensitive resin composition as described in any one of the above-mentioned items [1] to [5], wherein the component (D) is selected from the group consisting of bisphenol a, Between bisphenol £, bisphenol F and bisphenol S and a group of compounds obtained by hydrogenation of *, 139313.doc 201001066 is derived from one less compound and has at least one quinone at the end. . [7] A photosensitive resin layered body comprising at least a support, and a photosensitive resin layer formed from the photosensitive resin composition according to any one of the above [1] to [6]. [8] A photoresist roll which is formed into a roll shape as the photosensitive resin laminate described in the above m. f ϋ [9] A photoresist pattern fortunately > +, , ^ $ into a method's sequence includes: Photosensitivity as described in [8] above, and the sensitization of the layered body a step of laminating the resin layer on the substrate, and an exposure step of exposing the subtractive ground/secondary resin layer to a developing step of removing the photosensitive photosensitive resin layer. [10] The method for forming a photoresist pattern according to the above [9], wherein the exposure step is performed in a direct riding diagram (4), in the above [11], a printed circuit board, and a method for forming L, which further includes: (4) by reading the remaining lines of σ above [9] or [10]. Method (4) Forming a substrate with a photoresist pattern [12] Is the method of manufacturing a lead frame or the method described in Π0]? , including: by using the steps [9] above. The substrate having the first resist pattern is etched. [13] A semiconductor pattern is as described in the above [9] or [1G], which further includes the steps of performing button etching or mineral deposit. ^ Substrate in which a photoresist pattern is formed Π 4] - A film transistor is described in [9] or [10]. Wanfa, which includes:

Dry ~ ~ is the law to open the J 7 battle with the substrate of the photoresist pattern to etch 139313.doc 201001066 engraved or key step, step. [15] A photosensitive resin composition comprising (a) an alkali-soluble phenolic resin (B) 3 1,2-naphthyl diazide-based sensitizer, and (D) selected from the group consisting of two ages A Two-year-old E, double-test F, and two-year-old s, and a compound obtained by chlorination, and a compound obtained by at least one compound in the group and having at least one hydroxyl group at the terminal is used. [16] The photosensitive resin composition according to the above [15], wherein the component (D) is a group selected from the group consisting of a compound represented by the following formula (νπ) and a compound obtained by hydrogenating the same At least one compound: [Chemical 2]

(VII) {wherein, Y] is a thief, V, 2 is a stretching propyl 'Y3 is a carbon number 4 to 6 alkylene group 'Y4 and 丫5 are each independently a hydrogen atom or a methyl group, p' q And the integers above and above, which are 1~2G in total, and the repeating unit of the oxidized stretch ethyl group, the oxidized stretch propyl group, and the carbon number 4~6 oxidized stretching group contained on the right side and/or the left side of the structure may be random. Adding ground can also be added as a block}. The photosensitive resin composition according to the above [15] or [16], which contains the above-mentioned component (4) and h5 mass% of the component (B) in an amount of 20 to 9 % by mass, and further contains 1 to 75% by mass. The above component (D). [18] The above-mentioned [15] to [17], which contains quinonediazidesulfonic acid 139313.doc -10- which is a compound which is not combined with the photosensitive resin described in the following formula (1) 201001066 Stuffed as the above (B) ingredient: [Chemical 3]

{In the formula, respectively, independent A answer, horse wind, halogen, Cl~C4 alkyl, alkenyl or via the base 'R_7 and Rs respectively independent main bird ^ J is established as a halogen, halogen or Cl~C4 alkyl, Further, R9 to R11 are each independently hydrogen or an alkyl group of C1 to C4. [19] A photosensitive resin accumulation layer body comprising at least a support, and by any of the above [15] to [18] A photosensitive resin layer formed of the photosensitive resin composition contained in the item "1". [20] A resistive reel, i, which will be a reel of a photosensitive resin laminate as described in the above-mentioned Π9]. A method for forming a photoresist pattern, which comprises the steps of laminating a photosensitive (four) lipid layer (four) on a photosensitive resin layered body as described in the above [19], and exposing the photosensitive resin layer to exposure. And a developing step of removing the photosensitive photosensitive resin layer. [22] The method for forming a photoresist pattern according to [21] above, wherein the direct exposure is performed in the exposure step. 139313.doc • 11 - 201001066 [23] A method of manufacturing a printed circuit board, comprising: forming a u-war resist pattern by the method described in [2 1 ] or [22] above; The step of etching or plating is performed. 〃 It comprises: forming an inscribed step by etching the substrate of the photoresist pattern as described in [24], a method for manufacturing a lead frame, and the method described in [2 1 ] or [22]. And comprising: performing a substrate having a photoresist pattern as described above, comprising: performing the method of manufacturing a semiconductor pattern by the substrate having the photoresist pattern as described above [25] or [22] The method forms a step of surname or key placement. [26] A method of producing a thin film transistor, which comprises the steps described in [21] or [22] to form an etching or a money coating. [Effect of the Invention] According to the present invention, it is possible to provide a pattern capable of forming a pattern, and the photosensitive resin composition is relatively soft when the film is dry and the film is formed, and even if the film is diced, the sensitization of the genus can be sufficiently suppressed. Resin composition. [Embodiment] The present invention will be described in detail below. (A) Solubility-resolving resin (4) The solvent-soluble resin is obtained, for example, by a polycondensation reaction using a compound, a mixture of acetonide and/or _ as a raw material. 'As the compound of the above-mentioned age, for example, H-methyl, dimethyl-brown; ethyl benzoate, butyl benzene, 1-methylbenzene burning test; methoxybenzoquinone, 2-methoxy Alkylbenzene, etc.; acetophenone benzene 139313.doc -12- 201001066 Hope, allyl benzene, etc., phenyl group age; phenyl benzene age, etc. aryl benzene age; ¥ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Polyhydroxybenzene such as benzene phenol, resorcinol, bisphenol A, bisphenol F, etc.; and naphthene compound of α, _ naphthalene; base to 2-ethanol, p-hydroxyphenyl _3_propanol, p-hydroxyphenyl-4-butanol, etc., 9-based benzophenone; mercaptoethyl ketone, etc.; bisphenol monoethylene oxide adduct, a phenol compound containing an alcoholic hydroxyl group such as a monopropylene oxide adduct of bisphenol; and p-hydroxyphenylacetic acid, p-hydroxyphenylpropionamidine, p-hydroxyphenylbutyric acid, p-hydroxycinnamic acid, hydroxybenzoic acid, Hydroxyphenyl benzoic acid, Phenoxy stupid acid, bis acid-containing phenol compound, etc. carboxyl and the like. These phenol compounds may be used singly or in combination of two or more. Examples of the aldehyde and/or ketone include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxyphenylhydrazine 15, decyloxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, and crotonaldehyde. Gas acetaldehyde, gas phenylacetaldehyde 'acetone and glyceraldehyde. Further, examples of the aldehyde and/or ketone include glyoxylic acid, decyl glyoxylate, phenyl glyoxylate, hydroxy ester of glyoxylic acid, formazanic acid, methyl hydrazine acetate, and 2- Propionic acid, decyl 2-methylpropionate, pyruvic acid, acetopropionic acid, 4-ethyl phthalic acid, acetone dicarboxylic acid, and 3,3,,4,4, dioxin Formic acid. Further, a furfural precursor such as paraformaldehyde or trioxane may also be used. These may be used alone or in combination of two or more. It is preferred to use an acidic catalyst in the above polycondensation reaction. By using the 139313.doc -13 - 201001066 acid catalyst, it is easy to obtain a varnish-type resin, which can more effectively prevent the generation of chips. As the acidic catalyst, for example, citric acid, formic acid, acetic acid, p-toluene acid, and oxalic acid are used. The acidic catalysts may be used alone or in combination of two or more. Further, the conditions for synthesizing the (tetra) resin may be known conditions. The content of the aldehyde and/or ketone in the raw material for obtaining the alkali-soluble phenol resin is preferably θ' with respect to the above phenol compound. In this case, the above polycondensation reaction can be carried out more rapidly. Further, the (A) alkali-soluble phenol resin may be a polycondensation product of a compound other than phenol such as the above phenol compound and m-xylene. In this case, the compound other than the benzene used in the polycondensation is preferably less than 0.5 with respect to the compound. Ζ Ζ 验 验 验 之 之 之 之 之 之 之 之 之 之 之 之 之 之 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶 凝胶〇〇~1〇〇, _, and then better is 丨卿~冰纲. The weight average molecular weight is preferably 300 or more from the viewpoint of film coating properties. Further, it is preferably 100,000 or less from the viewpoint of developability on t. In addition, when the weight average molecular weight of the above resin is small, the chain extender can also be used to carry out the polymerization of the resin, so that the molecular weight is increased to achieve the above-mentioned weight average score of Ie, in the 10 knives. The track circumference. As the bond extender, for example, a diepoxide compound or a 4 (tetra) compound which can react with an m group, and a diisocyanate 3 compound which can react with a warp group can be used. σ (4) Detective decyl resin can be used alone or more than 2 kinds of plants I393i3.doc •] 4- 201001066. The alkali-soluble phenol resin in the case where two or more types are used in combination, for example, two or more kinds of test phenol resins obtained from monomers having different types of different types, and having different weight average molecular weights Two or more kinds of alkali-soluble phenol resins and two or more alkali-soluble phenol resins having different degrees of dispersion from each other. (A) The proportion of the test phenol resin in the photosensitive resin composition is preferably from 20 to 90% by mass based on the total amount of the photosensitive resin composition.

%, and further preferably 25 to 85 mass. Oh, especially good is 3〇~8〇 quality %. The blending ratio is preferably from the viewpoint of improving the pattern formability, and is preferably 90 Å or more in terms of preventing the photoresist film from being brittle. /. the following. (Β) A sensitizer containing 1,2-naphthoquinonediazide group (Β) containing 1,2-naphthoquinonediazide group is a sensitizer having a sulfo group and/or a sulfochlorinated group. a compound obtained by reacting a naphthoquinone diazide compound with an organic or organic group having a trans group or an amine group (hereinafter referred to as "organic compound"). At this time, the hydroxyl group or the amine group of the organic compound is 〗 〖 Sulfo or sulfonium chloride linkage of the azide compound. Further, the bond may be at least one in the molecule of the obtained diazide compound. Examples of the above-mentioned 1,2·quinonediazide compound having a sulfo group and/or a sulfonium chloride group include, for example, .i, 2—naphthalene diazide_heart acid, Cai Yi j-halide-5 - sulfonic acid, U-naphthoquinone_2_diazide_4_sulfonate, and " brewing I diazide to xanyl chloride. The above has a contiguous group and/or a hydrazine group: wherein: the bis-nitrogen compound is preferably selected from the group consisting of naphthalene, azide _ 4-1⁄2 acid, 1,2 _ naphthene, and diazide. 1,1_naphthalene-branches_2_diazepine·4· 139313.doc •15· 201001066 Shixing 1吼, and 1,2-naphthalene_2_diazide_5•continued chlorine 1 ^ or more of the compounds in the group. These m-enriched nitrogen compounds having a schistosyl group and/or a sulfonated chlorine group are sufficiently dissolved in a solvent, so that the reaction efficiency with organication can be improved. σ As the organic compound, for example, polyhydroxybenzophenones, bis[(poly)p-phenylene]hydrocarbons, tris(p-phenylphenyl)methanes or methyl substituents thereof, Bis(cyclohexylphenyl)phenyl (p-phenyl)methane or its methyl group: phenol, p-methoxyphenol, dimethylphenol, hydroquinone, phthalate , o-benzene three-year-old, o-benzene trimethoate _, catechol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, diaminobenzophenone And (4), orthophthalic acid-acetone resin, a homopolymer of styrene-based styrene or a monomer which can be copolymerized with the monomer, or the like, may be used singly or in combination of two or more. Examples of the above-mentioned poly-based benzophenone g include, for example, bisbenzoquinone, benzoic benzophenone, 2,3,6-trihydroxybenzophenone, and 2,3,4_3. Hydroxymethyl bis- bis, 2,3,4,4|-tetrahydroxydibenzophenone, 2,2,,4,4,·tetrahydroxy bis-ketone, 2,3',4,4', 6_pentahydroxybenzophenone, 2,2,3,4,4,pentahydroxyketone, 2,2',3,4,5_pentane group: benzene f _, may·hexanyl group: ketone, And 2,3,3',4,4,,5,. hexa- benzophene _. These may be used alone or in combination of two or more. Examples of the bis ((poly) phenyl group) include, for example, phenyl phenyl), bis (2, 3, 4 _ trisyl), sb. Base)-2-(4|_ 经基基基)propane, 2_(24_二经基基基二139313.doc -16- 201001066 hydroxyphenyl)propane, 2-(2,3,4-tri Hydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl Phenyl]ethylene}bisphenol, and 3,3'-dimercapto-{1-[4-[2-(3-mercapto-4-hydroxyphenyl)-2-propyl]phenyl ]Ethylene}bisphenol. These may be used alone or in combination of two or more. Examples of the tris(hydroxyphenyl)decane or its mercapto substituent include tris(4-hydroxyphenyl)methane and bis(4-hydroxy-3,5-dimercaptophenyl)_4_ / Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylindane, bis(4-hydroxy-3,5-dimethylphenyl)-2- Hydroxyphenyl decane, bis(4-cysyl 2,5-monomethylphenyl)-2-p-phenylene, bis(4-trans-yl-2,5-dimercapto) 3,4·dihydroxyphenylmethane, and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane. These may be used alone or in combination of two or more. Examples of the bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane or a methyl substituent thereof include bis(3-cyclohexyl-4-hydroxyphenyl)_3-hydroxyphenyl ij 甲· Bis(3-cyclohexyl-4-ylphenyl)-2-phenylphenyl, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenyl decane, bis(5-cyclohexyl) Hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4 -hydroxy-2-indolylphenyl)_4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenyldecane, bis(5-cyclohexyl-4-hydroxy-3) -nonylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl_4-hydroxy-3-methylphenyl)_3_hydroxyphenylmethane, bis(5-cyclohexyl_4_hydroxyl_ 3_曱基笨基)_2_hydroxyphenylmethane, (3 hexyl-2-butylidenephenyl)_4_p-phenylene, bis (3-cyclohexyl) 139313.doc -17- 201001066 2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxyl-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl_2_ hydroxyl _4_ methylphenyl) -4-hydroxyphenyl methane. These may be used alone or in combination of two or more. Among these, as the above organic compound, polyhydroxybenzophenone bis-[(poly)predomylphenyl]hydrocarbon, tris(phenylphenyl)methane, and/or double are preferred. (Cyclohexylhydroxyphenyl) (hydroxyphenyl)methane. Further, the above organic compound is preferably at least one compound selected from the group consisting of compounds represented by the following general formulae (1), (π) and (πι). In this case, the difference in solubility of the photosensitive resin composition with respect to the developer before and after the irradiation of the light becomes large, and there is an advantage that the image contrast is further excellent. Among them, from the viewpoint of sensitivity, a group selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula („), and a compound represented by the following formula _ is more preferable. At least _ kinds of compounds: [Chemical 4]

139313.doc 18- 201001066 {wherein R!~R6 are independently 虱, halogen, C1-C4 alkyl, alkenyl or hydroxyl, Han 7 and R8 are s丨丨1 and i is independently hydrogen, Halogen or a C to C4 alkyl group, and R9 to Rl 1 are each independently 氕+von or C1 to C4 alkyl};

(II) wherein R 15 is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted carbon number 5 alkoxy group; 6] III)

In the formula iJ, R16 to R19 are each independently a ^ 1 ^ fluorene atom, a substituted or unsubstituted oxime number 1 to 5, or a substituted ^ ^ 〇 ν ^ ο α sub-substituted carbon number An alkoxy group of 1 to 5, and X is an early bond, an oxygen atom or an extension based on an organic compound selected from the group consisting of the above formula (H), a compound represented by the above formula (I), and the above formula (II) And the compound represented by the above formula (III), in the case of at least one of the group consisting of the chemical compound and the substance, has a sulfo 139313.doc -19· 201001066 base and/or an item The gas-based 1,2-branched diazide compound is preferably 1,2-naphthoquinone-2-didiazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5- Sulfonic acid, 1,2-naphthalene-diazide-4-sulfonyl chloride, and/or hydrazine, 2-naphthoquinone-2-diazide-5-sulfonyl chloride. The 1,2-quinonediazide compound having a sulfo group and/or a sulfonium group, and a compound selected from the above formula (I), a compound represented by the above formula (π), and Since at least one of the compounds consisting of the compound represented by the above formula (111) has good compatibility, the amount of aggregate generated when the (Α) component and the component (7)) are mixed can be reduced. In addition, when the photosensitive resin composition containing these is used as a photosensitive component of a photoresist, sensitivity, image contrast, and heat resistance are more excellent. Again, selected from

Compound: [Chemistry 7]

[Chem. 8] 139313.doc 20- (V)201001066

OH

[Chemistry 9]

(VI) In this case, there is an advantage that the light sensitivity is more excellent. Among them, particularly preferred are the compounds represented by the following formula (IV). 1 using at least one compound selected from the group consisting of a compound represented by the above formula (I), a compound represented by the above formula (II), and a compound represented by the above formula (III) The method for synthesizing the 2-naphthoquinonediazide compound includes the following method. In other words, for example, a group selected from the group consisting of the compound represented by the above formula (I), the compound represented by the above formula (II), and the compound represented by the above formula (III) At least one compound and 1,2-naphthoquinone-2-diazide-sulfonium gas are added to a solvent such as dioxane or THF in triethylamine, triethanolamine, alkali metal carbonate or alkali metal A method of reacting in the presence of a base catalyst such as hydrogencarbonate. In this case, a compound selected from the above formula (I), a compound represented by the above formula (Π), and a compound represented by the above formula (III) 139313.doc -21 - 201001066 are synthesized. A sensitizer containing ruthenium, a 2-naphthoquinonediazide group formed by condensation of a hydroxyl group of at least one compound of the composition group with a sulfonyl group of ruthenium, 2-naphthoquinone-2-diazide-sulfonate. Further, in the obtained bismuth-containing, 2_naphthoquinonediazide-based sensitizer, selected from the group consisting of compounds represented by the general formulae (I), (11) and (111) The hydroxy group of at least one compound and the sulfonyl group of 丨'2-naphthoquinonediazide-sulfonyl chloride may be at least one. Further, as 1,2-naphthoquinone-2-diazide-sulfonyl chloride, hydrazine, 2_naphthoquinone-2_diazide-4-sulfonyl chloride, or hydrazine, 2_naphthoquinone-2 _Diazide _5_ sulfonium chloride is preferred. These may be used alone or in combination of two or more. (B) The blending ratio in the photosensitive resin composition is preferably 75 mass%, more preferably 5 to 50 mass%, based on the total amount of the photosensitive resin composition. Particularly preferably, it is 5 to 4% by mass. And especially good 疋10 30 shells $%. The blending ratio is preferably 疋1% by mass or more from the viewpoint of improving the light sensitivity. The &> is preferably 75 mass% or less from the viewpoint of preventing the photoresist film from being brittle. (6) A residual-soluble resin having a group derived from an aromatic mercapto group-containing compound in a side chain as a solvent-soluble resin having a group derived from an aromatic hydroxy compound on a side bond (C), for example, (1) poly(phenylene) The resin (9) contains a base 4 (meth) acrylate resin, a phenol group-containing polypropylene amide resin, and the like. As a method for producing a polyhydroxystyrene-based resin, the following methods and the like are known as a method known in the art: dehydration by ethoxylated phenyl group, decomposition by cinnamic acid, Vinyl benzene monomer obtained by various methods such as ethyl dehydrogenation, in cation or free 139313.doc -22* 201001066

Monomerization or copolymerization with other comonomers in the presence of a base initiator. Further, there is also known a method of synthesizing a monomer which protects a hydroxyl group of a vinyl phenol by an ethyl hydrazide group, a trimethyl decyl group, a tert-butyl group, a third butoxycarbonyl group, etc., in a cation, an anion The polymerization is carried out in the presence of a radical initiator, and then the protecting group is liberated to obtain a polymer. In this method, by selecting the kind of the protecting group and the kind of the initiator, it is also possible to manufacture a monodisperse polymer obtained by using the "living p〇lymerizati〇n" (Japanese Patent Special Kaiping) Bulletin No. 3_2776〇8). Further, a method of hydrolyzing the vinyl phenol-based polymer to obtain a modified hull having excellent light transmittance is known (Japanese Patent Laid-Open No. (9) nickname), or a vinyl stupid m A method for producing various kinds of vinegar derivatives by the reaction of the base of the compound (Japanese Patent Laid-Open No. 63 3123〇7, Fiber High Knife Materials Research Institute Report 128, page 65 (i98i)) and ethylene A method for producing various kinds of nuclear substitutes of a phenolic phenolic compound (Japanese Patent Laid-Open Publication No. SHO-63-69-A). Examples of the (1) polypyridyl styrene resin include: polypyridyl benzene, modified polyhydroxy styrene, hydrogenated polyhydroxy styrene, hydroxystyrene and styrene, (meth) acrylate, and cis. A copolymer such as a butylene diester or the like. The reset average molecular weight of the polystyrene styrene is ιοοο~ (, just, (10), preferably 5,000 to 50,000. As a modified polyhydroxybenzoic acid, ^• spot + G monument, it can be mentioned: alkaline In the presence of a catalyst, for example, a quinone chloro derivative, a butyl phthalocyanine derivative, a benzoquinone chloro derivative, a naphthoic acid chloro derivative, and a polyhydroxystyrene are reacted. 139313.doc •23· 201001066 Specific examples of the above-mentioned sulfonium chloride derivative or formazan chlorine derivative include acetaminophen benzene sulfonium chloride, benzene sulfonium chloride, and chloro chlorobenzene. Sulfonium chloride, benzyl sulfonium chloride, acetal benzene carbonylated carbonyl, benzamidine chloride, p-chlorobenzhydryl chloride, naphthyl benzamidine chloride, etc. In this case, relative to polyhydroxyl The above-mentioned hydrazine chloro derivative or the above-mentioned formazan chloro derivative is usually used in an amount of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 1 part by weight of the styrene. The weight average molecular weight of styrene is from 3,000 to 50,000, preferably from 5 〇〇〇 to 3 Å. Stupyl vinyl is a hydrogenated styrene and a two-part of the modified polyhydroxy styrene modified by a substituent to a part of the benzene ring. The weight average molecular weight of the hydrogenated polyhydroxystyrene is wanted. It is selected from the range of 3,000 to 30,000, preferably 5, 〇〇〇 to 25 。. The weight average molecular weight is preferably 3,000 or more in terms of mechanical properties or dry etching resistance. From the viewpoint of capacitiveness, it is better than 30,000. Knife is about the private laughter when it is copolymerized with other ingredients. The ratio of basic ethylene to 刀 吋 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 获得 迕 迕 迕 迕 迕 迕 迕 迕 迕Point 5, preferably 30% by mass or more, 100% by weight or less. Further preferably

The ratio of the basic ethylene of the xenon lamp is 4C mass ° /. Above 100% by mass. As a (Π) age-based poly(indenyl) acrylate acid tree, methacrylic acid _4-pyridyl benzene, methyl acrylate acid - 2 ♦ phenyl group) A polymer, a copolymer, and a potted modified body of an age-containing poly(meth)acrylic monomer. The weight of the (tetra)-containing poly(meth)acrylic acid vinegar resin is average; the amount is 5,000 to 1, and 〇〇〇, _ ' is preferably 1 〇, _~. 139313.doc -24- 201001066 Further, as the (in) polyacrylamide resin containing a phenol group, a phenol group-containing acrylonitrile such as 3,5-monodecyl-4-hydroxybenzyl acrylamide can be mentioned. Amine single: Polyether 4, copolymer and its modified body. The phenol group-containing polypropylene guanamine resin has a weight average molecular weight of 1 〇〇〇 to WOO'OOO, preferably 5,000 〜1 〇〇, and 〇〇〇0 (C) has an aromatic hydroxy compound derived from the side chain. The amount of the alkali-soluble resin to be blended is preferably from 1 to 75 % by mass based on the mass% of the photosensitive resin composition. Further preferably, it is 5 to 50% by mass. The blending ratio is preferably 丨% by mass or more from the viewpoint of preventing the photoresist film from being brittle, and is preferably 75 mass% or less from the viewpoint of solubility of the entire system. (D) Plasticizer It is preferred that the photosensitive resin composition contains (D) a plasticizer from the viewpoint of reducing v-cut. The (D) plasticizer' may be a compatible low molecular weight component, and examples thereof include polyethylene glycol, polypropylene glycol, and polyoxypropylene polyoxyethylene ether dioxyethylene monoterpene ether. Propylene monoterpene _, polyoxyethylene polyoxypropylene monomethyl scale t-oxyethylene single ethyl acetate ^, polyoxypropylene single ethyl, polyoxyethylene dioxypropylene monoethyl ether special alcohol _ esters; phthalic acid Ethyl formate such as o-benzoic acid, o-toluenesulfonamide, p-toluenesulfonamide, citric acid-sodium citrate, ethyl triethyl citrate, acetonitrile citrate Tri-n-propyl ester, tri-n-butyl citrate, and the like. The (D) plasticizer contained in the photosensitive resin composition can reduce the amount of chips at the time of film formation in the state of excellent pattern formation property. 1393I3.doc -25· 201001066 In general, it is preferably derived from at least one compound selected from the group consisting of bisphenol A, bisphenol E, bisphenol F, and bisphenol S, and a compound obtained by the hydrogenation, and has an end. A compound of at least one hydroxyl group. As such a compound, bisphenol A (2,2-bis(4,-hydroxyphenyl)propane) or bisphenol E (l,l-bis(4-hydroxyphenyl)ethane) or a hydroxyl group at both ends of bisphenol ρ (4,4,-methylene bisphenol) or bisphenol S (4,4,-sulfonyl bisphenol), introduced into an alkyl group, an alkylene oxide group, or a polyoxyalkylene A compound of an aliphatic molecular chain such as an alkyl group. Examples of the alkyl group include a mercapto group, an ethyl group, and a propyl group. Examples of the oxyalkylene group include an oxymethylene group, an oxidized ethyl group, an oxidized propyl group, an oxidized butyl group, and the like. Examples of the alkylene group include a polyoxymethylene group, a polyoxyalkylene group, a polyoxylated propyl group, a polyoxybutylene butyl group, or a block copolymer or a random copolymer formed therefrom. . The component (D) is premised on having at least one hydroxyl group at the terminal, and the terminal of the molecular chain introduced may have a structure other than a hydroxyl group. Among the above compounds, in terms of flexibility of the photoresist film, a compound derived from bisphenol A or a compound which hydrogenates it is preferred. Further, the component (D) is further preferably selected from the group consisting of the following formula (Yu).

a compound of the group consisting of compounds that are not hydrogenated and hydrogenated, and a compound: V

[化10]

139313.doc -26· 201001066 {wherein, Y! is an ethyl group, Υ2 is a propyl group, and Υ3 is an alkyl group having a carbon number of 4 to 6', and Υ4 and Υ5 are each independently a hydrogen atom or a methyl group, p, q and r are integers of 0 or more, and the total is 1 to 20, and the repeating unit of the oxidized ethyl group, the oxidized propyl group, and the oxyalkylene group having a carbon number of 4 to 6 contained in the right side and/or the left side of the structure may be The total amount of p, q, and r added to the right side and/or the left side of the above formula (VII) can be added as a block, and the total amount of p, q, and r in the above formula (VII) is 1 to 20, which is less likely to cause chip cutting at the time of film cutting. When it is 1 or more, it is 20 or less in terms of obtaining favorable pattern formability. The total of p, q and r is preferably from 1 to 10, more preferably from 2 to 6, and not more than 6. Further, in terms of the chip which is less likely to cause film cutting, it is preferred that the compound represented by the above formula (VII) has a repeating unit of oxidized propyl group, and particularly preferably the right side and/or the left side thereof. q is 1 or more and 10 or less, and more preferably 1 or more and 6 or less. a repeating unit of the oxidized ethyl group, the oxidized propyl group, and the oxyalkylene group having a carbon number of 4 to 6 contained on the right and/or left side of the structure of the compound of the above formula (VII), as long as the total of the repeating units is If it is 1~20, it can be added randomly or as a part. Specific examples of the compound represented by the above formula (VII) include ADEKA NOL (registered trademark) SDX-1569, ADEKA NOL (registered trademark) SDX-1570, and ADEKA NOL (registered trademark) SDX-1571. ADEKA NOL (registered trademark) SDX-479 (above is manufactured by Asahi Kasei Co., Ltd.), NEWPOL BP-23P, NEWPOL (registered trademark) BP-3P, NEWPOL (registered trademark) BP-5P, NEWPOL (registered trademark) BPE- 20T, NEWPOL (registered trademark) BPE-60, NEWPOL (registrar 139313.doc -27- 201001066 standard) ΒΡΕ-100, NEWPOL (registered trademark) ΒΡΕ-180 (above is Sanyo Chemical Co., Ltd.), UNIOL (registered) Trademark) DB-400, UNIOL (registered trademark) DAB-800, UNIOL (registered trademark) DA-350F, UNIOL (registered trademark) DA-400, UNIOL (registered trademark) DA-700 (above manufactured by Nippon Oil Co., Ltd.) ), BA-P4U GLYCOL, BA-P8 GLYCOL (above, manufactured by Japan Emulsifier). In the case where the component (D) is contained in the photosensitive resin composition, the content is preferably 1% by mass or more and 7% by mass or less based on the total amount of the photosensitive resin composition. In terms of ensuring the flexibility of the photoresist film, it is preferably 1% by mass or more, and in terms of ensuring the light sensitivity of the photoresist film, it is preferably 75 mass% or less. Further, it is preferably 5% by mass or more and 60% by mass or less. More preferably, it is 1% by mass or more and 50% by mass or less. Especially good is 20 to 40% by mass. Other components The photosensitive resin composition may contain a surfactant for the purpose of improving coatability, defoaming property, flatness, etc., if necessary. The surfactant is not particularly limited, and a fluorine-based surfactant is preferred. As such a fluorine-based surfactant, for example, BM-1000, BM-1100 (above, BM Chemie); MEGAFACE (registered trademark) F142D, MEGAFACE (registered trademark) F172, MEGAFACE (registered trademark) F173, MEGAFACE (registered trademark) F183, MEGAFACE (registered trademark) R-08, MEGAFACE (registered trademark) R-30, MEGAFACE (registered trademark) R-90PM-20, MEGAFACE (registered trademark) BL-20 (above is Dainippon Ink) FLORARD FC-135, 139313.doc -28- 201001066 FLORARD FC-170C 'FLORARD FC-430' FLORARD FC-431, FLORARD FC-4430 (above Sumitomo 3M); Surflon (registered trademark) ) S-112, Surflon (registered trademark) S-113, Surflon (registered trademark) S-131, Surflon (registered trademark) S-141, Surflon (registered trademark) S-145 (above, manufactured by Asahi Glass Co., Ltd.); 28PA, SH-190, SH-193, SZ-6032, SF-8428 (above is Toray

Commercial products such as those manufactured by Silicone. These may be used alone or in combination of two or more. f. The blending ratio of the surfactant is preferably 5% by mass or less based on the total amount of the photosensitive resin composition. When the blending ratio exceeds 5% by mass, the pattern formability tends to decrease as compared with the case where the blending ratio is in the above range. The photosensitive resin composition may further contain a bonding aid to improve adhesion to a substrate or the like. As the adhesion aid, a functional decane coupling agent is preferred. Here, the term "functional decane coupling agent" means a decane coupling agent having a reactive substituent such as a carboxyl group, a mercapto fluorenyl fluorenyl group, an isocyanate group or an epoxy group. Examples of the functional decane coupling agent include: tridecyloxydecyl benzoic acid, γ-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxy Basear, ¥-glycidoxypropyltrimethoxydecane, tridecyloxydecylpropyl isocyanate and 1,3,5-fluorene-tris(tridecyloxydecylpropyl)isocyanate. These may be used alone or in combination of two or more. The blending ratio of the above-mentioned auxiliary agent is preferably 20% by mass or less based on the total amount of the photosensitive resin composition. If the blending ratio exceeds 2 〇 mass 139313.doc -29- 201001066%, there is a tendency that development is likely to occur as compared with the case where the blending ratio is in the above range. The photosensitive resin composition may further contain an acid or a high boiling point solvent to finely adjust the solubility with respect to the alkaline developing solution. Examples of the acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoquinone, and cinnamic acid, which are mono-repules; lactic acid, 2-light-based butyric acid, and 3 - butylbutyric acid, salicylic acid 'm-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-cyanocinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, lilac Hydroxy monocarboxylic acid such as acid; oxalic acid, succinic acid, glutaric acid, hexamethylene, m glutenic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid , for stearic acid, 1,2-cyclohexanedidecanoic acid, 1,2, P. '1^ -田λ分^ acid, &quot; human not one formic acid, 1,2-ring 巳 π A defeat, 1,2 ί Yihexi dicarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentane tetracarboxylic acid, butane tetracarboxylic acid, 1,2,5,8-naphthalene tetradecanoic acid, etc. Carboxylic acid; phthalic anhydride, succinic anhydride, citraconic anhydride, dodecyl succinic anhydride, triterteryl phthalic anhydride maleic anhydride, hexahydrophthalic anhydride, methyl tetralin, scorpion Methyl bicycloheptanic acid anhydride, 1,2,3,4-butanetetracarboxylic acid, cyclopentafurone -Red^ Τ 酐-anhydride, phthalic anhydride, quaternary tetrazine needle, trimellidil 36 Χ anhydride, ketone ketone tetraphthalic acid dianhydride, ethylene glycol bis-phthalic anhydride ester, Gan , acid needles such as one / Α / two partial stearic anhydride esters. Further, 0 high boiling point solvent, for example, '1 gamma can be mentioned: Ν-methyl decylamine, hydrazine, hydrazine-dimethyl dimethyl amide, hydrazine - A certain — secret - * this amine, Ν-mercapto ethane Amine, hydrazine, hydrazine-dihydrazino amide, fluorene-fluorenyl η ratio 咕 咕 疋 疋 I brewing I, dimethyl sulfoxide, benzyl ethyl ether, di-e-ether, acetone propyl _, Li &quot; Vorketone, caproic acid, caprylic acid, 1-octyl alcohol, 1 alcohol, benzyl alcohol, ethyl brewing; ^ 卞酉曰, ethyl bromide, diethyl oxalate, cis 139313.doc -30· 201001066 diacid乙乙酷, γ·丁内醋, ethylene carbonate, propylene carbonate, phenyl cellosolve, etc. These may be used alone or in combination of two or more. The above acid or high boiling solvent The blending ratio can be adjusted according to the coating method by $, and is not limited as long as it can be uniformly mixed in the photosensitive resin composition. For example, 'the ratio of the acid or the high-foam solvent is relatively good. The total amount of the photosensitive resin composition is 6 〇 mass% or less, and further = 4 〇 mass% or less. In this case, there is an advantage that the characteristics of the photosensitive sapphire composition are not impaired. The photosensitive resin composition of the fine form may contain a sensitizer, a light absorbing agent (dye), a crosslinking agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, and a sealant as needed. Additives such as a property-imparting agent, a peeling accelerator, an antioxidant, a fragrance, a developer, and a thermal crosslinking agent, etc. These additives may be used singly or in combination of two or more. There is no particular limitation as long as the range of the characteristics of the photosensitive resin composition is not impaired, and the total amount of the yttrium of the photosensitive material is 5% by mass or less with respect to the photosensitive resin. Each of the above components may be combined with each other as an example. 丫 (There may be a photosensitive resin έ and a human-made m may be mixed and mixed: a preparation of the material may be carried out by a usual method, a resin combination In the case of things... Shi 1 material, pigment added to the photosensitive three _ mill "minute m2 points (four) mixer, homogenizer, can also be further used screens, membrane transitions, etc.. See also 139313. Doc -31 - 201001066 Next, the photosensitive resin laminate is explained The photosensitive resin laminate has the following structure. It contains at least a support and a photosensitive resin layer formed of the above-mentioned photosensitive resin composition. As the support, for example, copper, a copper alloy, iron, or iron can be used. A metal plate such as an alloy, or a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, etc. The thickness of the support is preferably 丨5丨μηι. Photosensitive resin layer The photosensitive resin composition of the present embodiment can be formed into a liquid form and applied to a support. When the photosensitive resin composition is applied onto a support, the photosensitive material can be used as needed. The resin composition is dissolved in a predetermined solvent to form a solution having a solid content of 30 to 60 s%, and this solution is used as a coating liquid. Examples of the solvent include decyl alcohol, ethanol, propanol, ethylene glycol, propylene di 2 octane, decane, petroleum ether, naphtha, hydrogenated naphtha, and naphtha. Mercaptoisobutyl ketone, methyl ethyl _, cyclohexanone, toluene, dioxane, tetramethyl benzene, hydrazine, hydrazine dimethyl dimethyl amide, ethylene glycol monoethanol hydrazine, ethylene Alcohol monobutyl glycol monoethyl ether, diethylene glycol early oxime ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl _, propylene glycol mono (tetra), dipropylene glycol diethylene H ethylene two materials = Diacid B, butyl acetate, ethylene glycol, single ethyl acetate, acetic acid, ethylene glycol, acetic acid, S, acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, ethylene glycol , π monomethyl ether acetate vinegar, dipropylene glycol monoterpene - a special organic agent, or a mixed solvent of these. Examples of the coating method include roll coating, doctor blade coating 139313.doc-32·201001066 cloth, gravure coating, air knife coating, slit extrusion coating, bar coating, and the like. The method. Further, the removal of the solvent can be carried out, for example, by heating, and the heating temperature at this time is preferably about 70 to 15 (rc, preferably a minute of heating time.) Remaining in the photosensitive resin layer formed in the above manner. The amount of the organic solvent is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. Further, the thickness of the photosensitive resin layer is different depending on the use, and the thickness after removing the solvent is about (8) μιη. In the support and the inductive resin layer, if necessary, the surface of the photosensitive resin layer opposite to the support side may be covered with a protective film. / / is a protective film, and may be exemplified by: A polymer such as ethylene or polypropylene is used exclusively. The 'protective film is preferably a film of a fish eye. The adhesion between the pancreas and the photosensitive resin layer is easy to self-photosensitive resin layer. The protective film is peeled off, and the adhesion between the positive a ^ is better than the photosensitive resin layer and the support between the support and the photosensitive resin layer and/or between the photosensitive film and the protective film. It can also have a buffer layer, The intermediate layer or the protective layer of the layer, the light-absorbing layer I, the moisture barrier layer, etc. The photosensitive resin layered body can be directly stored in the form of a flat plate: the surface is placed on one side of the photosensitive resin layer (not added) The surface that is covered by the protective film and wound up is staggered. If you sneak up the "rolled up", and the 4 heart 'as long as it is the previous one, there is no special limit, for example, ·Polyethylene resin, polypropylene resin, polystyrene 139313.doc -33- 201001066 :=, polyvinyl chloride resin, ABS resin (tetra) nitrile-butadiene styrene = material) 4 plastic. When storing, Preferably, the support is wound in the second-order manner. The photosensitive resin is wound into a roll-shaped photosensitive resin = the end face of the body. From the viewpoint of protecting the end face, it is preferable to provide the end face = Du (4) In view of the fusion of the edges, it is preferable to provide a moisture-proof end cow. When the photosensitive resin laminate is bundled, it is preferably packaged in a black sheet having a small moisture permeability and packaged. A method of forming a photoresist pattern is described. The method for forming a pattern is to use the above photosensitive resin. Photosensitive layer of the layer: 曰 layer: laminated on the substrate in a dense manner - image-like illuminating active light portion = (four) (four) part removal. For unilluminated (four) active light m: ° ' due to the inclusion of 1,2_Qin The nitrogen-based sensitizer interacts with the alkali-soluble phenol: two to function as a dissolution inhibitor, so it is insoluble in the test. However, the towel is used to irradiate the active light, and contains the drum: diazide. The sensitizer is photodecomposed to lose the dissolution inhibition, and the exposed portion irradiated with the active light becomes the solubility test. The method of laminating the photosensitive resin layer on the substrate is to protect the broad-light resin laminate. In the case of a film, when the protective film is removed, the photosensitive resin layer is heated to the left and right sides of the core, and the pressure is about 1 to 1 MPa (1 to 1, the pressure pressure = the method on the substrate, etc.). This lamination step can also be carried out under dust reduction. The surface of the substrate on which the photosensitive resin layer is laminated is not particularly limited. The photosensitive resin layer laminated on the substrate in the above-described manner is irradiated with active light in an image pattern to form an exposed portion. 139313.doc •34- 201001066 When the support present on the photosensitive tree layer is transparent to the active light, the active light can be irradiated through the support, and the support exhibits light-shielding to the active light. In the case where the support is removed, the photosensitive tree layer is irradiated with active light. As the light source of the active light, a known light source such as a carbon arc lamp, a mercury vapor orphan lamp, a high pressure mercury lamp, a gas lamp, or the like can be used to efficiently emit ultraviolet rays, visible light, or the like. X, laser direct drawing exposure method, etc. can also be used. ☆ After the exposure portion is formed, the photosensitive resin layer of the exposed portion is removed by development to thereby form a photoresist pattern. In the case where the support portion is present on the photosensitive resin layer, the support is removed by an auto peeler or the like, and an alkaline aqueous solution is used. The exposure is removed by wet development or dry development of a developer such as a liquid helium agent. The method of developing the p, etc. Examples of the wet development test include a weak inorganic compound such as sodium carbonate, potassium carbonate or ammonia; an alkali metal compound such as sodium hydroxide or potassium hydroxide; and an alkali-alkaline calcium hydroxide. Metal compound; monomethylamine, didecylamine, trimethylmoon female 'monoethylamine, diethylamine, triethylamine, monopropylamine, dimethyl 6-amine, monoethanolamine, two Awesome organic compounds such as ethanolamine, triethanolamine, ethylenediamine, diethylene sulfonium acrylamide-methylaminoacetate, polyethyleneimine, etc.; tetramethylammonium hydroxide, tetrachloroethylene oxide Base money and so on. These may be used singly or in combination of two or more kinds in the form of an aqueous solution. The pH of the aqueous test solution is preferably in the range of (4), and the temperature is adjusted in accordance with the developability of the photosensitive resin layer. Further, a surfactant, an antifoaming agent, an organic solvent or the like may be added to the aqueous test solution. As the above 139313.doc -35· 201001066 development method, you, 丨 ‘ 7 silver, cite the · dipping method, spray method, brushing, impact and so on. Further, if necessary, heating of about 60 to 2 Torr may be performed as a process after development, whereby the photoresist pattern is cured and used. : The method of obtaining the inch resist pattern. In this case, since the photosensitive resin layer which can sufficiently prevent the generation of chips is used, contamination of the substrate or the bonding machine operating environment caused by the chips can be sufficiently prevented, and as a result, a photoresist pattern having a sufficient defect can be formed. Further, the exposed portion of the resist film is easily dissolved in the weak test and peeled off from the substrate, and a resist pattern can be obtained by using the photosensitive resin composition of the present invention which is excellent in weak developability. The above description has been made on the preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the spirit and scope of the invention. <Manufacturing Method of Printed Circuit Board> The method of manufacturing a printed circuit board according to the present invention is carried out by the following steps of forming the resist pattern using a copper box laminate or a flexible substrate as a substrate. Field: First, a conductor pattern is formed on the copper surface of the substrate which is ejected by development by a known method such as etching or plating. Thereafter, the photoresist pattern is removed by re-exposure and development to obtain a desired printed circuit board. &lt;Manufacturing Method of Lead Frame&gt; The method of manufacturing the lead frame of the present invention is a method of forming the above-described resist pattern by using a metal plate such as copper, steel, or an iron-based alloy as a substrate 1393J3.doc - 36- 201001066 After the following steps. ''Firstly, the substrate exposed by 1% is left to form a conductor pattern. - After the same method as the above-described method of manufacturing a printed circuit board, the residual photoresist pattern is removed to obtain a desired lead frame. &lt;Manufacturing method of semiconductor package&gt;

- The manufacturing method of the half moon V-body package is carried out by using the following method as a method of forming the above-described resist pattern of the LSI (the circuit in which the circuit has been formed as a substrate). The exposed opening portion is subjected to columnar plating of copper or solder to form a conductor pattern. Then, the remaining photoresist pattern is removed in the same manner as the method for manufacturing the printed wiring board, and the columnar shape is further removed by contact. A portion of the thin metal layer other than the mineral deposit is removed to thereby obtain the desired semiconductor package. <Method for producing a thin film transistor> 1/-, a method for manufacturing an electric body, for example, in dream, glass, After a gate electrode having a predetermined shape is formed on a substrate such as a resin sheet by using a mask, a gate insulating film is formed by the photoresist pattern forming method and the removal method, and further on the entire surface of the film Forming a semiconductor thin film layer on the thin film layer

A thin film transistor can be obtained by forming a source electrode and a germanium electrode of a predetermined shape using a mask. X EXAMPLES The present invention will be described in more detail by way of examples. [Beast Example 1 to 9, Comparative Example 1, Examples 10 to 23, Comparative Example 2, 3] 139313.doc -37- 201001066 &lt;1 Preparation of Photosensitive Resin Composition&gt; Table 1 and Table 2 The compound shown is mixed to prepare a photosensitive resin composition. The values in Tables 1 and 2 are the amounts of solids. The symbols in the table are as follows. A-1: cresol novolak resin, weight average molecular weight of 10,000, molecular weight distribution of about 10, m body: P body = 6: 4 (asahi organic material (stock) manufacturing 'EP4020G (trade name)) A-2: Phenolic novolak resin, weight average molecular weight of 7,000, molecular weight distribution of about 6 (as manufactured by Asahi Organic Materials, PAPS-pN70 (trade name)) B-1 : 4,4,-(1-{4-[1 -(4-Phenylphenyl)_1-mercaptoethyl]phenyl}ethylidene) double-assay 6-diazide-5,6-dihydro-5-sideoxy-1-naphthalene acid Single, second or triple S (PA_3 (Shangkou name) manufactured by Daito Chemix) Β-2 : 2,3,4,4'-tetramethylene 2 abbreviated 6-diazide-5 , 6-Dihydro-5-oxo-1-naphthalenesulfonic acid mono-, di-, tri- or tetra- vinegar (DTEP-250 (trade name) manufactured by Daito Chemix Co., Ltd.) C-1: polyparaphenylene 6 The olefin' weight average molecular weight is 20,000 (Chemiway Manufacture 'MARUKA LYNCUR Μ H-2 Ρ (trade name)) C-2: 1:1 (mole ratio) copolymer of vinyl phenol and methyl methacrylate , weight average molecular weight is l〇, 〇〇〇 (Chemiway (manufactured by the company), MARUKA LYNCUR CMM (trade name)) D-1: bisphenol A compound having 3 moles of propylene glycol at both ends of A (manufactured by Toho Chemical Co., Ltd., BISOL 6PO (trade name)) D-2 ·· p=5, q=〇, r=〇 on both sides of the above formula (1) Compound 139313.doc •38· 201001066 BA-10 GLYCOL (manufactured by Japanese emulsifier) D-3: Compound PC-9〇3 of p = 0, q=3, r=〇 on both sides of the above formula (I) (manufactured by Japanese emulsifier) D-4 : Compound UNIOL DAB-800 (manufactured by Sakamoto Oil & Fat) of p=3, q=2, Γ=〇 on both sides of the above formula (1) D-5: the above formula (I) P=l5, q=2, Γ=〇 of the compound on both sides ΒΑΡ4-30 (manufactured by emulsifier) D-6: Sample of octane diol in each of the two ends of the bisphenol hydrazine compound Ε (Manufactured by Toho Chemical Co., Ltd.) D-7: Compound F having 3 moles of propylene glycol at both ends of the bisphenol F compound (manufactured by Toho Chemical Co., Ltd.) D-8: 3 moles of propylene glycol at both ends of the bisphenol S compound Compound Sample S (manufactured by Toho Chemical Co., Ltd.) D-9. Polyoxyethylene-polyoxypropylene condensate (Adeca Pluronic L-44 (trade name) manufactured by ADEKA Co., Ltd.) &lt;2. Manufacture of photosensitive resin laminate 〉 in Table 1 The solvent methyl ketone was added to the photosensitive resin composition which is not composed of Table 2 until the solid content reached 50% by mass, and the mixture was sufficiently stirred and mixed, and the photosensitive resin composition solution was uniformly applied by a bar coater. The Μμη^thick polyethylene terephthalate film was dried in a 9 〇 dry machine for 2 minutes to form a photosensitive resin layer of 1 μm thick. Then, a thick polyethylene film is bonded to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. &lt;3·Production of Evaluation Substrate&gt; 139313.doc -39- 201001066 Substrate Whole Surface: The evaluation substrate is prepared as follows: a copper foil laminate having a thickness of 3 5 μm of rolled steel pig _4 mm thick is used. The surface was subjected to sandblasting at a spray pressure of 2020 MPa (manufactured by Japan Carlit Co., Ltd., SAKURUNDUM R (registered trademark) #220). Lamination: The polyethylene film of the photosensitive resin laminate is peeled off and laminated on the entire surface by a roll of a hot roll laminator (made by Asahi Kasei Engineering Co., Ltd., AL_7〇) wi〇5t: Heat to the (29) copper foil laminate. The air pressure system was set to 0.35 MPa, and the laminating speed was set to 丨5 m/min. Exposure: The support was peeled off. The glass mask was exposed, and the evaluation substrate was subjected to projection exposure using an exposure machine having an ultrahigh pressure mercury lamp (projection exposure apparatus _ side 4: gal., manufactured by Electric Co., Ltd.). Development: Developer, developed at 2 。. Thereafter, the temperature of the obtained evaluation substrate was subjected to a temperature of (10) by a dipping method under the conditions of a water temperature of 2.38 mass% tetramethylammonium solution for about 20 seconds, and the temperature was (10) by the dipping method. Then use a dryer to dry. &lt;4. Evaluation&gt; Chip evaluation The above-mentioned photosensitive component and its periphery were formed by using an NT cutter to the side of the support as the upper resin laminate in a straight line. The results of the cross-checking test were divided into 139313.doc •40- 201001066 by visual inspection of the cutting section at 4 °. A: No chip is generated B: Swarf is generated. Evaluation of sensitivity: In the range of mJ/cm2, the spleen T elbow is subjected to the above-mentioned "exposure" process, and the gentleman specializes in you, 鄄, 鄄. If this is enough, the best feeling is formed."

The exposure amount from the above-mentioned pattern in the step of 200 mJ/cm2 to 1 〇〇2 is referred to as "the evaluation of the minimum development time: ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Into the η 里 Α Α Α Α Α Α Α Α Α Α Α Α 。 。 Α Α 。 。 。 。 。 。 。 。 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王 王Evaluation of the sensation: The exposure is carried out by a chrome glass reticle having a pattern of a gap of 1 · 〗 _ _ _ _ , 、 、 糸 1 1 , , 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41 · 2 times the time

At the time of development, it was visually observed whether the line portion and the gap portion were clearly separated, and classification was performed in the following manner. A: The line portion is clearly separated from the gap portion B: the line portion is not separated from the gap portion &lt;5. Evaluation Results&gt; The evaluation results of the examples and comparative examples are shown in the table! And Table 2. As is clear from Table 1, in the Example 9, the cut evaluation, the sensitivity, and the minimum development a pattern formation property were all excellent, but in Comparative Example 1, the (C) side chain was derived from the fragrance because it did not contain the present hair. The base of the group hydroxy compound i393l3.doc -41 . 201001066 The alkali-soluble resin produced chips and the photosensitive resin layer was very brittle, and other evaluations could not be performed. As is clear from Table 2, in the photosensitive resin compositions of Examples 1 to 22, 3, the generation of chips was sufficiently suppressed, and the balance of sensitivity, development time, and pattern formation property was excellent. In contrast, Comparative Examples 2 and 3 were obtained. Photosensitive resin. Since the material does not contain the component (D), chips are generated, and since the development cannot be performed, the pattern cannot be formed. 139313.doc -42- 201001066 [i] Comparative Example 1 00 «Embodiment 9 tn m 〇ιη &lt; Ν 800 Example 8 ο ΙΛ Ο \η 800 Example 7 ο Ο its 1000 Ο Example 6 〇ο 800 in &lt;Embodiment 5 in η ο yti ro 600 IT) &lt;s &lt; Embodiment 4 ΙΛ ο tn &lt; 1200 &lt; Embodiment 3 ο ο in &lt; 800 tn &lt; Example 2 in % &lt; 800 o &lt;Example 1 ο &lt; 800 jri &lt; 800 Ari &lt; Al A-2 Β-1 Β-2 C-1 C-2 D1 (Grade) B (Grade) Photosensitive resin composition (parts by mass) Chip evaluation exposure amount ( Sensitivity) Minimum development time pattern formation 筚敖#教丧#-·driving«I* 139313.doc -43- 201001066 [&lt;Νΐ comparison example 3 〇* comparison i example 2 _1 ca 〇英η &lt; 〇 00 ο PQ ITJ m % &lt;〇&lt; in &lt; 1200 &lt; ¥ ^ &lt; 〇00 &lt; 鸯Ξ! 驷军〇ο &lt; 〇§ &lt; 驷¥ S &lt; 〇g ΡΟ &lt;&lt; 〇90 &lt;Marriage; £ s % &lt; 〇 00 V) &lt; 驷 5 s &lt; 〇 00 IT) P〇 &lt; 鸯 2 V 5 % &lt; 〇g V) ro &lt; 鸯 2 驷 5 % &lt;ο茭沄&; 苳 苳 00 & & & & & & & 驷 驷 驷 驷 驷 驷 驷 驷 驷 驷 驷 驷 驷 f f f f S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S 〇a ά »Ti Ο Ο 卜 Q 00 〇〇 ά ά (grade) ϊ (grade) Photosensitive resin composition (parts by mass) Cutting evaluation exposure amount (sensitivity) Minimum development time pattern formation -44- 139313.doc 201001066 [Industrial Applicability] The present invention can be used for the manufacture of printed circuit boards, the manufacture of lead frames for ic chip mounting, the precision processing of metal foils such as metal mask manufacturing, and the manufacture of packages such as BGA and CSP, COF. (Chip On Film) or TAB (Tape Automated Bonding) manufacturing of strip substrates, fabrication of semiconductor bumps, isolation of flat displays such as ITO electrodes or address electrodes, electromagnetic wave masks Wall manufacturing, and profit A method of processing a substrate by sand blasting. As a blasting method, the glass is processed by an organic EL (Electroluminescence), a hole processing of a stone wafer, and a ceramic processing. Further, the processing by the blasting step of the present invention can be utilized for the production of electrodes of a ferroelectric film and a metal material layer selected from the group consisting of precious metals, precious metal alloys, high-point metals, and highly soluble metal compounds.

139313.doc -45 -

Claims (1)

201001066 VII. Patent Application Range 1. A photosensitive resin composition containing (8) an alkali-soluble phenol resin, (B) a sensitizer containing 1,2-naphthoquinonediazide, and (c) The base chain has an alkali-soluble resin derived from a group derived from an aromatic hydroxy compound. The photosensitive resin composition of claim 1, wherein the component (c) is a test resin containing a basic ethylene as a copolymerization component. 3. The photosensitive resin composition of claim 1, wherein the amount of the above-mentioned (A) component and 1 to 75 mass% of the above-mentioned (B) is contained in an amount of 20 to 9% by mass based on the total amount of the photosensitive resin composition. The component and the component (C) of the above-mentioned mass%. &quot;The photosensitive resin composition of the item 1 of the present invention further contains (D) a plasticizer. 5. The photosensitive resin composition according to claim 1, which comprises a compound of the formula (I), a 2-naphthoquinonediazidesulfonate as the component (B): ] 139313.doc 201001066 The base or the radical 'R7 and Rs are each independently hydrogen, halogen or C1~C4 alkyl, and R9~R&quot; are independently hydrogen or C1~C4 alkyl 6_ as in claim 4 The photosensitive resin composition, wherein the (〇) component is at least one compound selected from the group consisting of bisphenol A, bisphenol E, bisphenol F, bisphenol s, and a compound obtained by hydrogenating the same A compound derived and having at least one hydroxyl group at the end. A photosensitive resin laminate comprising at least a support and a photosensitive resin layer formed of the photosensitive resin composition according to any one of claims 1 to 6. • π Μ δ δ Month A photoresist roll that is made into a roll. A method for forming a photoresist pattern, comprising: a step of laminating a photosensitive resin layer of the photosensitive resin laminate according to claim 7 on a substrate; and an exposure step of exposing the photosensitive resin layer ' and a developing step of removing the photosensitive photosensitive resin layer. A method of forming a photoresist pattern of claim 9, wherein direct drawing is performed in the exposure step to expose. A method of manufacturing a printed circuit board, which further comprises the step of forming a bond by a method such as 9 or 1 . The substrate of the pattern is engraved or I2. A method for manufacturing a lead frame, the method of which is 10, +, and, and includes a photoresist pattern formed by the method of claim 9 or 1 . The substrate is ordered to be closed. • The method of manufacturing a variety of conductor patterns, and 忐 amp &; 求 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 The steps to apply. A method of producing a thin film transistor, comprising the step of etching or plating a substrate on which a photoresist pattern is formed by the method of claim 9 or 1. 15. A photosensitive m compound comprising (A) a solution (4) resin, (B) a sensitizer containing a 1,2-naphthalene diazide group, and (9) selected from the group consisting of E, a double brew F and a double _, and a compound derived from at least one of the compounds consisting of the compounds obtained by the hydrogenation and having at least one hydroxyl group at the terminal. 16. The photosensitive resin composition of claim 15, wherein the upper (10) component is at least one selected from the group consisting of a compound represented by the following formula (νπ) and a compound obtained by chlorinating the compound. a compound: [Chemical 2] In the formula, Υ丨 is an ethyl group, γ2 Α2 is a propyl group, Y3 is an alkyl group having a carbon number of 4 to 6, and Y4&amp;Y5 is independently an iron 4 atom or a methyl group 'p, q, and r are整数 The above integers, the total of which is 1~2 π ., ^ ',, σ, the right and/or left of the oxidized ethyl, oxidized propyl, and the inverse of the stone 4~6 The repeating unit of the radical can be added randomly, and π &amp; 1 , yoke can be added as a block}. 17. The photosensitive resin according to claim 15, which is contained in an amount of from 20 to 90% by mass of the above component (A) and from 1 to 75 mass. / * 0 of the above component (B), and contains 1 to 75% by mass of the above (D) component. 139313.doc 201001066 18. The photosensitive resin composition of claim 15, which contains the quinonediazide sulfonate of the compound represented by the following general formula (1) as the above (B) component: [Chem. 3] {where R! R6 knife is independently chlorine, dentate, C1~C4 alkyl, dilute or hydroxyl R7 and Rs are each independently hydrogen, dentate or c 1~C4 alkyl, and R9~R&quot; Separately, it is an alkyl group of 氲 or C1 to C4. 19. 20. 21. 22. A photosensitive resin laminate comprising at least a support and sensitization by any one of claims 15 to 18. A photosensitive resin layer formed of a resin composition. A resist roll which is formed into a roll shape as in the photosensitive resin laminate of claim 18 or 19. a method for forming a photoresist pattern, comprising: a step of laminating a photosensitive resin layer of a photosensitive resin laminate according to claim 1 on a substrate; an exposure step of exposing the photosensitive resin layer; A development step of removing the photosensitive resin layer of light. The method of forming the photoresist pattern of claim 21, wherein direct exposure is performed in the exposure step 139313.doc 201001066. A method of manufacturing a printed circuit board, which further comprises the step of stamping or applying a substrate on which a photoresist pattern is formed by the method of claim 21 or 22. 24. A method of manufacturing a lead frame, comprising: a step of making a residual of a substrate having a photoresist pattern formed by the method of claim (4) 22. 25. A method of semiconductor patterning, k, comprising the step of etching or plating a substrate of a resist pattern of a shape of a light or a photoresist according to the method of claim 21 or 22. And a method of thin film transistor, method 21 or 22, and method comprising: pairing by the steps as claimed. Substrate with photoresist pattern feed or money 139313.doc 201001066 IV. Designated representative map: (1) The representative representative of the case is: (none) If there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: Rg--Ri〇 139313.doc