WO2009125752A1 - Composition de résine photosensible et stratifié de résine photosensible comprenant ladite composition - Google Patents

Composition de résine photosensible et stratifié de résine photosensible comprenant ladite composition Download PDF

Info

Publication number
WO2009125752A1
WO2009125752A1 PCT/JP2009/057081 JP2009057081W WO2009125752A1 WO 2009125752 A1 WO2009125752 A1 WO 2009125752A1 JP 2009057081 W JP2009057081 W JP 2009057081W WO 2009125752 A1 WO2009125752 A1 WO 2009125752A1
Authority
WO
WIPO (PCT)
Prior art keywords
photosensitive resin
group
resin composition
compound
bisphenol
Prior art date
Application number
PCT/JP2009/057081
Other languages
English (en)
Japanese (ja)
Inventor
洋介 秦
陽一郎 井出
Original Assignee
旭化成イーマテリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to JP2010507240A priority Critical patent/JP5155389B2/ja
Publication of WO2009125752A1 publication Critical patent/WO2009125752A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides

Definitions

  • the present invention relates to the manufacture of printed wiring boards, IC chip mounting lead frames (hereinafter referred to as lead frames), metal foil precision processing such as metal mask manufacturing, thin film transistors such as liquid crystal display elements, BGA (ball grid array), CSP. Resist suitable as a protective mask member for manufacturing semiconductor packages such as (chip size package), manufacturing of members such as ITO electrodes, address electrodes, or electromagnetic wave shields in the field of flat panel displays, and processing a substrate by sandblasting
  • the present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution suitable for producing a pattern, a photosensitive resin laminate using the same, and uses thereof.
  • a positive using a photosensitive resin composition containing a novolac-type phenolic resin and a 1,2-naphthoquinonediazide compound as a raw material As an image forming method used for patterning and the like of semiconductor integrated circuits, liquid crystal display elements, printed wiring boards, etc., a positive using a photosensitive resin composition containing a novolac-type phenolic resin and a 1,2-naphthoquinonediazide compound as a raw material.
  • a method using a type photoresist is known.
  • the application thickness is generally 0.5 to several ⁇ m.
  • image pattern formation over a wide dimensional range is formed. The dimension range is wide, for example, from a sub-half micron region of about 0.3 ⁇ m to a considerably large width of several tens to several hundreds of ⁇ m.
  • the line width of an image becomes narrower with the progress of technologies such as TFT liquid crystal and STN liquid crystal, and the tendency of miniaturization is increasing.
  • the conventional device using TN or STN liquid crystal has an image design size of about 200 ⁇ m to several hundred ⁇ m, but recently, the minimum design size of an image has become 100 ⁇ m or less due to the development of a new technology. .
  • the image design dimension is improved to a level of several ⁇ m.
  • the characteristics expected for the photoresist material include the maintenance of the above-mentioned fine processing capability and the ability to increase the area. That is, it corresponds to a liquid crystal display whose substrate has been enlarged in recent years, a PDP or the like oriented from the beginning to a large screen. In these substrates, it is becoming an important technique to further improve the in-plane film thickness uniformity. In addition, common problems in large-area displays include further cost reduction and liquid saving of the photoresist used during manufacturing. Among the above-mentioned problems, in order to further improve the film thickness uniformity in the surface of the photoresist and achieve liquid-saving of the photoresist raw material, the investigation of the coating method has been continued.
  • the negative dry film photoresist uses a polyester film having a thickness of 15 to 25 ⁇ m as a support, and a negative photosensitive resin composition usually having a thickness of 10 to 100 ⁇ m is applied on the polyester film.
  • a polyolefin film having a thickness of ⁇ 40 ⁇ m is laminated as a protective film.
  • This negative dry film photoresist technique is also used for printed wiring boards with a width of about 600 mm. However, when used in the field of printed wiring boards, the resolution required for the negative dry film photoresist is at most about 30 to 300 ⁇ m.
  • a printed wiring board using a negative dry film photoresist will be briefly described. First, if there is a protective film on the negative dry film photoresist, remove the protective film, laminate it so that the negative photosensitive resin composition is in contact with the substrate for creating the printed wiring board, and expose the active light through the support. Then, the photosensitive resin composition is cured. Next, generally, the unexposed photosensitive resin composition is dispersed and removed using a weak alkaline aqueous solution typified by an aqueous sodium carbonate solution having a concentration of 1% by mass and developed. Thereafter, the copper on the substrate is etched with an aqueous cupric chloride solution. Then, all the cured photosensitive resin composition is peeled and removed with a caustic soda aqueous solution or a caustic potassium aqueous solution having a concentration of 2 to 3%.
  • a weak alkaline aqueous solution typified by an aqueous sodium carbonate solution having a concentration of 1% by mass and
  • the image processing technique required when manufacturing TFTs for LCDs is, for example, about 2 to 10 ⁇ m, and the resolution is much higher than the field of printed wiring boards.
  • metal ion-free development, stripping with an organic stripping solution, etching of metal thin films such as ITO, Ta, and Al and inorganic thin films such as SiNx and ITO are also required.
  • the photoresist has a film thickness of several ⁇ m, improved adhesion to various sputtered metal thin films and inorganic thin films, further improved film thickness uniformity, and unevenness of about 1 ⁇ m.
  • Patent Documents 1 and 2 disclose a conventional positive photoresist material that includes a phenol novolak resin as a main component and 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive component.
  • a phenol novolak resin as a main component
  • 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive component.
  • Patent Document 3 also discloses that a compound obtained by reacting a dry oil with a phenol resin is introduced in order to soften the film.
  • positive-type dry film photoresists using these materials have not been put into practical use. Details will be described below.
  • a roll-shaped product having a desired film width is obtained as follows. First, a wide roll is usually formed through application of a positive photosensitive resin composition to a support. Next, the roll is cut by a slit so that the roll has a desired film width. In order to laminate the photosensitive resin composition on the substrate on which the image pattern is formed, the dry film photoresist is usually drawn out from the roll-shaped product and thermally transferred while being pressed onto the substrate using a laminator. During or after the lamination, the dry film photoresist is cut to a predetermined length in the longitudinal direction of the substrate.
  • chips of the positive photosensitive resin composition (hereinafter simply referred to as chips) are generated at the time of the slit. The problem of end up occurs. Also, when the dry film photoresist is cut to a predetermined length in the longitudinal direction of the substrate during lamination, chips are likely to be generated from the cut surface. These chips become dust, contaminate the operating environment of the substrate and laminator, and adhere to the support laminated on the substrate. As a result, defects tend to occur in the image pattern.
  • the present invention has been made in view of the above circumstances, and pattern formation is possible.
  • the photosensitive resin composition is flexible, and generation of chips even when the film is cut.
  • An object of the present invention is to provide a photosensitive resin composition in which is sufficiently suppressed, and a photosensitive resin laminate using the same.
  • the present inventors have studied to solve the above problems, and found that the above problems can be solved by using a photosensitive resin composition having the following configuration, and have made the present invention.
  • the present invention is as follows.
  • a photosensitive resin composition (A) an alkali-soluble phenol resin, (B) a photosensitizer containing a 1,2-naphthoquinonediazide group, and (C) an alkali-soluble resin having a group derived from an aromatic hydroxy compound in the side chain.
  • the component (A) is 20 to 90% by mass
  • the component (B) is 1 to 75% by mass
  • the component (C) is 1 to The photosensitive resin composition according to [1] or [2], containing 75% by mass.
  • the component (D) is derived from at least one compound selected from the group consisting of bisphenol A, bisphenol E, bisphenol F and bisphenol S, and compounds obtained by hydrogenation thereof, and has a hydroxyl group at the end.
  • the photosensitive resin composition according to any one of [1] to [5], wherein the photosensitive resin composition is a compound having at least one.
  • a photosensitive resin laminate comprising at least a support and a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [6].
  • a resist roll in which the photosensitive resin laminate according to [7] is rolled.
  • a method for forming a resist pattern that includes, in order.
  • a method for manufacturing a printed wiring board further comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method described in [9] or [10].
  • a lead frame manufacturing method including a step of etching a substrate on which a resist pattern is formed by the method described in [9] or [10].
  • a method for producing a semiconductor pattern further comprising a step of etching or plating the substrate on which the resist pattern is formed by the method according to [9] or [10].
  • a method for manufacturing a thin film transistor including a step of etching or plating a substrate on which a resist pattern is formed by the method according to [9] or [10].
  • a photosensitive resin composition comprising a compound that is derived from at least one compound selected from the group consisting of compounds having at least one hydroxyl group at a terminal.
  • the component (D) is represented by the following general formula (VII): ⁇ Wherein Y 1 is an ethylene group, Y 2 is a propylene group, Y 3 is an alkylene group having 4 to 6 carbon atoms, and Y 4 and Y 5 are each independently a hydrogen atom Or p, q, and r are integers of 0 or more, and the sum thereof is 1 to 20, and ethylene oxide, propylene oxide, and carbon number 4 to 4 included in the right side and / or left side of the structure.
  • the repeating unit of 6 alkylene oxides may be included randomly or as a block.
  • the photosensitive resin composition according to [15] above which is at least one compound selected from the group consisting of a compound hydrogenated thereto.
  • the component (A) contains 20 to 90% by mass, the component (B) 1 to 75% by mass, and the component (D) 1 to 75% by mass.
  • the photosensitive resin composition as described.
  • a photosensitive resin laminate comprising at least a support and a photosensitive resin layer comprising the photosensitive resin composition according to any one of [15] to [18].
  • a laminating step of laminating the photosensitive resin layer of the photosensitive resin laminate according to [19] on a substrate, an exposure step of exposing the photosensitive resin layer, and a developing step of removing the exposed photosensitive resin layer A method for forming a resist pattern that includes, in order.
  • a method for manufacturing a printed wiring board further comprising a step of etching or plating the substrate on which the resist pattern is formed by the method described in [21] or [22].
  • a lead frame manufacturing method including a step of etching a substrate on which a resist pattern is formed by the method described in [21] or [22].
  • a semiconductor pattern manufacturing method including a step of etching or plating a substrate on which a resist pattern has been formed by the method described in [21] or [22].
  • a method of manufacturing a thin film transistor including a step of etching or plating a substrate on which a resist pattern is formed by the method described in [21] or [22].
  • the photosensitive resin composition when a pattern can be formed and formed as a dry film, the photosensitive resin composition is flexible, and generation of chips is sufficiently suppressed even when the film is cut, and the photosensitive resin A composition can be provided.
  • Alkali-soluble phenol resin (A) Alkali-soluble phenol resin is obtained by, for example, a polycondensation reaction using a phenol compound and an aldehyde and / or a ketone as raw materials.
  • phenol compound examples include phenol, cresol, xylenol; alkylphenols such as ethylphenol, butylphenol, and trimethylphenol; alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol; alkenylphenols such as vinylphenol and allylphenol.
  • Arylphenols such as phenylphenol; aralkylphenols such as benzylphenol; alkoxycarbonylphenols such as methoxycarbonylphenol; arylcarbonylphenols such as benzoyloxyphenol; halogenated phenols such as chlorophenol; polyhydroxybenzenes such as catechol and resorcinol; Bisphenols such as bisphenol A and bisphenol F; -Or naphthol compounds such as ⁇ -naphthol, hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol; hydroxyalkylcresols such as hydroxyethylcresol; Monoethylene oxide adducts of bisphenol; alcoholic hydroxyl group-containing phenolic compounds such as monopropylene oxide adducts of bisphenol; and p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic
  • the above-mentioned phenol compounds are used alone or in combination of two or more.
  • aldehyde and / or ketone include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone, and glyceraldehyde. .
  • aldehyde and / or ketone examples include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, and pyruvic acid. Also included are repric acid, 4-acetylbutyric acid, acetone dicarboxylic acid, and 3,3′-4,4′-benzophenone tetracarboxylic acid.
  • Formaldehyde precursors such as paraformaldehyde and trioxane may also be used. These are used singly or in combination of two or more.
  • an acidic catalyst for the condensation polymerization reaction.
  • this acidic catalyst By using this acidic catalyst, a novolac-type phenol resin can be easily obtained, and generation of chips can be more effectively prevented.
  • the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid.
  • An acidic catalyst is used individually by 1 type or in combination of 2 or more types.
  • the conditions for synthesizing the alkali-soluble phenol 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 0.7 to 1 mol with respect to 1 mol of the phenol compound.
  • the (A) alkali-soluble phenol resin may be a polycondensation product of the above-described phenol compound and a compound other than phenol such as m-xylene.
  • the molar ratio of the compound other than phenol to the phenol compound used for the condensation polymerization is preferably less than 0.5.
  • the polystyrene-converted weight average molecular weight of the alkali-soluble phenol resin by gel permeation chromatography is preferably from 300 to 100,000 from the viewpoints of improving the coating properties and suppressing the decrease in developability. 20,000 to 20,000 is more preferable.
  • the weight average molecular weight is preferably 300 or more from the viewpoint of coating properties. Further, from the viewpoint of developability, 100,000 or less is preferable.
  • the phenol resin may be multimerized using a chain extender to increase the molecular weight so that the weight average molecular weight is within the range. Examples of the chain extender include diepoxy compounds and dioxazoline compounds that can react with a carboxyl group, and diisocyanate compounds that can react with a hydroxyl group.
  • An alkali-soluble phenol resin is used individually by 1 type or in combination of 2 or more types.
  • Examples of the alkali-soluble phenol resin used in combination of two or more types include, for example, two or more types of alkali-soluble phenol resins obtained from different types of monomers, and two or more types of alkali-soluble resins having different weight average molecular weights.
  • Examples of the phenol resin include two or more alkali-soluble phenol resins having different dispersities.
  • the blending ratio of the alkali-soluble phenol resin in the photosensitive resin composition is preferably 20 to 90% by mass, and preferably 25 to 85% by mass with respect to the total amount of the photosensitive resin composition. More preferred is 30 to 80% by mass.
  • the blending ratio is preferably 20% by mass or more from the viewpoint of improving the pattern formability, and preferably 90% by mass or less from the viewpoint of preventing brittleness of the resist film.
  • Photosensitizer containing 1,2-naphthoquinonediazide group is an organic compound having a hydroxyl group or an amino group (hereinafter simply referred to as “organic compound”). It is a compound obtained by reacting a 1,2-naphthoquinonediazide compound having a sulfo group and / or a sulfonyl chloride group. At this time, the hydroxyl group or amino group of the organic compound is bonded to the sulfo group or sulfonyl chloride group of the 1,2-quinonediazide compound.
  • At least one bond may be present in the molecule of the resulting 1,2-quinonediazide compound.
  • 1,2-quinonediazide compound having a sulfo group and / or a sulfonyl chloride group include 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5-sulfone.
  • Examples include acids, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.
  • 1,2-quinonediazide compounds having a sulfo group and / or a sulfonyl chloride group 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid,
  • 1,2-naphthoquinone-2-diazide-4-sulfonic acid 1,2-naphthoquinone-2-diazide-5-sulfonic acid
  • One or more compounds selected from the group consisting of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride are preferred.
  • These 1,2-quinonediazide compounds having a sulfo group and / or a sulfonyl chloride group are well dissolved in a solvent
  • organic compound examples include polyhydroxybenzophenones, bis [(poly) hydroxyphenyl] alkanes, tris (hydroxyphenyl) methanes or methyl-substituted products thereof, bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes, or Its methyl substitution product, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, aniline, p-aminodiphenylamine, 4,4 ′ -Diaminobenzophenone, novolak, pyrogallol-acetone resin, homopolymer of hydroxystyrene or a copolymer with a monomer copolymerizable therewith. These are used singly or in combination of two or more.
  • polyhydroxybenzophenones examples include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and 2,3,6-trihydroxybenzophenone.
  • Examples of bis [(poly) hydroxyphenyl] alkanes 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-hydroxyphenyl) -2-propyl] phenyl] ethylidene ⁇ bisphenol, and 3 , 3′-dimethyl- ⁇ 1- [4- [2- (3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene ⁇ bisphenol It is. These are used singly or in combination of two or more.
  • tris (hydroxyphenyl) methanes or methyl-substituted products thereof include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, and bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane Is mentioned. These are used singly or in combination of two or more.
  • Examples of bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes or methyl-substituted products thereof include bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane and bis (3-cyclohexyl-4-hydroxyphenyl).
  • examples of the organic compound include polyhydroxybenzophenones, bis [(poly) hydroxyphenyl] alkanes, tris (hydroxyphenyl) methanes, and / or bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes. It is preferable that The organic compound is more preferably at least one compound selected from the group consisting of compounds represented by the following general formulas (I), (II), and (III). In this case, since the difference in solubility in the developer before and after the light irradiation to the photosensitive resin composition becomes large, there is an advantage that the image contrast is more excellent.
  • R 1 to R 6 are each independently hydrogen, halogen, C1-C4 alkyl group, alkenyl group or hydroxyl group
  • R 7 and R 8 are each independently hydrogen, halogen or C1-C4 A C4 alkyl group
  • R 9 to R 11 are each independently hydrogen or a C1 to C4 alkyl group.
  • 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, and X is a single bond, an oxygen atom or a phenylene group.
  • ⁇ It is more preferable from the viewpoint of sensitivity to be at least one compound selected from the group consisting of:
  • the organic compound is at least one compound selected from the group consisting of the compound represented by the general formula (I), the compound represented by the general formula (II), and the compound represented by the general formula (III).
  • the 1,2-quinonediazide compound having a sulfo group and / or a sulfonyl chloride group 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 / or 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride examples include compounds represented by the above general formula (I), compounds represented by the above general formula (II), and the above general formula (III). Since the compatibility with at least one compound selected from the group consisting of the compounds represented by the formula (1) is good, the amount of aggregates generated when the component (A) and the component (B) are mixed is reduced. be able to. In addition, when a photosensitive resin composition containing these is used as a photosensitive component of a photoresist, the sensitivity, image contrast, and heat resistance are improved.
  • At least one compound selected from the group consisting of the compound represented by the general formula (I), the compound represented by the general formula (II), and the compound represented by the general formula (III) is Chemical formulas (IV) to (VI): It is more preferable that it is at least one compound selected from the group consisting of compounds represented by: In this case, there is an advantage that it is more excellent in light sensitivity. Among these, a compound represented by the following general formula (IV) is particularly preferable.
  • Examples of the synthesis method of the 2-naphthoquinonediazide compound include the following methods.
  • 1,2-naphthoquinone-2-diazide-sulfonyl chloride is added to a solvent such as dioxane or THF and reacted in the presence of an alkali catalyst such as triethylamine, triethanolamine, alkali carbonate or alkali hydrogen carbonate.
  • a sensitizer containing a 1,2-naphthoquinonediazide group obtained by condensing the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride a sensitizer containing a 1,2-naphthoquinonediazide group obtained by condensing the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride.
  • At least one compound selected from the group consisting of compounds represented by formulas (I), (II), and (III) There may be at least one bond between the hydroxyl group and the sulfonyl group of 1,2-naphthoquinone-2-diazide-sulfonyl chloride.
  • the 1,2-naphthoquinone-2-diazide-sulfonyl chloride is preferably 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride or 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. is there. You may use these individually by 1 type or in combination of 2 or more types.
  • the blending ratio of the component (B) in the photosensitive resin composition is preferably 1 to 75% by mass and more preferably 5 to 50% by mass with respect to the total amount of the photosensitive resin composition. It is particularly preferably 5 to 40% by mass. Further particularly preferred is 10 to 30% by mass. This blending ratio is preferably 1% by mass or more from the viewpoint of improving photosensitivity, and is preferably 75% by mass or less from the viewpoint of preventing brittleness of the resist film.
  • (i) polyhydroxystyrene examples thereof include resins, (ii) phenol group-containing poly (meth) acrylate resins, (iii) phenol group-containing polyacrylamide resins, and modified products thereof.
  • a method for producing a polyhydroxystyrene-based resin for example, a vinylphenol monomer obtained by various methods such as dehydration of acetoxyphenylmethylcarbinol, decarboxylation decomposition of hydroxycinnamic acid, dehydrogenation of ethylphenol, cation or radical initiation
  • a method of homopolymerization or copolymerization with other comonomers in the presence of an agent is known as an industrial method.
  • a monomer in which the hydroxyl group of vinylphenols is protected with an acetyl group, a trimethylsilyl group, a t-butyl group, a t-butoxycarbonyl group, etc. is synthesized and polymerized in the presence of a cation, anion, or radical initiator, and then protected.
  • a method for obtaining a polymer by removing a group is also known. In this method, it is possible to produce a monodispersed polymer by so-called living polymerization by selecting the kind of the protecting group and the kind of the initiator (Japanese Patent Laid-Open No. 3-277608).
  • JP-A-1-103604 a method of hydrogenating these vinylphenol polymers into a modified product having excellent light transmittance (JP-A-1-103604), or various ethers by reaction of hydroxyl groups of vinylphenol polymers, and Production methods of ester derivatives (Japanese Patent Laid-Open No. Sho 63-312307, Report of Fiber and Polymer Materials Research Institute, Vol. 128, p. 65 (1981)) and various nuclear substitution products of vinyl phenol polymers (Japanese Patent Laid-Open No. Sho 51-83691) No. Publication) is known.
  • Polyhydroxystyrene resins include polyhydroxystyrene, modified polyhydroxystyrene, hydrogenated polyhydroxystyrene, copolymers of hydroxystyrene and styrene, (meth) acrylic acid ester, maleic acid ester, and the like. Can be mentioned.
  • the weight average molecular weight of polyhydroxystyrene is 1,000 to 1,000,00, preferably 5,000 to 50,000.
  • modified polyhydroxystyrene examples include those obtained by reacting polyhydroxystyrene with a benzenesulfonyl chloride derivative, a naphthalenesulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalenecarbonyl chloride derivative, etc. in the presence of a basic catalyst. It is done.
  • sulfonyl chloride derivative and the carbonyl chloride derivative include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetaminobenzenecarbonyl chloride, benzenecarbonyl chloride, p -Chlorobenzenecarbonyl chloride, naphthylbenzenecarbonyl chloride and the like.
  • the sulfonyl chloride derivative or the carbonyl chloride derivative is usually used at a ratio of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, with respect to 100 parts by weight of polyhydroxystyrene.
  • modified polyhydroxystyrene can have a weight average molecular weight in the range of 3,000 to 50,000, preferably 5,000 to 30,000.
  • Hydrogenated polyhydroxystyrene is obtained by hydrogenating part of the benzene ring of polyhydroxystyrene and modified polyhydroxystyrene in which part of the benzene ring is modified by a substituent.
  • the weight average molecular weight of the hydrogenated polyhydroxystyrene is usually selected in the range of 3,000 to 30,000, preferably 5,000 to 25,000. From the viewpoint of mechanical properties and dry etching resistance, the weight average molecular weight is preferably 3,000 or more, and preferably 30,000 or less from the viewpoint of compatibility.
  • the proportion of hydroxystyrene when copolymerizing with other components is preferably from 30% by mass to 100% by mass from the viewpoint of obtaining sufficient alkali developability upon exposure. A more preferable ratio of hydroxystyrene is 40% by mass or more and 100% by mass or less.
  • Phenol group-containing poly (meth) acrylic ester resins include 4-hydroxyphenyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate and other poly (meth) acrylic acid monomers And coalesced and modified products thereof.
  • the weight average molecular weight of the phenol group-containing poly (meth) acrylic acid ester resin is 5,000 to 1,000,000, preferably 10,000 to 200,000.
  • phenol group-containing polyacrylamide resin examples include polymers and copolymers of phenol group-containing acrylamide monomers such as 3,5-dimethyl-4-hydroxybenzylacrylamide, and modified products thereof.
  • the weight average molecular weight of the phenol group-containing polyacrylamide resin is 1,000 to 1,000,000, preferably 5,000 to 100,000.
  • the alkali-soluble resin having a group derived from an aromatic hydroxy compound in the side chain is preferably blended in an amount of 1 to 75% by mass with respect to 100% by mass of the photosensitive resin composition. More preferably, it is 5 to 50% by mass.
  • This blending ratio is preferably 1% by mass or more from the viewpoint of preventing brittleness of the resist film, and is preferably 75% by mass or less from the viewpoint of solubility in the entire system.
  • the photosensitive resin composition contains (D) a plasticizer from the viewpoint that chips can be reduced.
  • the plasticizer may be a low molecular weight component that is compatible, for example, polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene.
  • Glycol esters such as oxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalates such as diethyl phthalate, o-toluene Sulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri-n-pro Le, like acetyl citrate tri -n- butyl.
  • the (D) plasticizer contained in the photosensitive resin composition is bisphenol A, bisphenol E, bisphenol F, and bisphenol S from the viewpoint of reducing chips when it is made into a film while maintaining excellent pattern forming properties.
  • a compound derived from at least one compound selected from the group consisting of compounds obtained by hydrogenating these compounds and having at least one hydroxyl group at the terminal is preferable.
  • Such compounds include bisphenol A (2,2-bis (4′-hydroxyphenyl) propane) or bisphenol E (1,1-bis (4-hydroxyphenyl) ethane) or bisphenol F (4,4′- Methylene bisphenol) or bisphenol S (4,4'-sulfonyldiphenol) using a hydroxyl group at both ends to introduce an aliphatic molecular chain such as an alkyl group, an alkylene oxide group, or a polyalkylene oxide group Is mentioned.
  • the alkyl group include a methyl group, an ethyl group, and a propyl group.
  • Examples of the alkylene oxide group include a methylene oxide group, an ethylene oxide group, a propylene oxide group, and a tetramethylene oxide group.
  • Examples of the polyalkylene oxide group include a polymethylene oxide group, Examples thereof include a polyethylene oxide group, a polypropylene oxide group, a polytetramethylene oxide group, or a block copolymer or a group made of a random copolymer.
  • the component (D) may have a structure other than a hydroxyl group at the end of the introduced molecular chain, on the premise that it has at least one hydroxyl group at the end.
  • a compound derived from bisphenol A or a hydrogenated compound is preferable from the viewpoint of flexibility of the resist film.
  • (D) component is the following general formula (VII): ⁇ Wherein Y 1 is an ethylene group, Y 2 is a propylene group, Y 3 is an alkylene group having 4 to 6 carbon atoms, and Y 4 and Y 5 are each independently a hydrogen atom Or p, q, and r are integers of 0 or more, and the sum thereof is 1 to 20, and ethylene oxide, propylene oxide, and carbon number 4 to 4 contained in the right side and / or left side of the structure
  • the repeating unit of 6 alkylene oxides may be included randomly or as a block. ⁇ , And at least one compound selected from the group consisting of compounds hydrogenated thereto is more preferred.
  • the total of p, q, and r on the right side and / or the left side is 1 to 20, and is 1 or more from the point that chips are hardly generated at the time of film cutting. It is 20 or less from the point of obtaining.
  • the total of p, q, and r is preferably 1 to 10, and preferably 2 or more and 6 or less.
  • the compound shown by the said general formula (VII) has a repeating unit of a propylene oxide from the point which the chip at the time of film cutting
  • the repeating unit of ethylene oxide, propylene oxide, and alkylene oxide having 4 to 6 carbon atoms contained on the right side and / or left side of the structure of the compound of the general formula (VII) is 1 to 20 in total. It may be in random or in blocks.
  • Specific examples of the compound represented by the general formula (VII) include Adecanol (registered trademark) SDX-1569, Adecanol (registered trademark) SDX-1570, Adecanol (registered trademark) SDX-1571, Adecanol (registered trademark).
  • the content is preferably 1% by mass to 75% by mass with respect to the total amount of the photosensitive resin composition. It is preferably 1% by mass or more from the viewpoint of ensuring the flexibility of the resist film, and preferably 75% by mass or less from the viewpoint of ensuring the photosensitivity of the resist film. More preferably, it is 5 mass% or more and 60 mass% or less. More preferably, it is 10 mass% or more and 50 mass% or less. Particularly preferred is 20 to 40% by mass.
  • the other component photosensitive resin composition may contain a surfactant for the purpose of improving coating properties, antifoaming properties, leveling properties, and the like.
  • a surfactant is not particularly limited, but is preferably a fluorosurfactant.
  • fluorosurfactant include BM-1000 and BM-1100 (manufactured by BM Chemie); Mega-Fac (registered trademark) F142D, Mega-Fac (registered trademark) F172, and Mega-Fac (registered trademark).
  • the blending ratio of the surfactant is preferably 5% by mass or less with respect to the total amount of the photosensitive resin composition. When this blending ratio exceeds 5% by mass, the pattern formability tends to be lower than when the blending ratio is in the above range.
  • the photosensitive resin composition may contain an adhesion assistant in order to improve the adhesion with a substrate or the like.
  • an adhesion assistant a functional silane coupling agent is preferable.
  • the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group.
  • Examples of functional silane coupling agents include trimethoxysilylbenzoic acid, Y-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Y-glycidoxypropyltrimethoxysilane, and trimethoxysilylpropyl.
  • Examples include isocyanate and 1,3,5-N-tris (trimethoxysilylpropyl) isocyanate. These are used singly or in combination of two or more.
  • the blending ratio of the adhesion assistant is preferably 20% by mass or less with respect to the total amount of the photosensitive resin composition. When this blending ratio exceeds 20% by mass, a development residue tends to occur more easily than when the blending ratio is in the above range.
  • the photosensitive resin composition may contain an acid or a high boiling point solvent in order to finely adjust the solubility in an alkali developer.
  • the acid include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid, cinnamic acid, lactic acid, 2-hydroxybutyric acid, 3-hydroxy Hydroxy monocarboxylic acids such as butyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid and syringic acid, shu Acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-
  • the high boiling point solvent examples include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ⁇ -butyrolactone, ethylene carbonate, Examples include propylene carbonate and phenyl cellosolve acetate. These are used singly or in combination of two or more.
  • the mixing ratio of the above-mentioned acid or high boiling point solvent is not particularly limited as long as it can be adjusted according to the application and coating method, and can be uniformly mixed in the photosensitive resin composition.
  • the mixing ratio of these acids and high-boiling solvents is preferably 60% by mass or less, more preferably 40% by mass or less, based on the total amount of the photosensitive resin composition. In this case, there exists an advantage that the characteristic of the photosensitive resin composition is not impaired.
  • the photosensitive resin composition of the present embodiment includes a sensitizer, a light absorber (dye), a crosslinking agent, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, and an adhesion imparting agent as necessary.
  • additives such as a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent may be contained. These additives may be used alone or in combination of two or more.
  • the blending ratio of these additives is not particularly limited as long as it does not impair the characteristics of the photosensitive resin composition, but is preferably 50% by mass or less based on the total amount of the photosensitive resin composition. .
  • Each of the components described above may be combined with any of those exemplified above.
  • Preparation of the photosensitive resin composition may be performed by mixing and stirring by a usual method. Moreover, what is necessary is just to disperse
  • dispersers such as a dissolver, a homogenizer, and a 3 roll mill
  • the photosensitive resin laminate has a structure including at least a support and a photosensitive resin layer made of the above-described photosensitive resin composition.
  • a support for example, a metal plate such as copper, a copper alloy, iron, or an iron alloy, or a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used.
  • the thickness of the support is preferably 1 to 150 ⁇ m.
  • the photosensitive resin layer can be formed by applying the photosensitive resin composition of the present embodiment in a liquid state on a support.
  • the photosensitive resin composition When applying the photosensitive resin composition on the support, if necessary, the photosensitive resin composition is dissolved in a predetermined solvent to obtain a solution having a solid content of 30 to 60% by mass.
  • a predetermined solvent include methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, toluene, xylene.
  • the coating method examples include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater.
  • the solvent can be removed, for example, by heating.
  • the heating temperature is preferably about 70 to 150 ° C.
  • the heating time is preferably about 5 to 30 minutes.
  • the amount of the remaining organic solvent in the photosensitive resin layer thus formed is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
  • the thickness of the photosensitive resin layer varies depending on the application, but the thickness after removing the solvent is preferably about 0.5 to 100 ⁇ m.
  • the surface opposite to the support side of the photosensitive resin layer may be covered with a protective film as necessary.
  • the protective film examples include polymer films such as polyethylene and polypropylene. Further, the protective film is preferably a low fish eye film, and the adhesive force between the protective film and the photosensitive resin layer is such that the photosensitive resin layer can be easily peeled off from the photosensitive resin layer. It is preferable that it is smaller than the adhesive force between a support and a support. Further, an intermediate layer or a protective layer such as a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer is further provided between the support and the photosensitive resin layer and / or between the photosensitive resin layer and the protective film. It may be.
  • the photosensitive resin laminate is, for example, in the form of a flat plate as it is, or by laminating a protective film on one surface of the photosensitive resin layer (on the surface that is not protected and exposed) to form a cylindrical winding or the like. It can be wound on a core and stored in roll form.
  • the core is not particularly limited as long as it is conventionally used.
  • plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc.
  • the support is wound up so as to be the outermost side.
  • an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive resin laminate wound in a roll shape, and in addition, it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. .
  • a moisture-proof end face separator from the viewpoint of edge fusion resistance.
  • the resist pattern is formed by laminating the photosensitive resin laminate so that the photosensitive resin layer is in close contact with the substrate, irradiating it with an actinic ray in an image form, and removing the exposed portion by development. is there.
  • the portion not irradiated with actinic rays does not dissolve in alkali because the photosensitizer containing a 1,2-naphthoquinonediazide group interacts with the alkali-soluble phenol resin and acts as a dissolution inhibitor.
  • the photosensitizer containing 1,2-naphthoquinonediazide group is photolyzed and loses the dissolution inhibiting effect. Thereby, the exposed part irradiated with actinic light becomes alkali-soluble.
  • the photosensitive resin laminate includes a protective film
  • the protective film is removed, and then the photosensitive resin layer is heated to about 70 to 130 ° C. while being heated.
  • Examples thereof include a method of pressure-bonding the material with a laminator or the like at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm 2 ). Such a lamination process may be performed under reduced pressure.
  • the surface of the base material on which the photosensitive resin layer is laminated is not particularly limited.
  • the photosensitive resin layer thus laminated on the substrate is irradiated with actinic rays in an image form through a negative or positive mask pattern to form an exposed portion.
  • the support existing on the photosensitive resin layer is transparent to the actinic ray, the support can be irradiated with the actinic ray, and the support has a light shielding property against the actinic ray.
  • the photosensitive resin layer is irradiated with actinic rays after removing the support.
  • the active light source a conventionally known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, a laser direct drawing exposure method or the like may be used.
  • the photosensitive resin layer in the exposed portion is removed by development to form a resist pattern.
  • a method for removing the exposed portion when a support is present on the photosensitive resin layer, the support is removed with an auto peeler or the like, and wet development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, Alternatively, a method of developing by removing the exposed portion by dry development or the like can be mentioned.
  • alkali used for wet development examples include weak alkali inorganic compounds such as sodium carbonate, potassium carbonate and ammonia; alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; monomethylamine Weakly alkaline organic compounds such as dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine; Examples thereof include methylammonium hydroxide and tetraethylammonium hydroxide.
  • the pH of the alkaline aqueous solution is preferably in the range of 9 to 13, and the temperature is adjusted according to the developability of the photosensitive resin layer. Moreover, you may mix surfactant, an antifoamer, an organic solvent, etc. in alkaline aqueous solution.
  • the development method include a dip method, a spray method, brushing, and slapping.
  • the resist pattern may be cured and used by heating at about 60 to 250 ° C., if necessary. In this way, a resist pattern is obtained.
  • a photosensitive resin layer in which generation of chips is sufficiently prevented is used, contamination of the operating environment of the base material and laminator by chips is sufficiently prevented, and as a result, a resist having sufficiently few defects.
  • a pattern can be formed.
  • the preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the gist thereof.
  • the method for producing a printed wiring board according to the present invention is performed through the following steps following the above-described resist pattern forming method using a copper-clad laminate or a flexible substrate as a substrate.
  • a conductor pattern is formed on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method.
  • the resist pattern is removed again by exposure and development to obtain a desired printed wiring board.
  • the lead frame manufacturing method of the present invention is performed through the following steps following the above-described resist pattern forming method using a metal plate of copper, copper alloy, iron-based alloy or the like as a substrate. First, a conductive pattern is formed by etching the substrate exposed by development. Thereafter, the remaining resist pattern is removed by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.
  • the method for producing a semiconductor package of the present invention is performed by performing the following steps following the above-described resist pattern forming method using a wafer on which a circuit as an LSI has been formed as a substrate.
  • a conductor pattern is formed by performing columnar plating such as copper or solder on the opening exposed by development. Thereafter, the remaining resist pattern is removed by a method similar to the above-described printed wiring board manufacturing method, and a thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.
  • a method for manufacturing a thin film transistor includes, for example, forming a gate electrode having a predetermined shape using a mask on a substrate such as silicon, glass, or a resin sheet, and then forming a gate insulating film by the above-described resist pattern formation method and removal method. Further, a semiconductor thin film layer is formed on the entire surface of the insulating film, and a source electrode and a drain electrode having a predetermined shape are formed on the thin film layer using a mask.
  • A-2 Phenol novolac resin, weight average molecular weight 7,000, molecular weight distribution about 6, (Asahi Organic Materials Co., Ltd., PAPS-PN70 (trade name))
  • B-1 6,4 ′-(1- ⁇ 4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl ⁇ ethylidene) bisphenol) 6-diazo-5,6-dihydro-5-oxo -1-Naphthalenesulfonic acid mono-, di- or triester (PA-3 (trade name) manufactured by Daitokemix Co., Ltd.)
  • B-2 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid mono-, di-, tri- or tetraester of 2,3,4,4'-tetrahydroxybenzophenone (manufactured by Daitokemix Co., Ltd.) DTEP-250 (trade name))
  • C-1 Polyparahydroxystyrene, weight average molecular weight 20,000, (Chemway Co., Ltd., Markalinker MH-2P (trade name))
  • Uniol DAB-800 manufactured by NOF Corporation
  • D-7 Compound having three moles of propylene glycol at both ends of the bisphenol F compound Sample
  • photosensitive resin laminate The solvent methyl ethyl ketone is added to the photosensitive resin composition having the composition shown in Tables 1 and 2 until the solid content becomes 50% by mass, and the mixture is thoroughly stirred and mixed.
  • the solution of the photosensitive resin composition is polyethylene terephthalate having a thickness of 25 ⁇ m.
  • the film was uniformly applied using a bar coater and dried for 2 minutes in a 90 ° C. dryer to form a photosensitive resin layer having a thickness of 10 ⁇ m.
  • a 30 ⁇ m thick polyethylene film was laminated on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.
  • the substrate for evaluation was a 0.4 mm thick copper clad laminate on which 35 ⁇ m rolled copper foil was laminated, and the surface was jet scrubbed with a spray pressure of 0.20 MPa (Nippon Carlit Co., Ltd., Sacradund R (registered trademark)) # 220) was prepared.
  • laminate While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Electronics Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. .
  • the air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
  • the support was peeled off, and the evaluation substrate was projected and exposed with an exposure machine (projection exposure apparatus UX2003SM-MS04: manufactured by Ushio Inc.) having an ultrahigh pressure mercury lamp using a chromium glass photomask.
  • developing The obtained evaluation substrate was developed by a dipping method at a temperature of 20 ° C. using a 2.38 mass% aqueous solution of tetoramethylammonium as an alkaline developer. Thereafter, it was washed with pure water by a dip method for about 20 seconds at a temperature of 20 ° C. and dried with a drier.
  • Chip evaluation The photosensitive resin laminate having the support side as the upper surface was cut into 10 centimeters in a straight line using an NT cutter, and the cut portion and its periphery were visually observed. The evaluation results of the chip test were ranked as follows. A: No generation of chips B: Generation of chips and evaluation of sensitivity: As a result of passing through the “exposure” step and the above “development” step every 200 mJ / cm 2 to 100 mJ / cm 2 , the exposure amount capable of forming the best pattern was 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 with an exposure amount of 1,500 mJ / cm 2 and developed. The state where the completely exposed photosensitive resin layer was removed was visually confirmed, and the time taken to reach that state was defined as the minimum development time.
  • Evaluation of pattern formation It was exposed and developed through a chrome glass photomask having a pattern with 1: 1 lines and spaces. When developing for 1.2 times the minimum development time, it was visually observed whether the line portion and the space portion were clearly separated, and was ranked as follows. A: Line and space are clearly separated B: Line and space are not separated
  • the present invention relates to the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the manufacture of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA and CSP, the manufacture of tape substrates such as COF and TAB, the production of semiconductor bumps It can be used for manufacturing, manufacturing of partition walls of flat panel displays such as ITO electrodes, address electrodes and electromagnetic wave shields, and methods of processing a substrate by sandblasting. Examples of the processing by the sandblasting method include organic EL glass cap processing, drilling processing of a silicon wafer, and ceramic pinning processing.
  • the processing by the sand blasting process of the present invention can be used for manufacturing an electrode of a metal material layer selected from the group consisting of a ferroelectric film and a noble metal, a noble metal alloy, a refractory metal, and a refractory metal compound.

Abstract

L'invention concerne une composition de résine photosensible permettant la formation d'un motif sur cette dernière, et pouvant être formée sous forme d'un film sec souple qui produit une quantité suffisamment réduite de poussières de découpe lorsque ledit film est découpé. L'invention concerne plus spécifiquement : une composition de résine photosensible comprenant (A) une résine phénolique alcalino-soluble, (B) un agent photosensibilisant comprenant un groupe 1,2-naphthoquinonediazide, et (C) une résine alcalino-soluble comprenant un groupe dérivé d'un composé hydroxy aromatique dans une chaîne latérale; et/ou une composition de résine photosensible comprenant (A) une résine phénolique alcalino-soluble, (B) un agent photosensibilisant comprenant un groupe 1,2-naphthoquinonediazide, et (D) un composé qui est induit à partir d'au moins un composé sélectionné dans le groupe constitué par bisphénol A, bisphénol E, bisphénol F, bisphénol S et un composé produit par hydrogénation de l'un quelconque des composés précités et qui comprend au moins un groupe hydroxy au niveau de la terminaison.
PCT/JP2009/057081 2008-04-10 2009-04-06 Composition de résine photosensible et stratifié de résine photosensible comprenant ladite composition WO2009125752A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010507240A JP5155389B2 (ja) 2008-04-10 2009-04-06 感光性樹脂組成物及びそれを用いた感光性樹脂積層体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2008-102038 2008-04-10
JP2008102038 2008-04-10
JP2008102036 2008-04-10
JP2008-102036 2008-04-10

Publications (1)

Publication Number Publication Date
WO2009125752A1 true WO2009125752A1 (fr) 2009-10-15

Family

ID=41161884

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/057081 WO2009125752A1 (fr) 2008-04-10 2009-04-06 Composition de résine photosensible et stratifié de résine photosensible comprenant ladite composition

Country Status (3)

Country Link
JP (2) JP5155389B2 (fr)
TW (1) TWI398725B (fr)
WO (1) WO2009125752A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2400344A1 (fr) * 2010-06-28 2011-12-28 Everlight USA, Inc. Composition de photoréserve positive
JP2015166866A (ja) * 2014-02-12 2015-09-24 日立化成株式会社 感光性エレメント
WO2018117047A1 (fr) * 2016-12-20 2018-06-28 旭化成株式会社 Rouleau à couche photosensible à deux couches
JP2020020978A (ja) * 2018-08-01 2020-02-06 旭化成株式会社 感光性樹脂組成物及びそれを用いた感光性樹脂積層体
JP2020071280A (ja) * 2018-10-30 2020-05-07 住友ベークライト株式会社 感光性樹脂組成物および電子デバイスの製造方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6641217B2 (ja) * 2016-03-30 2020-02-05 東京応化工業株式会社 金属酸化物膜形成用塗布剤及び金属酸化物膜を有する基体の製造方法
WO2019088268A1 (fr) 2017-11-06 2019-05-09 旭化成株式会社 Stratifié de résine photosensible et procédé de production d'un motif de réserve
KR101920783B1 (ko) * 2018-03-14 2018-11-21 동우 화인켐 주식회사 감광성 수지 조성물 및 이를 사용한 패턴 형성 방법

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0348249A (ja) * 1989-04-19 1991-03-01 Nippon Zeon Co Ltd ポジ型レジスト組成物
JPH06194835A (ja) * 1992-12-24 1994-07-15 Sumitomo Chem Co Ltd カラーフィルター用レジスト組成物
JPH10147561A (ja) * 1997-12-01 1998-06-02 Jsr Corp １，２−ナフトキノンジアジド化合物の製造方法および該製造方法により得られた１，２−ナフトキノンジアジド化合物を含有する感放射線性樹脂組成物
JP2002341525A (ja) * 2001-05-14 2002-11-27 Fuji Photo Film Co Ltd ポジ型フォトレジスト転写材料およびそれを用いた基板表面の加工方法
JP2004170953A (ja) * 2002-11-01 2004-06-17 Sumitomo Chem Co Ltd 着色感光性樹脂組成物およびそれを用いたカラーフィルタ
JP2005215137A (ja) * 2004-01-28 2005-08-11 Fuji Photo Film Co Ltd 感光性樹脂組成物、感光性転写材料、液晶配向制御用突起及びその製造方法、並びに液晶表示装置
JP2005221726A (ja) * 2004-02-05 2005-08-18 Fuji Photo Film Co Ltd 感光性転写材料、液晶配向制御用突起及びその形成方法、並びに、液晶表示装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4655882B2 (ja) * 2004-10-29 2011-03-23 Ｊｓｒ株式会社 ポジ型感光性絶縁樹脂組成物およびその硬化物
KR101240643B1 (ko) * 2005-07-08 2013-03-08 삼성디스플레이 주식회사 포토레지스트 조성물, 상기 포토레지스트 조성물을 이용한 패턴의 형성 방법 및 이를 이용한 박막 트랜지스터표시판의 제조 방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0348249A (ja) * 1989-04-19 1991-03-01 Nippon Zeon Co Ltd ポジ型レジスト組成物
JPH06194835A (ja) * 1992-12-24 1994-07-15 Sumitomo Chem Co Ltd カラーフィルター用レジスト組成物
JPH10147561A (ja) * 1997-12-01 1998-06-02 Jsr Corp １，２−ナフトキノンジアジド化合物の製造方法および該製造方法により得られた１，２−ナフトキノンジアジド化合物を含有する感放射線性樹脂組成物
JP2002341525A (ja) * 2001-05-14 2002-11-27 Fuji Photo Film Co Ltd ポジ型フォトレジスト転写材料およびそれを用いた基板表面の加工方法
JP2004170953A (ja) * 2002-11-01 2004-06-17 Sumitomo Chem Co Ltd 着色感光性樹脂組成物およびそれを用いたカラーフィルタ
JP2005215137A (ja) * 2004-01-28 2005-08-11 Fuji Photo Film Co Ltd 感光性樹脂組成物、感光性転写材料、液晶配向制御用突起及びその製造方法、並びに液晶表示装置
JP2005221726A (ja) * 2004-02-05 2005-08-18 Fuji Photo Film Co Ltd 感光性転写材料、液晶配向制御用突起及びその形成方法、並びに、液晶表示装置

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI485521B (zh) * 2010-06-28 2015-05-21 Everlight Chem Ind Corp 正型感光樹脂組成物
EP2400344A1 (fr) * 2010-06-28 2011-12-28 Everlight USA, Inc. Composition de photoréserve positive
US10345704B2 (en) 2014-02-12 2019-07-09 Hitachi Chemical Company, Ltd. Photosensitive element
JP2015166866A (ja) * 2014-02-12 2015-09-24 日立化成株式会社 感光性エレメント
CN110088680A (zh) * 2016-12-20 2019-08-02 旭化成株式会社 双层感光层卷
KR20190085077A (ko) * 2016-12-20 2019-07-17 아사히 가세이 가부시키가이샤 2 층 감광층 롤
WO2018117047A1 (fr) * 2016-12-20 2018-06-28 旭化成株式会社 Rouleau à couche photosensible à deux couches
JPWO2018117047A1 (ja) * 2016-12-20 2019-08-08 旭化成株式会社 ２層感光層ロール
KR102293963B1 (ko) * 2016-12-20 2021-08-25 아사히 가세이 가부시키가이샤 2 층 감광층 롤
JP2020020978A (ja) * 2018-08-01 2020-02-06 旭化成株式会社 感光性樹脂組成物及びそれを用いた感光性樹脂積層体
JP7076329B2 (ja) 2018-08-01 2022-05-27 旭化成株式会社 感光性樹脂組成物及びそれを用いた感光性樹脂積層体
JP2020071280A (ja) * 2018-10-30 2020-05-07 住友ベークライト株式会社 感光性樹脂組成物および電子デバイスの製造方法
JP7338142B2 (ja) 2018-10-30 2023-09-05 住友ベークライト株式会社 感光性樹脂組成物および電子デバイスの製造方法

Also Published As

Publication number Publication date
JP5155389B2 (ja) 2013-03-06
JPWO2009125752A1 (ja) 2011-08-04
TWI398725B (zh) 2013-06-11
TW201001066A (en) 2010-01-01
JP2013054363A (ja) 2013-03-21

Similar Documents

Publication Publication Date Title
JP3710717B2 (ja) 厚膜用ポジ型ホトレジスト組成物、ホトレジスト膜およびこれを用いたバンプ形成方法
JP5155389B2 (ja) 感光性樹脂組成物及びそれを用いた感光性樹脂積層体
JP4600477B2 (ja) 感光性樹脂組成物及び感光性エレメント
JP6323337B2 (ja) 感光性樹脂組成物及びこれを用いた感光性フィルム
JP4899986B2 (ja) ２層積層膜およびこれを用いたパターン形成方法
JP4840068B2 (ja) 感光性樹脂組成物及び感光性エレメント
JP2012252095A (ja) ポジ型感光性樹脂組成物及び感光性フィルム
KR20080049141A (ko) 포지티브형 포토레지스트 조성물 및 이것을 이용한포토레지스트 패턴 형성 방법
JP5741179B2 (ja) 感光性フィルム
JP2013228416A (ja) ポジ型感光性樹脂組成物及びこれを用いた感光性フィルム
JP7076329B2 (ja) 感光性樹脂組成物及びそれを用いた感光性樹脂積層体
JP7340329B2 (ja) 感光性樹脂積層体及びレジストパターンの製造方法
JP2004219536A (ja) 感光性樹脂組成物、回路形成用基板、レジストパターンの製造法、プリント配線板の製造法
JP5076611B2 (ja) 電極パターンの形成方法
JP2010039214A (ja) 感光性樹脂組成物及びこれを用いた感光性エレメント
JP7376989B2 (ja) 感光性樹脂組成物及びそれを用いた感光性樹脂積層体
JP7340328B2 (ja) 感光性樹脂組成物
JP5592064B2 (ja) ポジ型レジスト組成物
JP2003303692A (ja) インクジェット方式による有機ｅｌ表示素子の絶縁膜形成に用いる感放射線性樹脂組成物、それから形成された有機ｅｌ表示素子の絶縁膜、および有機ｅｌ表示素子
KR101291935B1 (ko) 필름형 광분해성 전사재료
JP2005037712A (ja) パターン化されたレジスト膜の製造方法、レジスト膜形成済回路形成用基板、及びプリント配線板の製造方法
JP3757408B2 (ja) 硬化膜、電子部品用膜およびその製造法
JP2007272138A (ja) レジストパターン形成方法及び感光性樹脂組成物
JP2008241798A (ja) 新規なポジ型感光性樹脂組成物を用いるレジストパターン形成方法
JP2008241797A (ja) 新規なポジ型感光性樹脂組成物を用いるレジストパターン形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09729683

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2010507240

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09729683

Country of ref document: EP

Kind code of ref document: A1