TWI398725B - A photosensitive resin composition and a photosensitive resin laminate using the same - Google Patents

Description

Photosensitive resin composition and photosensitive resin laminate using the same

The present invention relates to a photosensitive resin composition which can be developed by using an aqueous alkaline solution, and a photosensitive resin laminate using the same, and the use of the above-mentioned photosensitive resin composition for the production of a printed circuit board, IC chip Manufacturing of lead frames (hereinafter referred to as lead frames), precision machining of metal foils such as metal mask manufacturing, thin film transistors such as liquid crystal display elements, BGA (Ball Grid Array), and CSP (Chip Size Package) Fabrication of semiconductor packages such as wafer size packages, fabrication of ITO (Indium Tin Oxide) electrodes, address electrodes, or electromagnetic wave masks in the field of flat panel displays, and suitable for use in sandblasting The manufacture of a photoresist pattern for a protective cover member during processing.

As an image forming method used for patterning of a semiconductor integrated circuit, a liquid crystal display element, a printed circuit board, etc., it is known that a photosensitive resin containing a novolac type phenol resin and a 1,2-naphthoquinonediazide compound is used. A method of using a resin composition as a positive resist of a raw material. In the case where a positive photoresist is formed by applying the photosensitive resin composition, the coating thickness thereof is generally 0.5 to several μm. If the positive photoresist is used, image pattern formation in a wide size range can be achieved. The size range is, for example, from a sub-half micron range of about 0.3 μm to a considerable size range of about several tens to several hundreds of μm. Thereby, it is possible to perform microfabrication on a wide variety of substrate surfaces.

In the field of LCD (Liquid Crystal Display), etc., with the progress of technologies such as TFT (Thin Flim Transistor), STN (Super Twisted Nematic), and the like. As the line width becomes thinner, the tendency to be finer is enhanced. For example, in the previous components using TN (Twisted Nematic) and STN liquid crystals, an image design size of about 200 μm to several hundreds μm was used. In contrast, recently, the image was developed due to the development of new technologies. The minimum design size is less than 100 μm. Further, in a TFT display element having good responsiveness or image formation, the image design size is increased to a level of several μm.

As a characteristic expected as a photoresist material, the above-mentioned fine processing ability can be maintained, and the area can be increased. In other words, a liquid crystal display that has been increasing in size in recent years, and a PDP (Plasma Display Panel) that has been initially designed for large screens. For these substrates, it is an important technique to make the film thickness uniformity in the surface more excellent. Further, as a common problem of a large-area display, it is possible to further reduce the cost and the liquefaction of the photoresist used in the production.

In order to further improve the uniformity of the film thickness in the surface of the photoresist and to achieve the liquefaction of the photoresist material, the company has continuously studied 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 technologies can handle substrates up to 550 mm x 680 mm. However, in the case of larger substrates, it is expected that the application of such technologies will be difficult.

Further, in the field of printed circuit boards, so-called negative dry film photoresists are widely used at present. The negative-type dry film resist is a negative-type photosensitive resin composition having a thickness of usually 10 to 100 μm, which is coated with a polyester film having a thickness of 15 to 25 μm as a support. A polyolefin film having a thickness of 4 to 40 μm is laminated 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, in the case of use in the field of printed circuit boards, the resolution required for negative dry film photoresist is at most about 30 to 300 μm.

Hereinafter, the production of a printed circuit board using a negative dry film photoresist will be briefly described. First, when a protective film is present in the negative dry film resist, the protective film is removed, and the negative photosensitive resin composition is laminated in contact with the substrate used for the printed circuit board. The support is exposed to active light to cure the photosensitive resin composition. Next, the unexposed photosensitive resin composition is usually dispersed and removed using a weak alkali aqueous solution represented by a sodium carbonate aqueous solution having a concentration of 1% by mass. Thereafter, the copper on the substrate is etched using an aqueous solution of copper chloride. Then, the cured photosensitive resin composition was completely peeled off by using a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution having a concentration of 2 to 3%.

However, the image processing technique required for manufacturing a TFT for LCD is as described above, and the resolution is, for example, about 2 to 10 μm, which is significantly higher than that in the field of printed circuit boards. In addition to this, the following techniques are required: no metal ion development, peeling using an organic stripping solution, etching of a metal thin film such as ITO or Ta, Al, or an inorganic thin film such as SiNx or ITO. In order to cope with these technologies, the photoresist has the following requirements: the film thickness is several μm, the adhesion of the metal film or the inorganic film after various sputtering is improved, and the film thickness uniformity is further improved, and the film thickness is about 1 μm. The follow-up property of the conventional pattern of the TFT of the unevenness is increased, and the lamination speed of the substrate of 1 to 2 m width is completely exceeded, and thus the limit of the conventional dry film photoresist is completely exceeded. 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.

As a material of the positive-type resist of the prior art, for example, Patent Documents 1 and 2 disclose a phenol novolak resin as a main component and 1,2-naphthoquinonediazidesulfonate as a photosensitive component. However, when it is directly applied to the dry film photoresist, it is not applied to the support thickly due to poor coatability, and 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. Further, Patent Document 3 discloses that a compound obtained by reacting a drying oil with a phenol resin is introduced in order to soften the film. However, the positive dry film photoresists currently using such materials have 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, a wide roll is usually formed by applying a positive photosensitive resin composition to a support or the like. The roll is then cut by slits to have the desired film width. Further, in order to laminate the photosensitive resin composition on the substrate on which the image pattern is formed, a dry film photoresist is usually taken out from the rolled product, and thermal transfer is performed while being pressed against the substrate by a bonding machine. The dry film photoresist is cut into a prescribed length in the longitudinal direction of the substrate during or after the lamination.

When a dry film resist having a film-type positive photosensitive resin composition is used, there is a problem in that chips of the positive photosensitive resin composition (hereinafter referred to as chips) are generated at the time of the above cutting. . Further, even if the dry film photoresist is cut into a predetermined length in the longitudinal direction of the substrate at the time of lamination, it is easy to generate chips from the cut surface. These chips become dust and contaminate the operating environment of the substrate or laminator, and adhere to the support layer deposited on the substrate. As a result, the image pattern is prone to defects.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 06-027657

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-105466

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-316577

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin which can form a pattern and is formed into a dry film, and which is relatively soft, and which can sufficiently suppress the generation of chips even if the film is cut. A composition and a photosensitive resin laminate using the same.

In order to solve the above problems, the present inventors have found that the above problems can be solved by using a photosensitive resin composition having the following constitution, and the present invention has been completed.

The present invention is as follows.

[1] A photosensitive resin composition comprising (A) an alkali-soluble phenol resin, (B) a sensitizer containing a 1,2-naphthoquinonediazide group, and (C) a side chain having an aromatic origin An alkali-soluble resin based on a group of hydroxy compounds.

[2] The photosensitive resin composition according to the above [1], wherein the component (C) is an alkali-soluble resin containing hydroxystyrene as a copolymerization component.

[3] The photosensitive resin composition according to the above [1] or [2], which contains 20 to 90% by mass of the above-mentioned (A) component, 1 to 75, based on the total amount of the photosensitive resin composition. The component (B) of the above-mentioned mass (%) contains 1 to 75% by mass of the above component (C).

[4] The photosensitive resin composition according to any one of the above [1] to [3] further comprising (D) a plasticizer.

[5] The photosensitive resin composition according to any one of the above [1] to [4], which contains 1,2-naphthoquinonediazidesulfonic acid of the compound represented by the following formula (I) Ester as the above component (B): Wherein R ₁ to R ₆ are each independently hydrogen, halogen, C1 to C4 alkyl, alkenyl or hydroxy, and R ₇ and R ₈ are each independently hydrogen, halogen or C1 to C4 alkyl, and R ₉ ~R _{11 is} independently hydrogen or a C1 to C4 alkyl}.

[6] The photosensitive resin composition according to any one of the above [1], wherein the component (D) is selected from the group consisting of bisphenol A, bisphenol E, bisphenol F, and bisphenol S. And a compound derived from at least one compound of the group consisting of the compounds obtained by the hydrogenation, and having at least one hydroxyl group at the terminal.

[7] A photosensitive resin layered body comprising at least a support and a photosensitive resin layer formed of the photosensitive resin composition according to any one of the above [1] to [6].

[8] A photosensitive reel according to the above [7], which is formed into a roll shape.

[9] A method of forming a photoresist pattern, comprising the step of laminating a photosensitive resin layer of the photosensitive resin laminate according to the above [8] on a substrate, and exposing the photosensitive resin layer The exposure step and the development step of removing the photosensitive photosensitive resin layer.

[10] The method for forming a photoresist pattern according to [9] above, wherein the direct exposure is performed by exposure in the exposure step.

[11] A method of producing a printed circuit board, further comprising the step of etching or plating a substrate on which a photoresist pattern is formed by the method according to [9] or [10] above.

[12] A method of manufacturing a lead frame, comprising the step of etching a substrate on which a photoresist pattern is formed by the method according to [9] or [10] above.

[13] A method of producing a semiconductor pattern, which further comprises the step of etching or plating a substrate on which a photoresist pattern is formed by the method according to [9] or [10] above.

[14] 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 according to [9] or [10] above.

[15] A photosensitive resin composition comprising (A) an alkali-soluble phenol resin, (B) a sensitizer containing 1,2-naphthoquinonediazide, and (D) selected from bisphenol A, A compound obtained by at least one compound selected from the group consisting of bisphenol E, bisphenol F, and bisphenol S, and a compound obtained by the hydrogenation, and having at least one hydroxyl group at the terminal.

[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 (VII) and a compound obtained by hydrogenating the same. At least one compound: In the formula, Y ₁ is an ethylidene group, Y ₂ is a stretching propyl group, Y ₃ is an alkylene group having a carbon number of 4 to 6, and Y ₄ and Y ₅ are each independently a hydrogen atom or a methyl group, p, q and r. An integer of 0 or more, which is a total of 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 on the right side and/or the left side of the structure may be randomly Add, or add as a block}.

[17] The photosensitive resin composition according to the above [15] or [16], which contains 20 to 90% by mass of the component (A) and 1 to 75% by mass of the component (B), and contains 1 ~75% by mass of the above component (D).

[18] The photosensitive resin composition according to any one of the above [15], which contains the quinonediazidesulfonate of the compound represented by the following formula (I) as the above (B) )ingredient: Wherein R ₁ to R ₆ are each independently hydrogen, halogen, C1 to C4 alkyl, alkenyl or hydroxy, and R ₇ and R ₈ are each independently hydrogen, halogen or C1 to C4 alkyl, and R ₉ ~R _{11 is} independently hydrogen or a C1 to C4 alkyl}.

[19] A photosensitive resin layered body comprising at least a support, and a photosensitive resin layer formed of the photosensitive resin composition according to any one of the above [15] to [18].

[20] A resist roll according to the above [19], wherein the photosensitive resin laminate is formed into a roll.

[21] A method of forming a photoresist pattern, comprising: a step of laminating a photosensitive resin layer of the photosensitive resin laminate according to the above [19] on a substrate, and exposing the photosensitive resin layer The exposure step and the development 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 by exposure in the exposure step.

[23] A method of producing a printed circuit board, comprising the step of etching or plating a substrate on which a photoresist pattern is formed by the method according to [21] or [22] above.

[24] A method of manufacturing a lead frame, comprising: a step of etching a substrate on which a photoresist pattern is formed by the method according to [21] or [22] above.

[25] A method of producing a semiconductor pattern, comprising the step of etching or plating a substrate on which a photoresist pattern is formed by the method according to [21] or [22] above.

[26] 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 according to [21] or [22] above.

According to the present invention, it is possible to provide a photosensitive resin composition which is capable of forming a pattern and forming a photosensitive resin composition when it is formed by a dry film, and which can sufficiently suppress the generation of chips even if the film is cut.

Hereinafter, the present invention will be described in detail.

(A) alkali-soluble phenolic resin

(A) The alkali-soluble phenol resin is obtained, for example, by using a phenol compound, an aldehyde and/or a ketone as a raw material, and a polycondensation reaction.

Examples of the phenol compound include phenol, cresol, and xylenol; alkylphenols such as ethylphenol, butylphenol, and trimethylphenol; methoxyphenol and 2-methoxy-4- An alkoxyphenol such as methylphenol; an alkenylphenol such as a vinyl phenol or an allylphenol; an arylphenol such as a phenylphenol; an aralkylphenol such as a benzylphenol; or a methoxycarbonylphenol; Alkoxycarbonylphenol; arylcarbonylphenol such as benzyl methoxy phenol; halogenated phenol such as chlorophenol; polyhydroxybenzene such as catechol or resorcin; bisphenol A, bisphenol F, etc. Bisphenol; and naphthol compounds such as α- or β-naphthol; hydroxyalkyl groups such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol a phenolic compound containing a hydroxy group such as hydroxyethyl cresol; a monoethylene oxide adduct of bisphenol; a monopropylene oxide adduct of bisphenol; Phenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutyric acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxybenzene a phenol compound containing a carboxyl group such as oxybenzoic acid or bisphenolic acid.

These phenol compounds may be used alone or in combination of two or more.

Examples of the aldehyde and/or ketone include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, and chloroacetate. Aldehyde, chlorophenylacetaldehyde, acetone and glyceraldehyde. Further, examples of the aldehyde and/or ketone include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formazanic acid, methyl formazanacetate, and 2- Methionine, methyl 2-methylpropionate, pyruvic acid, acetopropionic acid, 4-acetamidine butyric acid, acetone dicarboxylic acid, and 3,3',4,4'-benzophenone tetracarboxylic acid . Also, you can use paraformaldehyde, three A formaldehyde precursor such as an alkane. 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 acidic catalyst, the novolac type phenol resin can be easily obtained, and the generation of chips can be more effectively prevented. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. The acid catalyst may be used singly or in combination of two or more. Further, the synthesis conditions of the alkali-soluble phenol resin may be well-known conditions.

The content of the aldehyde and/or ketone in the raw material for obtaining the alkali-soluble phenol resin is preferably from 0.7 to 1 mol per mol of the 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 phenol used in the polycondensation is preferably less than 0.5 with respect to the molar of the phenol compound.

The polystyrene-equivalent weight average molecular weight obtained by the gel permeation chromatography of the (A) alkali-soluble phenol resin is preferably from 300 to 100,000 from the viewpoint of improving the coating property and suppressing the deterioration of developability. More preferably, it is 1,000 to 20,000. The weight average molecular weight is preferably 300 or more from the viewpoint of film coating properties. Further, from the viewpoint of developability, it is preferably 100,000 or less.

Further, when the weight average molecular weight of the above phenol resin is small, the chain extender may be used to polymerize the phenol resin to increase the molecular weight to achieve the above weight average molecular weight. Examples of the chain extender include a diepoxide compound or a second capable of reacting with a carboxyl group. An oxazoline compound and a diisocyanate compound capable of reacting with a hydroxyl group.

(A) The alkali-soluble phenol resin may be used alone or in combination of two or more. The alkali-soluble phenol resin in the case of using two or more types of the alkali-soluble phenol resin, for example, two or more kinds of alkali-soluble phenol resins obtained from monomers having 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 alkali-soluble phenol resin in the photosensitive resin composition is preferably from 20 to 90% by mass, more preferably from 25 to 85% by mass, based on the total amount of the photosensitive resin composition. Good is 30~80% by mass. The blending ratio is preferably 20% by mass or more from the viewpoint of improving the pattern formation property, and is preferably 90% by mass or less from the viewpoint of preventing the photoresist film from being brittle.

(B) sensitizer containing 1,2-naphthoquinonediazide

(B) A sensitizer containing 1,2-naphthoquinonediazide is a 1,2-naphthoquinonediazide compound having a sulfo group and/or a sulfonyl chloride group and an organic compound having a hydroxyl group or an amine group ( Hereinafter, the compound obtained by the reaction of "organic compound" is referred to as "organic compound". At this time, the hydroxyl group or the amine group of the organic compound is bonded to the sulfo group or the sulfonyl chloride group of the 1,2-quinonediazide compound. Further, the bond may be at least one in the molecule of the obtained 1,2-quinonediazide compound.

Examples of the above-mentioned 1,2-quinonediazide compound having a sulfo group and/or a sulfonium chloride group include 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2- Naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 1,2-naphthoquinone-2-diazide-5-sulfonate Chlorine. Among the above 1,2-quinonediazide compounds having a sulfo group and/or a sulfonium chloride group, preferred is 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2. -naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 1,2-naphthoquinone-2-diazepine-5- One or more compounds selected from the group consisting of sulfonium chloride. These 1,2-quinonediazide compounds having a sulfo group and/or a sulfonium chloride group are sufficiently dissolved in a solvent, so that the reaction efficiency with an organic compound can be improved.

Examples of the organic compound include polyhydroxybenzophenones, bis[(poly)hydroxyphenyl]alkanes, tris(hydroxyphenyl)methanes or methyl substituents thereof, and bis(cyclohexylhydroxyl) groups. Phenyl)(hydroxyphenyl)methane or its methyl substituent, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol, o-benzene Trisphenol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, 4,4'-diaminobenzophenone, phenolic, neighbor a homopolymer of benzenetriol-acetone resin, hydroxystyrene or a copolymer with a monomer copolymerizable therewith. These may be used alone or in combination of two or more.

Examples of the polyhydroxybenzophenones include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, and 2,4,6-trihydroxyl. Benzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxydiphenyl Methyl ketone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4' - pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, and 2 , 3,3',4,4',5'-hexahydroxybenzophenone. These may be used alone or in combination of two or more.

Examples of the bis[(poly)hydroxyphenyl]alkane include bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, and 2-(4). -hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-( 2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxybenzene) 2-propyl]phenyl]ethylidene}bisphenol, and 3,3'-dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)- 2-propyl]phenyl]ethylidene}bisphenol. These may be used alone or in combination of two or more.

Examples of the tris(hydroxyphenyl)methane or a methyl substituent thereof include tris(4-hydroxyphenyl)methane and bis(4-hydroxy-3,5-dimethylphenyl)-4-. Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxybenzene Methane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxy Phenylmethane, 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-hydroxyphenylmethane and a double (3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4- Hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl- 4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxyl) 3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4 -hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxybenzene 2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-2-hydroxy-4-) Methylphenyl)-4-hydroxyphenylmethane. These may be used alone or in combination of two or more.

Among these, as the above organic compound, polyhydroxybenzophenones, bis[(poly)hydroxyphenyl]alkanes, tris(hydroxyphenyl)methanes, and/or bis(cyclohexyl) are preferred. Hydroxyphenyl) (hydroxyphenyl) methane. Further, the organic compound is more preferably at least one compound selected from the group consisting of compounds represented by the following general formulae (I), (II) and (III). In this case, since the difference in solubility with respect to the developer before the irradiation of the photosensitive resin composition with light is increased, there is an advantage that the image contrast is further excellent.

Among them, from the viewpoint of sensitivity, a compound represented by the following formula (I), a compound represented by the following formula (II), and a compound represented by the following formula (III) are more preferable. At least one compound of the group consisting of: Wherein R ₁ to R ₆ are each independently hydrogen, halogen, C1 to C4 alkyl, alkenyl or hydroxy, and R ₇ and R ₈ are each independently hydrogen, halogen or C1 to C4 alkyl, and R ₉ ~R _{11 is} independently hydrogen or C1 to C4 alkyl}; Wherein R ₁₂ to R ₁₅ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms; Wherein R ₁₆ to R ₁₉ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms; X is a single bond, an oxygen atom or a phenyl group}.

The organic compound is at least one compound 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). In the case, the 1,2-quinonediazide compound having a sulfo group and/or a sulfonium chloride group is preferably 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2- Naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and/or 1,2-naphthoquinone-2-diazide-5 - sulfonium chloride. The 1,2-quinonediazide compound having a sulfo group and/or a sulfonyl chloride group, and a compound selected from the above formula (I), a compound represented by the above formula (II), and Since at least one of the compounds consisting of the compound represented by the above formula (III) has good compatibility, the amount of aggregate generated when the component (A) and the component (B) 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.

Further, at least one compound 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) It is preferably at least one compound selected from the group consisting of compounds represented by the following chemical formulas (IV) to (VI):

[化8] In this case, there is an advantage that the light sensitivity is more excellent. Among them, a compound represented by the following formula (IV) is particularly preferable.

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-sulfonyl chloride are added to the second A method of reacting in a solvent such as alkane or THF in the presence of a base catalyst such as triethylamine, triethanolamine, an alkali metal carbonate or an alkali metal hydrogencarbonate. In this case, at least one 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) is synthesized. A sensitizer containing 1,2-naphthoquinonediazide group obtained by condensing a hydroxyl group of a compound with a sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride. Further, in the obtained molecule of the sensitizer containing 1,2-naphthoquinonediazide group, selected from the group consisting of compounds represented by the general formulae (I), (II) and (III) The bond of the hydroxyl group of at least one compound to the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride may be at least one.

Further, as 1,2-naphthoquinone-2-diazide-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonium chloride, or 1,2-naphthoquinone-2 - Diazide-5-sulfonyl chloride is preferred. These may be used alone or in combination of two or more.

The blending ratio of the component (B) in the photosensitive resin composition is preferably from 1 to 75% by mass, and more preferably from 5 to 50% by mass, based on the total amount of the photosensitive resin composition. Especially good is 5 to 40% by mass. Further preferably, it is 10 to 30% by mass. The blending ratio is preferably 1% by mass or more from the viewpoint of improving the light sensitivity, and is preferably 75% by mass or less from the viewpoint of preventing the photoresist film from being brittle.

(C) an alkali-soluble resin having a group derived from an aromatic hydroxy compound in a side chain

Examples of the alkali-soluble resin having a group derived from an aromatic hydroxy compound in the side chain of (C) include (i) a polyhydroxystyrene resin, and (ii) a phenol group-containing poly(meth)acrylate. Resin, (iii) a phenol-based polypropylene amide resin, and the like.

As a method for producing a polyhydroxystyrene-based resin, the following methods and the like are known as methods used in the industry: dehydration by ethoxylated phenylmethylmethanol, decarboxylation of hydroxycinnamic acid, and The vinyl phenol monomer obtained by various methods such as dehydrogenation of phenol is mono-polymerized in the presence of a cation or a radical initiator or copolymerized with other comonomers. 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 protective group is removed to obtain a polymer. In this method, a monodisperse polymer obtained by a so-called living polymerization can be produced by selecting the type of the protecting group and the type of the initiator (Japanese Patent Laid-Open No. Hei-3-277608). Further, a method of hydrolyzing the vinyl phenol-based polymer to obtain a modified body having excellent light transmittance is known (Japanese Patent Laid-Open Publication No. Hei 1-103604), or a vinyl phenol-based polymer is used. A method for producing various ethers and ester derivatives by the reaction of a hydroxyl group (Japanese Patent Laid-Open Publication No. SHO63-312307, Fiber Polymer Materials Research Institute, Vol. 128, p. 65 (1981)), and vinyl phenol polymerization A manufacturing method of various nuclear substitutes of the materials (Japanese Patent Laid-Open Publication No. SHO-51-83691).

Examples of the (i) polyhydroxystyrene resin include polyhydroxystyrene, modified polyhydroxystyrene, hydrogenated polyhydroxystyrene, hydroxystyrene and styrene, (meth) acrylate, and cis-butene. A copolymer such as a diester or the like. The polyhydroxystyrene has a weight average molecular weight of 1,000 to 1,000, 00, preferably 5,000 to 50,000.

The modified polyhydroxystyrene may, for example, be a benzenesulfonium chloride derivative, a naphthalenesulfonium chloride derivative, a benzamidine chlorine derivative or a naphthoquinone chloride derivative in the presence of a basic catalyst. Such as the reaction with polyhydroxystyrene and so on.

Specific examples of the sulfonium chloride derivative or the formazan chlorine derivative include p-acetamide benzene sulfonium chloride, benzene sulfonium chloride, p-chlorobenzene sulfonium chloride, and naphthyl benzene sulfonium chloride. P-acetamidobenzene carbonyl chloride, benzamidine chloride, p-chlorobenzoguanidine chloride, naphthyl benzamidine chloride, and the like. In this case, the above-mentioned sulfonium chloride derivative or the above-described formazan chloride derivative is usually used in an amount of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 100 parts by weight of the polyhydroxystyrene. . The modified polyhydroxystyrene has a weight average molecular weight of 3,000 to 50,000, preferably 5,000 to 30,000.

The hydrogenated polyhydroxystyrene is a hydrogenated polyhydroxystyrene and a part of a benzene ring of a modified polyhydroxystyrene modified by a substituent to a part of the benzene ring. The weight average molecular weight of the hydrogenated polyhydroxystyrene is usually selected from the range of 3,000 to 30,000, preferably 5,000 to 25,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of mechanical properties or dry etching resistance, and is preferably 30,000 or less from the viewpoint of compatibility.

The ratio of the hydroxystyrene in the case of copolymerization with other components is preferably 30% by mass or more and 100% by mass or less from the viewpoint of obtaining sufficient alkali developability at the time of exposure. Further, the ratio of the hydroxystyrene is preferably 40% by mass or more and 100% by mass or less.

Examples of the (ii) poly(meth)acrylate resin containing a phenol group include a phenol group such as 4-hydroxyphenyl methacrylate or 2-(4-hydroxyphenyl)ethyl methacrylate. Polymers, copolymers and modified bodies of the poly(meth)acrylic monomers. The phenol group-containing poly(meth) acrylate resin has a weight average molecular weight of 5,000 to 1,000,000, preferably 10,000 to 200,000.

In addition, (iii) a phenol group-containing polypropylene guanamine resin, a polymer of a phenol group-containing acrylamide monomer such as 3,5-dimethyl-4-hydroxybenzyl acrylamide or the like, Copolymer and its modified body. The phenol group-containing polypropylene guanamine resin has a weight average molecular weight of 1,000 to 1,000,000, preferably 5,000 to 100,000.

The amount of the alkali-soluble resin having a group derived from the aromatic hydroxy compound in the side chain (C) is preferably from 1 to 75% by mass based on 100% by mass of the photosensitive resin composition. Further preferably, it is 5 to 50% by mass. The blending ratio is preferably 1% by mass or more from the viewpoint of preventing the photoresist film from being brittle, and is preferably 75% by mass or less from the viewpoint of solubility of the entire system.

(D) plasticizer

From the viewpoint of reducing chipping, it is preferred that the photosensitive resin composition contains (D) a plasticizer.

The plasticizer (D) may be a compatible low molecular weight component, and examples thereof include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, and polyoxygen. a diol-ester of propylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, etc.; diethyl phthalate Phthalates such as o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl citrate, tri-n-propyl citrate, Acetyl tri-n-butyl citrate and the like.

The (D) plasticizer contained in the photosensitive resin composition is preferably selected from the viewpoint of reducing chips at the time of film formation while maintaining excellent pattern formability. A compound having at least one hydroxyl group derived from a group consisting of bisphenol A, bisphenol E, bisphenol F, and bisphenol S, and a compound obtained by the hydrogenation, and having at least one hydroxyl group at the terminal.

As such a compound, bisphenol A (2,2-bis(4'-hydroxyphenyl)propane) or bisphenol E (1,1-bis(4-hydroxyphenyl)ethane) or a hydroxyl group at both ends of bisphenol F (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 methyl 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, and an oxybutylene group. 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 introduced molecular chain 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 obtained by hydrogenating it is preferred.

Further, the component (D) is more preferably at least one compound selected from the group consisting of a compound represented by the following formula (VII) and a compound obtained by hydrogenating the compound: In the formula, Y ₁ is an ethylidene group, Y ₂ is a stretching propyl group, Y ₃ is an alkylene group having a carbon number of 4 to 6, and Y ₄ and Y ₅ are each independently a hydrogen atom or a methyl group, p, q and r. An integer of 0 or more, which is a total of 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 on the right side and/or the left side of the structure may be randomly Add, or add as a block}.

In the above formula (VII), the total of p, q, and r on the right side and/or the left side is 1 to 20, and in the case where chips are less likely to be generated at the time of film cutting, 1 or more is obtained, and good pattern formability is obtained. In terms of aspect, it is 20 or less. 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 an oxidized ethyl group, an oxidized stretched propyl group, and a carbon number of 4 to 6 oxyalkylene groups 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 block.

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 (registered trademark) BPE-100, NEWPOL (registered trademark) BPE-180 (above is manufactured by 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 75% 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% by mass or less. Further, it is preferably 5% by mass or more and 60% by mass or less. More preferably, it is 10 mass% or more and 50 mass% or less. Especially good is 20~40% by mass.

Other ingredients

In the photosensitive resin composition, a surfactant may be contained for the purpose of improving coatability, defoaming property, flatness, and the like as needed. 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) Chemical Industry Company); FLORARDFC-135, 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 is manufactured by Asahi Glass Co., Ltd.); SH-28PA, SH-190, SH- 193. Commercial products such as SZ-6032 and SF-8428 (above, manufactured by Toray Silicone Co., Ltd.). These may be used alone or in combination of two or more.

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 functional decane coupling agent means a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group or an epoxy group. Examples of the functional decane coupling agent include trimethoxydecyl benzoic acid, Y-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethoxy decane. Y-glycidoxypropyltrimethoxydecane, trimethoxydecylpropyl isocyanate and 1,3,5-N-tris(trimethoxydecylpropyl)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. When the blending ratio exceeds 20% by mass, the development residue tends to be generated 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 monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, and 3- Hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc. Monocarboxylic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8 a polycarboxylic acid such as naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecyl succinic anhydride, triphenylamine anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, methyl bicycloheptylene anhydride, 1,2,3,4-butane tetracarboxylic acid, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic dianhydride Pyromellitic anhydride Benzophenone tetracarboxylic dianhydride, ethylene glycol bis trimellitic anhydride ester, trimellitic anhydride triglyceride partial esters of anhydride. Further, examples of the high boiling point solvent include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N. - dimethyl acetamide, N-methyl pyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl acetate Base cellosolve, etc. These may be used alone or in combination of two or more.

The blending ratio of the above-mentioned acid or high-boiling solvent can be adjusted according to the application and the coating method, and is not particularly limited as long as it can be uniformly mixed in the photosensitive resin composition. For example, the blending ratio of the acid or the high-boiling solvent is preferably 60% by mass or less, and more preferably 40% by mass or less based on the total amount of the photosensitive resin composition. In this case, there is an advantage that the characteristics of the photosensitive resin composition are not impaired.

Further, the photosensitive resin composition of the present embodiment 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 seal, as needed. Additives such as a sex-imparting agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent. These additives may be used alone or in combination of two or more.

The blending ratio of the additives is not particularly limited as long as it does not impair the characteristics of the photosensitive resin composition, and is preferably 50% by mass or less based on the total amount of the photosensitive resin composition.

For each of the above components, any of the examples may be combined.

The preparation of the photosensitive resin composition may be carried out by mixing and stirring in a usual manner. In the case where the filler or the pigment is added to the photosensitive resin composition, it may be dispersed and mixed by a disperser such as a dispersing mixer, a homogenizer or a three-roll mill. Further, it may be further filtered by a sieve, a membrane filter or the like as needed.

Next, the photosensitive resin laminate will be described. The photosensitive resin laminate has a structure including at least a support and a photosensitive resin layer formed of the photosensitive resin composition.

As the support, for example, a metal plate such as copper, a copper alloy, iron, or an iron-based alloy, or a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The thickness of the support is preferably from 1 to 150 μm.

The photosensitive resin layer can be formed by forming the photosensitive resin composition of the above-described embodiment into a liquid form and applying it to a support.

When the photosensitive resin composition is applied to a support, the photosensitive resin composition may be dissolved in a predetermined solvent to form a solution having a solid content of 30 to 60% by mass, and the solution may be used as the solution. Coating solution. Examples of the solvent include methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, naphtha, hydrogenated naphtha, naphtha solvent, acetone, and methyl group. Butyl ketone, methyl ethyl ketone, cyclohexanone, toluene, xylene, tetramethylbenzene, N,N-dimethylformamide, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene Alcohol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, Triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl An organic solvent such as ether acetate, propylene glycol monomethyl ether acetate or dipropylene glycol monomethyl ether acetate, or a mixed solvent thereof.

Examples of the coating method include a roll coating method, a doctor blade coating method, a gravure coating method, an air knife coating method, a slit extrusion coating method, and a bar coating method. Further, the removal of the solvent can be carried out, for example, by heating. The heating temperature at this time is preferably about 70 to 150 ° C, and the heating time is preferably about 5 to 30 minutes.

The amount of the residual organic solvent in the photosensitive resin layer formed as described above 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 varies depending on the application, and it is preferred that the thickness after removal of the solvent is about 0.5 to 100 μm.

In the support and the photosensitive resin layer, a surface of the photosensitive resin layer opposite to the support side may be coated with a protective film as needed.

The protective film may, for example, be a polymer film such as polyethylene or polypropylene. Further, the protective film is preferably a film of a fish eye, and the adhesion between the protective film and the photosensitive resin layer is such that the protective film is easily peeled off from the photosensitive resin layer, and preferably is smaller than The adhesion between the photosensitive resin layer and the support.

Further, an intermediate layer or a protective layer such as a buffer layer, an adhesive layer, a light absorbing layer, or a gas barrier layer may be further provided between the support and the photosensitive resin layer and/or between the photosensitive resin layer and the protective film.

The photosensitive resin laminate may be stored, for example, in the form of a flat plate, or may be laminated on one surface of the photosensitive resin layer (the surface exposed without being protected) and wound around a cylindrical shape. The core is stored in a roll form. The core is not particularly limited as long as it is a user, and examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene). Copolymers, etc., etc. When storing, it is preferred to wind the support so that it is the outermost side. Further, in the end face of the photosensitive resin laminate which is wound into a roll shape, it is preferable to provide an end face spacer from the viewpoint of protecting the end face, and it is preferable to provide a moisture-proof end face from the viewpoint of edge fusion resistance. Separator. Further, when the photosensitive resin laminate is bundled, it is preferably packaged in a black sheet having a small moisture permeability and packaged.

Hereinafter, a method of forming a photoresist pattern will be described.

In the method of forming a photoresist pattern, the photosensitive resin layer of the photosensitive resin laminate is laminated on the substrate in an adhesive manner, and the active light is irradiated in an image form, and the exposed portion is removed by development. In the portion which is not irradiated with the active light, since the photosensitive agent containing the 1,2-naphthoquinonediazide group interacts with the alkali-soluble phenol resin to function as a dissolution inhibitor, it is insoluble in alkali. However, for the portion irradiated to the active light, the sensitizer containing the 1,2-naphthone diazide group undergoes photodecomposition, thereby losing the dissolution inhibiting effect. Thereby, the exposed portion irradiated with the active light becomes alkali-soluble.

In the case where the photosensitive resin layered body has a protective film, the protective film is removed, and the photosensitive resin layer is heated to about 70 to 130 ° C. A method in which a pressure is applied to a substrate by a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf/cm ² ) by a laminator or the like. This lamination step can also be carried out under reduced pressure. 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 manner is irradiated with active light rays in an image form by a negative or positive mask pattern to form an exposed portion. In this case, when the support existing on the photosensitive resin layer is transparent to the active light, the active light can be irradiated through the support, and when the support exhibits light-shielding properties to the active light, the support is removed. The photosensitive resin layer is irradiated with active light. As the light source of the active light, a previously known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp or the like can be used to efficiently emit ultraviolet rays, visible light or the like. Further, a laser direct drawing exposure method or the like can also be employed.

After the exposure portion is formed, the photosensitive resin layer of the exposed portion is removed by development, thereby forming 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 or a water-based developer is used. A method of performing development by removing an exposed portion such as wet development or dry development of a developing solution such as an organic solvent. Examples of the base to be used in the wet development include a weakly basic inorganic compound such as sodium carbonate, potassium carbonate or ammonia; an alkali metal compound such as sodium hydroxide or potassium hydroxide; and an alkaline earth metal such as calcium hydroxide. a compound; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, A weakly basic organic compound such as triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate or polyethyleneimine; tetramethylammonium hydroxide or tetraethylammonium hydroxide. These are used alone or in combination of two or more kinds in the form of an aqueous solution. The pH of the alkaline aqueous solution is preferably in the range of 9 to 13, 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 mixed in the alkaline aqueous solution. Examples of the development method include an immersion method, a spray method, a brushing, and an impact.

Further, if necessary, heating at a temperature of about 60 to 250 ° C may be performed as a treatment after development, whereby the photoresist pattern is cured and used.

A photoresist pattern is obtained in the above manner. 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 sufficiently small defect can be formed. Further, the exposed portion of the resist film is easily dissolved in the weak base and peeled off from the substrate, and a resist pattern can be obtained by using the photosensitive resin composition of the present invention having excellent weak alkali developability.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. The present invention can be modified in various ways without departing from the spirit thereof.

<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 after the above-described photoresist pattern forming method using a copper foil laminate or a flexible substrate as a substrate.

First, a conductor pattern is formed on the copper surface of the substrate exposed 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.

<Method of manufacturing lead frame>

The method for producing a lead frame according to the present invention is carried out by the following steps after a method of forming the resist pattern using a metal plate such as copper, a copper alloy or an iron-based alloy as a substrate.

First, a substrate exposed by development is etched to form a conductor pattern.

Thereafter, the remaining photoresist pattern is removed in the same manner as in the above-described method of manufacturing a printed circuit board to obtain a desired lead frame.

<Method of Manufacturing Semiconductor Package>

The method of manufacturing a semiconductor package of the present invention is carried out by the following steps by a method of forming the above-described photoresist pattern using a wafer formed as a circuit of an LSI as a substrate.

A columnar plating of copper, solder, or the like is performed on the opening exposed by development to form a conductor pattern.

Thereafter, the remaining photoresist pattern is removed in the same manner as in the above-described method of manufacturing a printed wiring board, and a portion of the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.

<Method of Manufacturing Thin Film Transistor>

In the method of manufacturing a thin film transistor, for example, a gate electrode having a predetermined shape is formed on a substrate such as tantalum, glass, or a resin sheet by using a mask, and then a gate insulating film is formed by the resist pattern forming method and the removing method. Further, a film is formed on the entire surface of the insulating film, and a mask electrode is used to form a source electrode and a germanium electrode having a predetermined shape on the film layer, whereby a thin film transistor can be obtained.

Example

Hereinafter, the present invention will be described in more detail by way of examples.

[Examples 1 to 9, Comparative Example 1, Examples 10 to 23, Comparative Examples 2, 3]

<1. Preparation of Photosensitive Resin Composition>

The compounds shown in Tables 1 and 2 were 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: a cresol novolac resin having a weight average molecular weight of 10,000 and a molecular weight distribution of about 10, m body: p body = 6:4 (manufactured by Asahi Organic Materials Co., Ltd., EP4020G (trade name))

A-2: phenol novolac resin, having a weight average molecular weight of 7,000 and a molecular weight distribution of about 6 (as manufactured by Asahi Organic Materials Co., Ltd., PAPS-PN70 (trade name))

B-1: 4,4'-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene bisphenol 6-diazide-5 , 6-dihydro-5-oxo-l-naphthalenesulfonic acid mono-, di- or triester (PA-3 (trade name) manufactured by Daito Chemix Co., Ltd.)

B-2: 2,3,4,4'-tetrahydroxybenzophenone 6-diazide-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid single, second, third or Tetraester (DTEP-250 (trade name) manufactured by Daito Chemix)

C-1: polyparaxyl styrene having a weight average molecular weight of 20,000 (manufactured by Chemiway, MARUKA LYNCUR M H-2P (trade name))

C-2: a 1:1 (mole ratio) copolymer of p-vinylphenol and methyl methacrylate, having a weight average molecular weight of 10,000 (manufactured by Chemiway, MARUKA LYNCUR CMM (trade name))

D-1: a compound having 3 moles of propylene glycol at both ends of bisphenol A (manufactured by Toho Chemical Co., Ltd., BISOL 6PO (trade name))

D-2: Compound BA-10 GLYCOL (manufactured by Japanese emulsifier) having p=5, q=0, and r=0 on both sides of the above formula (I)

D-3: Compound PC-903 (manufactured by Japanese emulsifier) having p=0, q=3, and r=0 on both sides of the above formula (I)

D-4: Compound UNIOL DAB-800 (manufactured by Nippon Oil & Fats Co., Ltd.) having p=3, q=2, and r=0 on both sides of the above formula (I)

D-5: Compound BAP4-30 (manufactured by Japanese emulsifier) having p=15, q=2, and r=0 on both sides of the above formula (I)

D-6: Compound E having 3 moles of propylene glycol at both ends of the bisphenol E compound (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: a sample of a compound having 3 moles of propylene glycol at both ends of a bisphenol S compound (manufactured by Toho Chemical Co., Ltd.)

D-9: Polyoxyethylene-polyoxypropylene condensate (Adeca Pluronic L-44 (trade name) manufactured by ADEKA Co., Ltd.)

<2. Manufacturing of Photosensitive Resin Laminate>

The solvent methyl ethyl ketone was added to the photosensitive resin composition of the composition shown in Tables 1 and 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 dried by a bar coater. The film was coated on a 25 μm thick polyethylene terephthalate film and dried in a dryer at 90 ° C for 2 minutes to form a photosensitive resin layer of 10 μm thick. Next, a 30 μm-thick polyethylene film was bonded to the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

<3. Production of Evaluation Substrate> The entire surface of the substrate:

The substrate for evaluation was prepared by sandblasting the surface with a 0.4 mm thick copper foil laminate having a laminated copper foil of 35 μm and a spray pressure of 0.20 MPa (Japan Carlit, SAKURUNDUM R (registered trademark) )# 220).

laminated:

The polyethylene film of the photosensitive resin laminate was peeled off and laminated on the entire surface by a roll bonding machine (AL-70, manufactured by Asahi Kasei Engineering Co., Ltd., AL-70) at a roll temperature of 105 ° C and preheated to 60. °C copper foil laminate. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

exposure:

The support was peeled off, and the evaluation substrate was subjected to projection exposure using a chrome glass reticle using an exposure machine (projection exposure apparatus UX2003SM-MS04: manufactured by Ushio Electric Co., Ltd.) having an ultrahigh pressure mercury lamp.

development:

The obtained evaluation substrate was developed by a dipping method using a 2.38 mass% tetramethylammonium aqueous solution as an alkaline developing solution at a temperature of 20 °C. Thereafter, the mixture was washed with pure water for about 20 seconds by a dipping method at a temperature of 20 ° C, and dried by a drier.

<4. Evaluation> Chip evaluation:

The photosensitive resin laminate having the support side as the upper surface was cut by 10 cm in a straight line by an NT cutter, and the cut portion and its periphery were visually observed. The evaluation results of the chip test were classified in the following manner.

A: no chips are produced

B: Producing chips

Evaluation of sensitivity:

In the range of 200 mJ/cm ² to 100 mJ/cm ² , the exposure amount which can form the most favorable pattern after the above-mentioned "exposure" step and the above-mentioned "development" step is referred to as "sensitivity".

Evaluation of minimum development time:

The substrate on which the photosensitive resin layer of the photosensitive resin laminate was laminated was exposed to an exposure amount of 1,500 mJ/cm ² and developed. The state in which the photosensitive resin layer in the fully exposed portion was removed was visually confirmed, and the time taken until it reached this state was taken as the minimum development time.

Evaluation of pattern formation:

Exposure was carried out by a chrome glass reticle having a pattern of lines: a gap of 1:1, and development was carried out. When the development was carried out at a time which was 1.2 times the minimum development time described above, it was visually observed whether the line portion and the gap portion were clearly separated, and classification was carried out 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

<5. Evaluation results>

The evaluation results of the examples and comparative examples are shown in Tables 1 and 2.

As is clear from Table 1, in Examples 1 to 9, the chip evaluation, the sensitivity, the minimum development time, and the pattern formation property were all excellent. However, in Comparative Example 1, the (C) side chain having the source used in the present invention was not included. Since the alkali-soluble resin based on the aromatic hydroxy compound generates chips, the photosensitive resin layer is very brittle, and other evaluations cannot be performed.

As is clear from Table 2, in the photosensitive resin compositions of Examples 10 to 22, the generation of chips was sufficiently suppressed, and the balance of sensitivity, development time, and pattern formation property was excellent, whereas Comparative Examples 2 and 3 were used. Since the photosensitive resin composition does not contain the component (D), chips are generated, and since the development cannot be performed, the pattern cannot be formed.

[Industrial availability]

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 for metal mask manufacturing, and the fabrication of packages such as BGA and CSP, COF (Chip On Film). Or the manufacture of a strip substrate such as TAB (Tape Automated Bonding), the manufacture of a semiconductor bump, the fabrication of a partition wall of a flat panel display such as an ITO electrode or an address electrode, an electromagnetic wave mask, and the use of a sandblasting method. A method of processing a substrate. Examples of the processing by the sand blast method include glass cover processing of organic EL (electroluminescence), opening of a silicon wafer, and pin processing of ceramics. Further, the processing by the blasting step of the present invention can be utilized for the production of a ferroelectric film and an electrode of a metal material layer selected from the group consisting of a noble metal, a noble metal alloy, a high melting point metal, and a high melting point metal compound.

Claims (12)

A photosensitive resist composition comprising at least a support resin and a photosensitive resin layer formed of a photosensitive resin composition, wherein the photosensitive resin composition contains (A) an alkali-soluble phenol resin, (B) A photosensitive agent containing a 1,2-naphthoquinonediazide group and (C) an alkali-soluble resin having a group derived from an aromatic hydroxy compound in a side chain. The resist roll according to claim 1, wherein the component (C) is an alkali-soluble resin containing hydroxystyrene as a copolymerization component. The photoresist roll according to claim 1, wherein the component (A) and the component (B) in an amount of from 20 to 90% by mass based on the total amount of the photosensitive resin composition are contained in an amount of from 20 to 90% by mass. 1 to 75% by mass of the above component (C). The photoresist roll of claim 1 further comprising (D) a plasticizer. The resist roll according to claim 1, which contains 1,2-naphthoquinonediazidesulfonate of the compound represented by the following formula (I) as the above component (B): Wherein R ₁ to R ₆ are each independently hydrogen, halogen, C1 to C4 alkyl, alkenyl or hydroxy, and R ₇ and R ₈ are each independently hydrogen, halogen or C1 to C4 alkyl, and R ₉ ~R _{11 is} independently hydrogen or a C1 to C4 alkyl}. The photoresist roll of claim 4, wherein the component (D) is a group consisting of a compound selected from the group consisting of bisphenol A, bisphenol E, bisphenol F, and bisphenol S, and the hydrogenation thereof A compound derived from at least one compound and having at least one hydroxyl group at the end. A method for forming a photoresist pattern, comprising: a step of laminating a photosensitive resin layer of a photosensitive resin laminate of the photoresist roll of claim 1 on a substrate, and exposing the photosensitive resin layer An exposure step and a development step of removing the photosensitive photosensitive resin layer. A method of forming a photoresist pattern according to claim 7, wherein the direct exposure is performed in the exposure step. A method of manufacturing a printed circuit board, which further comprises the step of etching or plating a substrate on which a photoresist pattern is formed by the method of claim 7 or 8. A method of manufacturing a lead frame, comprising the step of etching a substrate on which a photoresist pattern is formed by the method of claim 7 or 8. A method of fabricating a semiconductor pattern, which further comprises the step of etching or plating a substrate on which a photoresist pattern is formed by the method of claim 7 or 8. A method of manufacturing 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 7 or 8.