TWI685714B - Chemically-amplified type positive photo sensitive resin composition, method for manufacturing substrate with casting mold, and method for manufacturing plating molded article - Google Patents

Abstract

A chemically-amplified type positive photosensitive resin composition with excellent sensitivity and rectangularity, a method for manufacturing substrate with casting mold, and a method for manufacturing plating molded article are provided.  The chemically-amplified type positive photosensitive resin composition includes a resin (A) with acid-dissociated protecting group and obtained by polymerizing a mixture, a novolac resin (B), a photoacid generator (C), and a solvent(D).  The novolac resin (B) includes a high-ortho novolac resin (B-1), which 18%~25% of methylene group in the resin is bonded in ortho-ortho arrangement.

Description

Method of manufacturing chemically amplified positive photosensitive resin composition, substrate with mold, and method of manufacturing electroplated molded body

The present invention relates to a method of manufacturing a chemically amplified positive photosensitive resin composition, a substrate with a mold, and a method of manufacturing an electroplated molded body, and particularly relates to a chemical capable of improving the problems of poor sensitivity and rectangularity Amplified positive photosensitive resin composition, method for manufacturing a mold-attached substrate made from the chemically amplified positive photosensitive resin composition, and an electroplated molded body made from the mold-attached substrate Manufacturing method.

Today, optoelectronic processing has become the mainstream of precision microfabrication technology. The so-called "photoelectric processing" refers to applying a photoresist composition on the surface of the object to form a photoresist layer, using photolithography technology to pattern the photoresist layer, and then patterning the photoresist layer (light (Resistance pattern) is a general term for the technology of manufacturing various precision parts such as semiconductor packages by chemical etching, electrolytic etching, or electroforming with electroplating as the main part of the mask.

In addition, in recent years, with the miniaturization of electronic devices, the high-density assembly technology of semiconductor packages has progressed rapidly, and the assembly of multi-pin thin films of packages, the miniaturization of package sizes, and the two-dimensional assembly of flip chip systems have been sought. Technology, three-dimensional assembly technology to improve the assembly density. In such high-density assembly technology, as connection terminals, for example, protruding electrodes (assembly terminals) for connecting bumps protruding toward the package, rewiring and assembly terminals extending from peripheral terminals on the wafer The metal pillars are placed on the substrate with high precision.

The photoelectric processing system described above uses a photoresist composition. As such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (refer to Patent Documents 1, 2 and the like). The chemically amplified photoresist composition generates an acid from an acid generator by radiation irradiation (exposure), promotes the diffusion of the acid through heat treatment, and causes an acid catalyst reaction with the matrix resin in the composition to change its alkali dissolution Sex.

Such a chemically amplified positive photoresist composition is used, for example, in forming a plated body such as bumps or metal pillars in a plating step. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired film thickness on a support such as a metal substrate, and exposure and development are performed through a predetermined mask pattern to form light used as a template The resist pattern in which the portion where the bump or the metal pillar is to be formed is selectively removed (stripped). After that, a conductor such as copper is embedded in the removed portion (non-photoresist portion) by plating, and then the photoresist pattern around it is removed to form a bump or a metal pillar.

However, the aforementioned chemically amplified positive photoresist composition has the disadvantages of poor sensitivity and poor rectangularity of the formed photoresist pattern, which cannot be accepted by the industry. Therefore, how to provide a chemically amplified positive electrode that can form a photoresist pattern with good sensitivity and rectangularity The photoresist composition is actually a problem that those skilled in the art urgently want to solve.

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 9-176112

[Patent Document 2] Japanese Patent Laid-Open No. 11-52562

In view of this, the present invention provides a chemically amplified positive photosensitive resin composition, and the use of the chemically amplified positive photosensitive resin composition can improve the problems of poor sensitivity and rectangularity.

The invention provides a chemically amplified positive photosensitive resin composition, comprising: a resin (A), which is obtained by copolymerization of a monomer mixture, and contains an acid dissociable protective group, a novolac resin (B), and a photoacid generator (C) and the solvent (D), the above novolak resin (B) includes high ortho-position novolak resin (B-1), and the high ortho-position novolak resin (B-1) has an extension of 18% to 25% The methyl group is bonded to the ortho-ortho position.

In an embodiment of the present invention, the above monomer mixture includes a monomer (a1) and has a structure represented by the following formula (A-1):

In formula (A-1), L ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched group having 1 to 6 carbon atoms Fluorinated alkyl groups; L ² , L ³ , and L ⁴ independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms Fluoroalkyl group, or L ³ and L ⁴ are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms.

In an embodiment of the present invention, the above monomer mixture includes a monomer (a2), and the monomer (a2) contains a cyclic ether group.

In an embodiment of the present invention, the aforementioned chemically amplified positive photosensitive resin composition further includes a thiol compound (E) and has a structure represented by the following formula (E-1):

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents a single bond or an alkylene group having 1 to 10 carbon atoms, R ⁴ Represents an u-valent organic group; u represents an integer from 2 to 6.

In an embodiment of the present invention, the aforementioned chemically amplified positive photosensitive resin composition further includes an anthracene compound (F).

In an embodiment of the present invention, based on the total usage of the resin (A) is 100 parts by weight, the usage of the novolak resin (B) is 20 to 150 parts by weight, and the use of the photoacid generator (C) The amount is 0.5 to 5 parts by weight, and the amount of the solvent (D) used is 30 to 360 parts by weight.

In an embodiment of the present invention, based on the total usage of the resin (A) is 100 parts by weight, the usage of the high ortho-position novolak resin (B-1) is from 20 to 120 parts by weight.

In an embodiment of the present invention, based on the total usage of the monomer mixture is 100 parts by weight, the usage of the monomer (a1) is 10 to 60 parts by weight.

In an embodiment of the present invention, based on the total usage amount of the monomer mixture is 100 parts by weight, the usage amount of the monomer (a2) is 5 to 30 parts by weight.

In an embodiment of the present invention, based on the total amount of resin (A) used is 100 parts by weight, and the amount of thiol compound (E) used is 0.3 parts by weight to 3 parts by weight.

In an embodiment of the present invention, based on the total amount of resin (A) used is 100 parts by weight, and the amount of anthracene compound (F) used is 0.2 parts by weight to 1.5 parts by weight.

The present invention also provides a method for manufacturing a substrate with a mold, including: a laminating step, on the metal surface of a substrate having a metal surface, laminating a photosensitive composition composed of the chemically amplified positive photosensitive resin composition as described above In the resin layer, the exposure step, the photosensitive resin layer is irradiated with active light or radiation, and the development step, the exposed photosensitive resin layer is developed, and a mold for forming an electroplated molded body is formed.

The present invention further provides a method of manufacturing an electroplated molded body, which includes the steps of forming a plated molded body in the mold by performing electroplating on the mold-attached substrate manufactured by the above-described mold-attached substrate manufacturing method.

Based on the above, the chemically amplified positive photosensitive resin composition of the present invention contains a high ortho-position novolak resin (B-1) having 18% to 25% of methyl groups bonded to the ortho-ortho position, Therefore, the problem of poor sensitivity and rectangularity can be improved.

In order to make the above features and advantages of the present invention more obvious and understandable, The embodiments are described in detail in conjunction with the attached drawings as follows.

100‧‧‧ substrate

120‧‧‧Photoresist pattern

122‧‧‧Photoresist

124‧‧‧non-photoresist

L _b ‧‧‧ bottom width

L _t ‧‧‧Top width

FIG. 1 is a schematic diagram of measuring the rectangularity of a photoresist pattern.

<Chemical amplification type positive photosensitive resin composition>

The invention provides a chemically amplified positive photosensitive resin composition, comprising: a resin (A), which is obtained by copolymerization of a monomer mixture, and contains an acid dissociable protective group, a novolac resin (B), and a photoacid generator (C) and the solvent (D), the above novolak resin (B) includes high ortho-position novolak resin (B-1), and the high ortho-position novolak resin (B-1) has an extension of 18% to 25% The methyl group is bonded to the ortho-ortho position. In addition, the chemically amplified positive photosensitive resin composition of the present invention may further contain a thiol compound (E), an anthracene compound (F), and an additive (G).

Hereinafter, each component of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail.

It is explained here that in the following, (meth)acrylic acid means acrylic acid and/or methacrylic acid, and (meth)acrylic acid ester means acrylate and/or methacrylic acid ester; similarly, (meth)acrylic acid Acryloyl means acryloyl and/or methacryloyl.

Resin (A)

The resin (A) is obtained by copolymerization of a monomer mixture and contains an acid-dissociable protective group. Specifically, the monomer mixture may include a monomer (a1) having a structure represented by formula (A-1), a monomer (a2) containing a cyclic ether group, a monomer having a formula (A-2) or ( A-3) The monomer (a3) of the structure shown and other monomers (a4).

Monomer (a1) having a structure represented by formula (A-1)

The monomer (a1) having the structure represented by formula (A-1) is as follows:

In formula (A-1), L ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched group having 1 to 6 carbon atoms Fluorinated alkyl groups; L ² , L ³ , and L ⁴ independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms The fluorinated alkyl group, or L ³ and L ⁴ are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms.

In addition, examples of the linear or branched alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, and isopentyl. Neopentyl, etc. In addition, the fluorinated alkyl group means a part or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms.

When L ³ and L ^{4 are} not bonded to each other to form a hydrocarbon ring, L ² , L ³ and L ^{4 are} preferably linear or branched alkyl groups having 2 to 4 carbon atoms.

The above L ³ and L ⁴ can form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atoms to which they are bonded. As a specific example of such an aliphatic cyclic group, a group in which one or more hydrogen atoms are removed from polycycloalkanes such as monocycloalkanes, dicycloalkanes, tricycloalkanes, and tetracycloalkanes can be given. Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornene, tricyclodecane, and tetracyclododecane. Wait for polycycloalkane to remove more than one hydrogen atom. In particular, a group in which one or more hydrogen atoms are removed from cyclohexane and adamantane (which may further have a substituent) is preferred.

In addition, when the aliphatic cyclic group formed by the above L ³ and L ⁴ has a substituent on the ring skeleton, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom ( =O) and other polar groups, or linear or branched alkyl groups having 1 to 4 carbon atoms. As a polar group, an oxygen atom (=O) is particularly preferred.

As specific examples of the monomer (a1) having the structure represented by the formula (A-1), the following compounds represented by the formula (A-1-1) to the formula (A-1-33) can be cited:

In formula (A-1-1) to formula (A-1-33), L ¹¹ represents a hydrogen atom or a methyl group.

Based on the total amount of the monomer mixture being 100 parts by weight, the usage amount of the monomer (a1) is 10 to 60 parts by weight, preferably 12 to 55 parts by weight, more preferably 15 to 50 parts by weight .

When the monomer mixture (a1) having the structure represented by the formula (A-1) is included in the monomer mixture, the rectangularity of the chemically amplified positive photosensitive resin composition can be further improved.

Monomer containing cyclic ether group (a2)

Examples of the cyclic ether group-containing monomer (a2) include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, -3,4-epoxy (meth)acrylic acid Butyl ester, (meth)acrylic acid-6,7-epoxyheptyl ester, (meth)acrylic acid-3,4-epoxycyclohexyl ester or (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester Three-membered ring class; 3-(meth)acryloyloxymethyl propylene oxide (3-[(meth)acryloyloxymethyl]oxetane), 3-(meth)acryloyloxymethyl-3-ethyl ring Oxypropane, 3-(meth)acryloyloxymethyl-2-methylpropylene oxide, 3-(meth)acryloyloxymethyl-2-trifluoromethylpropylene oxide, 3-(methyl ) Acryloyloxymethyl-2-pentafluoroethyl propylene oxide, 3-(meth)acryloyloxymethyl-2-phenylpropylene oxide, 3-(meth)acryloyloxymethyl-2 ,2-difluoropropylene oxide, 3-(meth)acryloyloxymethyl-2,2,4-trifluoropropylene oxide, 3-(meth)acryloyloxymethyl-2,2,4 ,4-tetrafluoropropylene oxide, 3-(meth)acryloxyethyloxypropylene oxide, 3-(meth)acryloxyethyl-3-ethylpropylene oxide, 2-ethyl-3 -(Meth)acryloyloxyethyloxypropylene oxide, 3-(meth)acryloyloxyethyl-2-trifluoromethylpropylene oxide, 3-(meth)acryloyloxyethyl-2-propylene Pentafluoroethyl propylene oxide, 3-(meth)acryloyloxyethyl-2-phenyloxypropylene, 2,2-difluoro-3-(meth)acryloyloxyethyloxypropylene, 3-(meth)acryloyloxyethyl-2,2,4-trifluoropropylene oxide, 3-(meth)acryloyloxyethyl-2,2,4,4-tetrafluoropropylene oxide, 2-(meth)acryloyl oxymethyl propylene oxide, 2-methyl-2-(meth)acryloyl oxymethyl propylene oxide, 3-methyl-2-(meth)acryloyl oxypropylene Propylene oxide, 4-methyl-2-(methyl Group) Acryloyloxymethyloxypropylene, 2-(meth)acryloyloxymethyl-2-trifluoromethylpropylene oxide, 2-(meth)acryloyloxymethyl-3-trifluoromethyl Propylene oxide, 2-(meth)acryloyloxymethyl-4-trifluoromethylpropylene oxide, 2-(meth)acryloyloxymethyl-2-pentafluoroethyl propylene oxide, 2 -(Meth)acryloyloxymethyl-3-pentafluoroethyl propylene oxide, 2-(meth)acryloyloxymethyl-4-pentafluoroethyl propylene oxide, 2-(meth)propylene Acetyloxymethyl-2-phenylepoxypropane, 2-(meth)acryloyloxymethyl-3-phenylepoxypropane, 2-(meth)acryloyloxymethyl-4-phenyl ring Oxypropane, 2,3-difluoro-2-(meth)acryloyloxymethylpropylene oxide, 2,4-difluoro-2-(meth)acryloyloxymethylpropylene oxide, 3,3 -Difluoro-2-(meth)acryloyloxymethyl propylene oxide, 2,4-difluoro-2-(meth)acryloyloxymethyl propylene oxide, 3,4-difluoro-2- (Meth)acryloyloxymethylpropylene oxide, 4,4-difluoro-2-(meth)acryloyloxymethylpropylene oxide, 2-(meth)acryloyloxymethyl-3,3 ,4-trifluoropropylene oxide, 2-(meth)acryloyloxymethyl-3,4,4-trifluoropropylene oxide, 2-(meth)acryloyloxymethyl-3,3,4 ,4-tetrafluoropropylene oxide, 2-(meth)acryloyloxyethylpropylene oxide, 2-(meth)acryloyloxyethyl-2-methylpropylene oxide, 2-(methyl) Acryloyloxyethyl-4-methyloxypropylene, 2-(meth)acryloyloxyethyl-2-trifluoromethylpropylene oxide, 2-(meth)acryloyloxyethyl-3- Trifluoromethyl propylene oxide, 2-(meth)acryloyloxyethyl-4-trifluoromethylpropylene oxide, 2-(meth)acryloyloxy-2-pentafluoroethyl epoxy Propane, 2-(meth)acryloyloxyethyl-3-pentafluoroethyl propylene oxide, 2-(meth)acryloyloxyethyl-4-pentafluoroethyl propylene oxide, 2-(methyl ))Acryloyloxyethyl-2-phenyloxypropylene, 2-(meth)acryloyloxyethyl-3-phenylpropylene oxide, 2-(meth)acryloyloxyethyl-4- Phenyl propylene oxide, 2,3-difluoro-2-(meth)acryloyloxypropylene oxide, 2,4-difluoro-2-(meth)acryloyloxypropylene oxide, 3,3-difluoro-2-(meth)propene Acetyloxypropylene oxide, 3,4-difluoro-2-(meth)acrylic acid ethyloxypropylene oxide, 4,4-difluoro-2-(meth)acrylic acid ethyleneoxypropylene Propane, 2-(meth)acryloyloxyethyl-3,3,4-trifluoropropylene oxide, 2-(meth)acryloyloxyethyl-3,4,4-trifluoropropylene oxide, 4-membered rings such as 2-(meth)acryloyloxyethyl-3,3,4,4-tetrafluoropropylene oxide; (meth)acrylic acid tetrahydrofuran, caprolactone-modified (methyl ) Tetrahydrofuran acrylate, (2-methyl-2-isobutyl-1,3-dioxol-4-yl)methyl (meth)acrylate ((2-methyl-2-isobutyl-1, 3-dioxolan-4-yl)methyl(meth)acrylate), (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate ((2 -ethyl-2-methyl-1,3-dioxolan-4-yl)methyl(meth)acrylate), (1,4-dioxospiro[4,5]dec-2-yl)methyl(methyl) Acrylic ester ((1,4-dioxaspiro[4,5]dec-2-yl)methyl(meth)acrylate), (2,2-dimethyl-1,3-dioxol-4-yl)methyl Five-membered rings such as (meth)acrylate ((2,2-dimethyl-1,3-dioxolan-4-yl)methyl(meth)acrylate); (meth)acryloyl morpholine ((meth) Six-membered rings such as acryloyl morpholine), (meth)acrylic acid tetrahydropyranyl ester, (meth)acrylic acid 2-methyltetrahydropyranyl ester and the like. Among them, a cyclic ether acrylate monomer having a four-member ring or more is preferable, and a cyclic ether acrylate monomer having a five-member ring or more is more preferable.

The cyclic ether group-containing monomer (a2) can be used alone or in combination.

Based on the total amount of the monomer mixture being 100 parts by weight, the usage amount of the monomer (a2) is 5 to 30 parts by weight, preferably 8 to 28 parts by weight, more preferably 10 to 25 parts by weight .

If the monomer mixture (a2) containing a cyclic ether group is included in the monomer mixture, the sensitivity of the chemically amplified positive photosensitive resin composition can be further improved.

Monomer (a3) having a structure represented by formula (A-2) or formula (A-3)

The monomer (a3) having the structure represented by formula (A-2) or formula (A-3) is as follows:

In formula (A-2) and formula (A-3), L ⁵ to L ¹⁰ independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a carbon atom The linear or branched fluorinated alkyl group having a number of 1 to 6; Y represents an alicyclic group or alkyl group which may have a substituent, p represents an integer of 0 to 4, and q represents 0 or 1.

In addition, in formulas (A-2) and (A-3), the definitions of linear or branched alkyl groups of L ⁵ to L ¹⁰ and linear or branched fluorinated alkyl groups are as defined above The linear or branched alkyl group defined by L ¹ in formula (A-1) is the same as the linear or branched fluorinated alkyl group, and will not be repeated here.

When Y is an alicyclic group or an alkyl group, a group in which one or more hydrogen atoms are removed from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes can be given. Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or adamantane, norbornane, isobornene, tricyclodecane, and tetracyclododecane. Wait for the polycycloalkane to remove 1 The base of the hydrogen atom. In particular, a group in which one or more hydrogen atoms are removed from adamantane (which may further have a substituent) is preferable.

Furthermore, when the alicyclic group represented by Y has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O), or Linear or branched alkyl group with 1 to 4 carbon atoms. As a polar group, an oxygen atom (=O) is particularly preferred.

In addition, when Y is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferably alkoxyalkyl groups. Examples of such alkoxyalkyl groups include 1-methoxyethyl, 1-ethoxyethyl, and 1-n-propoxyethyl. Group, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-third butoxyethyl, 1-methoxypropyl, 1-ethyl Oxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl, etc.

Specific examples of the monomer (a3) having a structure represented by formula (A-2) or formula (A-3) include the following formula (A-2-1) to formula (A-2-24) , Compounds represented by formula (A-3-1) to formula (A-3-15):

Of formula (A-2-1) ~ Formula (A-2-24), the formula (A-3-1) of the formula - (A-3-15), L ¹¹ represents a hydrogen atom or a methyl group.

Other monomers (a4)

In the monomer mixture, other monomers (a4) that do not belong to the above-mentioned monomers (a1) to (a3) may be included as long as the effects of the present invention are not affected. The other monomer (a4) is, for example, a well-known radical polymerizable compound or anionic polymerizable compound.

Examples of such a polymerizable compound include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxyethyl amber Acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. with carboxyl groups and ester bonds Of methacrylic acid derivatives; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. ; (Meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester and other (meth)acrylic acid hydroxyalkyl esters; (meth)acrylic acid phenyl ester, (meth)acrylic acid benzyl (Meth) acrylates such as esters; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethyl Vinyl-containing aromatic compounds such as styrene, vinyl toluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene; vinyl-containing aliphatic compounds such as vinyl acetate; butyl Conjugated diolefins such as diene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; propylene amide and methyl Polymerization of acrylamide and other amide bonds Sex compounds etc.

In addition, examples of the polymerizable compound include (meth)acrylates having an acid-dissociative aliphatic polycyclic group, vinyl-containing aromatic compounds, and the like. As the acid-non-dissociative aliphatic polycyclic group, tricyclic decyl group, adamantyl group, tetracyclododecyl group, isobornyl group, norbornyl group, etc. are preferred, and it is preferable from the viewpoint of industrial availability. These aliphatic polycyclic groups may also have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

As the (meth)acrylates having an acid non-dissociative aliphatic polycyclic group, specifically, the following formulas (A-4-1) to (A-4-5) can be exemplified Compound:

In formula (A-4-1) to formula (A-4-5), L ¹¹ represents a hydrogen atom or a methyl group.

Based on the total amount of the monomer mixture being 100 parts by weight, the usage amount of the other monomer (a4) is 20 to 85 parts by weight, preferably 25 to 80 parts by weight Parts, more preferably 30 parts by weight to 75 parts by weight.

Manufacturing method of resin (A)

Solvents used in the preparation of resin (A) include but are not limited to (1) alcohol compounds: methanol, ethanol, benzyl alcohol, 2-phenylethanol, or 3-phenyl-1-propanol, etc.; (2) ether compounds : Tetrahydrofuran, etc.; (3) glycol ether compounds: ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; (4) ethylene glycol alkyl ether acetate: ethylene glycol butyl Ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, etc.; (5) Diethylene glycol compounds: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc.; (6) dipropylene glycol compounds: dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, etc.; (7) Propylene glycol monoalkyl ether compounds: propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; 8) Propylene glycol alkyl ether acetate compounds: Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; (9) propylene glycol alkyl ether propylene Ester compounds: propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc.; (10) aromatic hydrocarbon compounds: toluene, xylene, etc.; (11) Ketone compounds: methyl ethyl ketone, cyclohexanone, diacetone alcohol, etc.; (12) ester compounds: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, glycolic acid Ethyl ester, butyl glycolate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate Ester, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, butyl Ethyl oxyacetate, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate , Butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate , Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate , Butyl 3-butoxypropionate, etc., this solvent can be used alone or mixed.

The polymerization initiator used when preparing the resin (A) includes, but is not limited to, azo compounds or peroxides, and can be used alone or in combination.

Azo compounds such as but not limited to: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) [2,2'-Azobis(2,4 -dimethylvaleronitrile)], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile [2,2'-azobis-2-methyl butyronitrile], 4,4'-azobis (4-cyanovaleric acid), dimethyl 2,2'-azobis (2-methylpropionate) ), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc.

Peroxides such as but not limited to: dibenzoyl peroxide, dodecyl peroxide, third butyl peroxytrivalerate, 1,1-bis(third butyl peroxy) cyclohexane, Hydrogen peroxide, etc.

The reaction temperature when preparing the resin (A) is 40 to 120°C, and the polymerization time is 3 to 12 hours.

The weight average molecular weight of the resin (A) is 5,000 to 50,000; preferably 6,000 to 45,000; more preferably 7,000 to 40,000.

Novolac resin (B)

The novolak resin (B) contains a high ortho-position novolak resin (B-1), and the high-ortho-position novolak resin (B-1) has 18% to 25% of methyl groups bonded to the ortho-ortho position . The novolak resin (B) may optionally contain other novolak resins (B-2).

High ortho-position novolak resin (B-1)

High ortho-position novolak resin (B-1) is generally composed of aromatic hydroxy compounds and aldehydes, in the presence of a divalent metal salt catalyst, under acidic (pH 1 to 5) under reduced pressure dehydration and condensation Get. Secondly, an acid catalyst can be optionally added to carry out the dehydration condensation reaction, and unreacted monomers are removed. The reaction methods disclosed in JP-A 55-090523, JP-A 59-080418 and JP-A 62-230815 will not be repeated here.

Specific examples of the aforementioned aromatic hydroxy compounds are: phenol; m-cresol, m-cresol, p-cresol, or o-cresol, etc. cresol); xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol; m-ethylphenol , P-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol , 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol or 6-tert-butyl-3-methylphenol Alkyl phenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol or m-propoxyphenol, etc. Of alkoxy phenol; o-isopropenyl phenol, p-isopropenyl phenol, 2-methyl-4-isopropenyl phenol or 2-ethyl-4-isopropenyl phenol, etc. Isopropenyl phenols; aryl phenols of phenyl phenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, Polyhydroxyphenols such as hydroquinone or 1,2,3-pyrogallol. The above aromatic hydroxy compounds may be used alone or in combination. Among them, the aromatic hydroxy compound is preferably o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol or 2,3,5-trimethylphenol Wait.

Specific examples of the above aldehydes condensed with aromatic hydroxy compounds, such as formaldehyde, paraformaldehyde, trioxane, acetaldehyde, and propylene Aldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, acrolealdehyde, crotonaldehyde, cyclo hexanealdehyde, furfural, furylacrolein, benzaldehyde, para Terephthal aldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde , M-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde or cinnamaldehyde, etc. The above aldehydes can be used alone or in combination. The aldehyde is preferably formaldehyde.

When preparing the high ortho-position novolak resin (B-1) of the present invention, the molar ratio of the aromatic hydroxy compound and the aldehyde is usually 1:0.5 to 0.85, preferably 1:0.55 to 0.82, more preferably 1: 0.6 to 0.8.

Specific examples of the above divalent metal salt catalyst include zinc acetate, manganese acetate, barium acetate, manganese nitrate, zinc borate, zinc chloride, and zinc oxide. The above divalent metal catalysts can be used alone or in combination. Based on the aromatic hydroxy compound being 100 parts by weight, the usage amount of the divalent metal catalyst is usually 0.01 parts by weight to 1.0 parts by weight, preferably 0.03 parts by weight to 0.8 parts by weight, and more preferably 0.05 parts by weight to 0.5 parts by weight Copies.

Specific examples of the above acid catalyst include dimethyl sulfate, diethyl sulfate, or dipropyl sulfate. The above acid catalysts can be used alone or in combination. Based on the aromatic hydroxy compound being 100 parts by weight, the amount of the acid catalyst used is usually 0.005 to 1.0 part by weight, preferably 0.008 to 0.8 part by weight, and more preferably 0.01 to 0.5 part by weight.

The high ortho novolak resin (B-1) of the present invention generally has 18% to 25% The methylidene group is bonded to the ortho-ortho position, preferably 19% to 25% of the methylidene bond is bonded to the ortho-to-ortho position, and more preferably 20% to 25% The base bond is in the ortho-ortho position.

The weight average molecular weight of the high ortho-position novolak resin (B-1) is 4,000 to 36,000; preferably 5,000 to 30,000; more preferably 6,000 to 24,000.

Based on the total amount of resin (A) used is 100 parts by weight, the amount of high ortho-position novolak resin (B-1) used is 20 parts by weight to 120 parts by weight, preferably 25 parts by weight to 110 parts by weight, more preferably From 30 parts by weight to 100 parts by weight.

When the high-position novolak resin (B-1) is not included in the chemically amplified positive photosensitive resin composition, the rectangularity of the chemically amplified positive photosensitive resin composition is not good.

Other novolac resin (B-2)

Other novolak resins (B-2) are generally composed of the aforementioned aromatic hydroxy compounds and aldehydes, in contact with known organic acids and/or inorganic acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid. In the presence of a medium, the condensation reaction is carried out under normal pressure, and is obtained by dehydration and removal of unreacted monomers. Other novolac resins (B-2) are bonded to methyl groups on the ortho-para position, para-para position, or ortho-o position in a random manner.

Photoacid generator (C)

The photoacid generator (C) is a compound that generates an acid by irradiation of active light or radiation, as long as it is a compound that can directly or indirectly generate an acid by light Yes, no special restrictions. As the photoacid generator (C), the acid generators of the first to fifth aspects described below are preferred. Hereinafter, preferred ones of the photoacid generator (C) suitable for use in the photosensitive resin composition will be described in the first to fifth aspects.

As the first form of the photoacid generator (C), a compound represented by the following formula (C-1) can be mentioned:

In formula (C-1), X ¹ represents a g-valent sulfur atom or an iodine atom, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. W ¹ is an organic group bonded to X ¹ , and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and the number of carbon atoms Is an alkenyl group of 2 to 30, or an alkynyl group of 2 to 30 carbon atoms, and W ¹ may be through an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group , Acetyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkoxy, At least one selected from the group consisting of amine, cyano, nitro, and halogen. The number of W ¹ is g+h(g-1)+1, and W ¹ may be the same or different from each other. Further, two or more W ¹ may be directly bonded to each other, or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NW ² -, -CO-, -COO-, -CONH-, alkylene group having a carbon number of 1 to 3, or phenylene bonded to form a ring structure containing X ¹ is. W ² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ² is a structure represented by the following formula (C-1a);

In formula (C-1a), X ⁴ represents an alkylene group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 8 to 20 carbon atoms, X ^{4 It} can be formed by an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, a nitro group, and a halogen At least one substitution selected from the group. X ⁵ represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NW ² -, -CO-, -COO-, -CONH-, and the number of carbon atoms is 1 to 3. Alkyl or phenylene. h represents the number of repeating units of the structure in parentheses. The h+1 X ⁴ and h X ⁵ may be the same or different. W ² is the same as defined above.

(X ^{3) -} the onium ion (counter ion), may be exemplified by the following formula (C-1b) of FIG fluoroborate fluoroalkyl phosphate anions or the following formula (C-1c) shown in the anion _{^{: [(W 3) j PF}} 6-j] - formula (C-1b)

In formula (C-1b), W ³ represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. j represents its number, which is an integer of 1 to 5. The j W ^3s may be the same or different.

In formula (C-1c), W ⁴ to W ⁷ each independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms in the phenyl group may be selected from at least a group consisting of a fluorine atom and a trifluoromethyl group. 1 kind of replacement.

Examples of the onium ion in the compound represented by formula (C-1) include triphenyl alkane, tri-p-tolyl alkane, 4-(phenylthio)phenyl diphenyl alkane, and bis[4-( Diphenyl alkynyl) phenyl] sulfide, bis[4-{bis[4-(2-hydroxyethoxy) phenyl] amidyl} phenyl] sulfide, bis{4-[bis(4- (Fluorophenyl)amyl]phenyl) sulfide, 4-(4-benzoyl-2-chlorophenylthio) phenyl bis (4-fluorophenyl) alkane, 7-isopropyl-9- Oxygen-10-thia-9,10-dihydroanthracene-2-yldi-p-tolyl alkane, 7-isopropyl-9-oxy-10-thia-9,10-dihydroanthracene- 2-yldiphenylammonium, 2-[(diphenyl)amyl]thioxanthone, 4-[4-(4-tertiary butylbenzyl)phenylthio]phenyldi-p Tolyl benzoyl, 4-(4-benzylphenylthio) phenyl diphenyl amide, diphenyl phenyl ethyl acetoyl amide, 4-hydroxyphenyl methyl benzyl amide, 2-naphthyl methyl (1-ethoxycarbonyl) ethyl alkane, 4-hydroxyphenylmethyl phenethylacetoyl alkane, phenyl [4- (4-biphenylthio) phenyl] 4-biphenyl alkane, phenyl [ 4-(4-biphenylthio) phenyl] 3-biphenyl alkene, [4-(4-acetylphenylthio) phenyl] diphenyl alkene, octadecylmethyl phenethyl alkyl alkane, Diphenyliodonium, di-p-tolylphosphonium, bis(4-dodecylphenyl)phosphonium, bis(4-methoxyphenyl)phosphonium, (4-octyloxyphenyl)phenylphosphonium, bis (4-dodecyloxy)phenylphosphonium, 4-(2-hydroxytetradecyloxy)phenylphenylphosphonium, 4-cumylphenyl (p-tolyl)phosphonium, or 4-isobutylphenyl ( P-tolyl) and so on.

Among the onium ions in the compound represented by the above formula (C-1), examples of preferred onium ions include those of the following formula (C-1d):

In formula (C-1d), W ⁸ independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, an optionally substituted aryl group, an aromatic group A group selected from the group consisting of carbonyl groups. X ² has the same meaning as X ² in the above formula (C-1).

Specific examples of the cerium ions represented by the above formula (C-1d) include 4-(phenylthio)phenyldiphenylcarboxamide and 4-(4-benzoyl-2-chlorophenylthio) ) Phenyl bis (4-fluorophenyl) alkene, 4- (4-benzylphenylthio) phenyl diphenyl alkane, phenyl [4- (4-biphenylthio) phenyl] 4 -Biphenyl benzoyl, phenyl [4-(4-biphenylthio)phenyl] 3-biphenyl benzoyl, [4-(4-acetylphenylthio) phenyl] diphenyl amide, diphenyl [4-(p-triphenylthio)phenyl]diphenyl alkane.

In the fluoroalkyl fluorophosphate anion represented by the above formula (C-1b), W ³ represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; isopropyl, isobutyl, secondary butyl, tertiary butyl Equi-branched alkyl; even cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups, etc., the proportion of hydrogen atoms of the alkyl group substituted by fluorine atoms is usually 80% or more, preferably 90% or more , More preferably 100%. If the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the above formula (C-1) will decrease.

Particularly preferred W ³ is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ and CF ₃ CF ₂ . (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ )CF, (CF ₃ ) ₃ C. The number j of W ^{3 is} an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.

As specific examples of preferred fluoroalkyl fluorophosphate anions, [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , Or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, the best is [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , or [ ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- .

As a preferred specific example of the borate anion represented by the above formula (C-1c), there may be mentioned (pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ), and [(three Fluoromethyl) phenyl] borate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis(pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ) , Trifluoro(pentafluorophenyl) borate ([(C ₆ F ₅ )BF ₃ ] ^- ), (difluorophenyl) borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ), etc. . Among these, Tejia is (pentafluorophenyl) borate ([B(C ₆ F ₅ ) ₄ ] ^- ).

As the second form of the acid generator (A), 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl Group)-6-[2-(2-furanyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furanyl)ethylene Radical] symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl] symmetric triazine, 2,4-bis(trichloromethyl Group)-6-[2-(5-propyl-2-furyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethyl Oxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]symmetric triazine, 2, 4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2 -(3-methoxy-5-ethoxyphenyl)vinyl]symmetric triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propane Oxyphenyl) vinyl] symmetric triazine, 2,4-bis (tri Chloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl] symmetric triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylene (Dimethoxyphenyl) symmetric triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl symmetric triazine, 2,4-bis-trichloromethane Yl-6-(2-bromo-4-methoxy)phenyl symmetric triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl Symmetric triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl Symmetric triazine, 2-(4-methoxyphenyl)-4 ,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5- Triazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl- 2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl] -4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(tri Chloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine , Ginseng (1,3-dibromopropyl)-1,3,5-triazine, ginseng (2,3-dibromopropyl)-1,3,5-triazine and other halogen-containing triazine compounds, And a halogen-containing triazine compound represented by the following formula (C-2) such as ginseng (2,3-dibromopropyl) trimer isocyanate.

In formula (C-2), W ⁹ to W ¹¹ are each independently represented as a haloalkyl group.

In addition, as the third aspect of the photoacid generator (C), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2 ,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4- Methoxyphenylacetonitrile, α-(ethylsulfonylimido)-1-chloropentane The compound represented by the following formula (C-3) containing alkenyl acetonitrile and a sulfoxime group.

In formula (C-3), W ¹² represents a monovalent, divalent, or trivalent organic group, W ¹³ represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group, and n represents a parenthesis The number of repeating units of the structure.

In the above formula (C-3), the aromatic compound group means a group of a compound that shows the unique physical and chemical properties of the aromatic compound, and examples thereof include aryl groups such as phenyl and naphthyl, or furyl and thienyl Wait for heteroaryl. These may also have one or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, and the like. In addition, W ^{13 is} particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. In particular, compounds in which W ¹² is an aromatic compound group and W ¹³ is an alkyl group having 1 to 4 carbon atoms are preferred.

As the acid generator represented by the above formula (C-3), when n=1, a compound in which W ¹² is any of phenyl, methylphenyl, and methoxyphenyl, and W ¹³ is methyl , Specific examples include α-(methanesulfonyloxyimino)-1-phenylacetonitrile, α-(methanesulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(Methanesulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(Prosulfonyloxyimino)-2,3-dihydroxythiophene-3- Subunit] (o-tolyl) acetonitrile, etc. When n=2, as the acid generator represented by the above formula (C-3), specifically, the acids represented by the following formula (C-3-1) to formula (C-3-8) Generator:

In addition, as the fourth aspect of the photoacid generator (C), an onium salt having a naphthalene ring in the cationic portion can be mentioned. This "has a naphthalene ring" means having a structure derived from naphthalene, It means the structure of at least 2 rings and can maintain their aromaticity. The naphthalene ring may also have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, etc. . The structure derived from the naphthalene ring may be a monovalent group (free atomic valence of 1), or a divalent group (free atomic valence of 2) or more, preferably a monovalent group (however, at this time, it is deducted from the above Calculate the free atomic valence of the part where the substituent is bonded). The number of naphthalene rings is preferably 1 to 3.

As the cationic part of such an onium salt having a naphthalene ring as the cationic part, a structure represented by the following formula (C-4) is preferable:

In formula (C-4), at least one of W ¹⁴ to W ¹⁶ represents a group represented by the following formula (C-4a), and the rest represents a linear or branched alkyl group having 1 to 6 carbon atoms , A phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of W ¹⁴ to W ¹⁶ is a group represented by the following formula (C-4a), and the other two are each independently a linear or branched alkylene group having ¹⁴ to ¹⁶ carbon atoms, These ends can be bonded to form a ring.

In formula (C-4a), W ¹⁷ and W ¹⁸ independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear chain having 1 to 6 carbon atoms In the form of a branched or branched alkyl group, W ¹⁸ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m independently represent integers from 0 to 2, and l+m is 3 or less. When there are plural W ^17s , they may be the same or different from each other. When there are plural W ^18s , they may be the same or different from each other.

The number of groups represented by the above formula (C-4a) in the above W ¹⁴ to W ^{16 is} preferably one from the viewpoint of the stability of the compound, and the rest are linear or branched with 1 to 6 carbon atoms Alkyl extension, these ends can be bonded to form a ring. At this time, the above two alkylene groups may contain a sulfur atom to constitute a 3-9 member ring. The number of atoms (sulfur-containing atoms) constituting the ring is preferably 5-6.

In addition, examples of the substituent that the alkylene group may have include an oxygen atom (in this case, together with the carbon atom constituting the alkylene group to form a carbonyl group), a hydroxyl group, and the like.

In addition, examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched group having 1 to 6 carbon atoms. Alkyl and so on.

Suitable examples of these cationic moieties include those represented by the following formulas (C-4b) and (C-4c), and the structure represented by the following formula (C-4c) is particularly preferred.

As such a cationic part, it may be a iodium salt or a monium salt; from the viewpoint of acid generation efficiency and the like, it is more preferably a monium salt.

Therefore, those suitable as anion moieties having an onium salt having a naphthalene ring as the cationic moiety are preferably anions capable of forming a monium salt.

As an anionic part of such an acid generator, a part or all of a hydrogen atom is fluorinated fluoroalkylsulfonate ion or arylsulfonate ion.

The alkyl group in the fluoroalkyl sulfonate ion may be linear, branched or cyclic with 1 to 20 carbon atoms. Based on the volume of the acid generated and its diffusion distance, the number of carbon atoms is preferably 1 To 10. The branched or ring-shaped ones are particularly preferable because the diffusion distance is short. In addition, from the viewpoint of being able to synthesize at low cost, methyl, ethyl, propyl, butyl, octyl and the like are preferred.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted with an alkyl group and a halogen atom. In particular, it is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized inexpensively. Specific examples of preferred ones include phenyl, tosyl, ethylphenyl, naphthyl, and methylnaphthyl.

In the above fluoroalkyl sulfonate ion or aryl sulfonate ion, a part or all of the hydrogen atoms are fluorinated. The fluorination rate is preferably 10 to 100%, more preferably 50 to 100%, especially substituted with fluorine atoms All hydrogen atoms are preferred because the strength of the acid is increased. Those belonging to this category specifically include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among these, preferred as the anionic moiety include (C-4d) are represented by the following formula: W ²⁰ SO ₃ ^- of formula (C-4d)

In formula (C-4d), W ²⁰ is a group represented by the following formulas (C-4e), (C-4f), and (C-4g).

-C _x F _2x+1 (C-4e)

In formula (C-4e), x represents an integer of 1 to 4. In formula (C-4f), W ²¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms Alkoxy, y represents an integer from 1 to 3. Among these, from the viewpoint of safety, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred.

In addition, as the anion portion, nitrogen-containing ones represented by the following formula (C-4h) and formula (C-4i) may also be used.

In formula (C-4h) and formula (C-4i), X ^a represents a linear or branched alkylene group substituted with at least one hydrogen atom by a fluorine atom, and the carbon number of the alkylene group is 2~ 6, preferably 3 to 5, and most preferably 3 carbon atoms. In addition, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. The number of carbon atoms of the alkyl group is 1 to 10, preferably 1 to 7, more Preferably it is 1~3.

The smaller the carbon number of the alkylene group of X ^a or the carbon number of the alkyl group of Y ^a and Z ^a is, the better the solubility in the organic solvent is, which is preferable.

And, X ^a or an alkylene group of Y ^a, Z ^a in the alkyl group, the number of substituted hydrogen atoms in the more fluorine atoms, the stronger acid strength, and therefore preferred. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkylene group in which all hydrogen atoms are replaced by fluorine atoms Radical or perfluoroalkyl.

Those suitable as an onium salt having a naphthalene ring in such a cationic part include compounds represented by the following formula (C-4j) and formula (C-4k):

Furthermore, as the fifth form of the photoacid generator (C), bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, Bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane and other disulfonyldiazomethanes; 2-nitrobenzyl p-toluenesulfonate Ester, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate , Dinitrobenzyl carbonate and other nitrobenzyl derivatives; pyrogallol triflate, pyrogallol tritosylate, benzyl toluenesulfonate, benzyl sulfonate , N-methanesulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methanesulfonyloxy-ortho Sulfonates such as xylylenediimide; trifluoromethanesulfonates such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenylphosphonium hexafluorophosphate, (4 -Methoxyphenyl)phenylphosphonium trifluoromethanesulfonate, bis(p-tertiary butylphenyl)phosphonium trifluoromethanesulfonate Salt, triphenylammonium hexafluorophosphate, (4-methoxyphenyl) diphenylammonium trifluoromethanesulfonate, (p-tertiary butylphenyl) diphenylammonium trifluoromethanesulfonate Isonium salts; benzoin tosylate such as benzoin tosylate, α-methyl benzoin tosylate; other diphenyl iodonium salts, triphenyl alkane salts, phenyl diazonium salts, carbonic acid Benzyl methyl ester etc.

The photoacid generator (C) may be used alone or in combination of two or more. Moreover, based on the total usage of the resin (A) is 100 parts by weight, the usage of the photoacid generator (C) is 0.5 to 5 parts by weight, preferably 0.6 to 4.5 parts by weight, more preferably 0.7 Parts by weight to 4 parts by weight.

Solvent (D)

The type of the solvent (D) is not particularly limited as long as it does not hinder the purpose of the present invention, and can be appropriately selected and used from organic solvents conventionally used for positive photosensitive resin compositions.

Specific examples of the solvent (D) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate , Diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropylene Polyols such as ether, monobutyl ether, monophenyl ether and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, Methyl pyruvate, methyl acetoacetate, ethyl acetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxyl Methyl propionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2- Esters such as methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol methyl ether acetate; toluene, di Aromatic hydrocarbons such as toluene. These can be used alone or in combination of two or more.

The total amount of resin (A) is 100 parts by weight, and the amount of solvent (D) is 30 to 360 parts by weight, preferably 40 to 300 parts by weight, more preferably 50 to 240 parts by weight Copies.

Thiol compound (E)

The thiol compound (E) has a structure represented by the following formula (E-1):

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents a single bond or an alkylene group having 1 to 10 carbon atoms, R ⁴ Represents an u-valent organic group; u represents an integer from 2 to 6.

When R ¹ and R ² are alkyl groups, the alkyl group may be linear or branched, preferably linear. When R ¹ and R ² are alkyl groups, the number of carbon atoms of the alkyl group is preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1. As a combination of R ¹ and R ² , one is preferably a hydrogen atom, the other is an alkyl group, and particularly preferably one is a hydrogen atom and the other is a methyl group.

When R ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When R ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1-10, more preferably 1-5, particularly preferably 1 or 2, and most preferably 1.

The u-valent organic group defined by R ⁴ is specifically a 2 to 6-valent aliphatic group that may contain atoms other than carbon. Examples of atoms other than carbon that R ⁴ may include include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The structure of the aliphatic group to which R ⁴ belongs may be linear, branched, or cyclic, or a combination of these structures.

Among the thiol compounds (E) represented by the formula (E-1), the compounds represented by the following formula (E-2) are more preferable:

In formula (E-2), R ⁴ and u are the same as in formula (E-1), and R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the thiol compound (E) include the following specific examples of formula (E-3) to formula (E-16), but are not limited to these specific examples:

The total amount of the resin (A) used is 100 parts by weight, and the amount of the thiol compound (E) is 0.3 parts by weight to 3 parts by weight, preferably 0.4 parts by weight to 2.8 parts by weight, and more preferably 0.5 parts by weight to 2.5 parts by weight.

When the thiol compound (E) is included in the chemically amplified positive photosensitive resin composition, the rectangularity of the chemically amplified positive photosensitive resin composition can be further improved.

Anthracene (F)

The anthracene compounds (F) may include the following specific examples, but are not limited to these specific examples: anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 2-ethyl -9,10-dimethoxyanthracene, 2-tert-butyl-9,10-dimethoxyanthracene, 2,3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy Yl-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene , 2-ethyl-9,10-dipropoxyanthracene, 2-tert-butyl-9,10-dipropoxyanthracene, 2,3-dimethyl-9,10-dipropoxyanthracene , 9-isopropoxy-10-methylanthracene, 9,10-xyloxyanthracene, 2-ethyl-9,10-xyloxyanthracene, 2-tert-butyl-9,10- Xyloxyanthracene, 2,3-dimethyl-9,10-xyloxyanthracene, 9-tolyl-10-methylanthracene, 9,10-bis-α-methyltolylanthracene , 2-ethyl-9,10-di-α-methyltoluene anthracene, 2-third butyl-9,10-di-α-methyltoluene anthracene, 2,3-dimethyl -9,10-bis-α-methyltolylanthracene, 9-(α-methyltolyloxy)-10-methylanthracene, 9,10-diphenylanthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9-methylanthracene, 9-bromoanthracene, 9-methylthioanthracene, 9-ethylthioanthracene and other compounds.

Based on the total amount of resin (A) used is 100 parts by weight, the amount of anthracene compound (F) used is 0.2 parts by weight to 1.5 parts by weight, preferably 0.25 parts by weight to 1.3 parts by weight, more preferably 0.3 parts by weight to 1.1 parts by weight.

When the chemically amplified positive photosensitive resin composition includes an anthracene compound (F), the sensitivity of the chemically amplified positive photosensitive resin composition can be further improved.

Additive (G)

The chemically amplified positive photosensitive resin composition may further contain an additive (G) as long as it does not affect the effect of the present invention. The additive (G) may be used alone or in combination, depending on actual needs. The specific content of the additive (G) will be described below.

The chemically amplified positive photosensitive resin composition may further contain a polyethylene resin as an additive (G) in order to improve plasticity. Specific examples of polyethylene resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyethylene ether, polyvinyl alcohol, and polyvinylpyrrole. Pyridone, polyvinyl phenol, and these copolymers. The polyethylene resin is preferably polyvinyl methyl ether because of its low glass transition point.

In addition, the chemically amplified positive photosensitive resin composition may further contain an adhesion aid as an additive (G) in order to improve the adhesion between the template formed using the photosensitive resin composition and the metal substrate.

As specific examples of the adjuvant, mention may be made of products manufactured by CYTEC Corporation with the model number of Cymel-300 or Cymel-303; manufactured by Sanwa Chemicals, with model numbers of MW-30MH, MW-30, MS-11, MS-001, Melamine compounds such as MX-750 or MX-706; vinyl trimethoxysilane, vinyl triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-propenyloxypropyl Trimethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2 -Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Propylpropyldimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethane Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis-1,2-(trimethoxysilane Silane compounds such as ethane.

In addition, the chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (G) in order to improve coating properties, defoaming properties, and leveling properties. Specific examples of the surfactant include BM-1000, BM-1100 (all made by BM Chmie), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all made by DIC), FLUORAD FC-135 , FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (all made by Sumitomo 3M), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (all It is manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone) and other commercially available fluorine-based surfactants, but not limited to these.

In addition, the chemically amplified positive photosensitive resin composition may further contain an acid, an acid anhydride, or a high boiling point solvent as an additive (G) in order to fine-tune the solubility of the developer.

Specific examples of acids and anhydrides include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid and other monocarboxylic acids; lactic acid, 2-hydroxybutyric acid, 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 and other hydroxyl groups Monocarboxylic acids; 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 Acid, butane tetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentane tetracarboxylic acid, butane tetracarboxylic acid, 1,2,5,8-naphthalene tetracarboxylic acid and other polycarboxylic acids; Yikang Anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, propane tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3 ,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride , Anhydrides such as glycerol phthalic trimellitic anhydride; etc.

In addition, as specific examples of the high-boiling solvent, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ether, dihexyl ether, acetoneacetone, isophorone, hexanoic acid, caprylic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellulose Acetate, etc.

In addition, the chemically amplified positive photosensitive resin composition may further contain a sensitizer as an additive (G) in order to improve sensitivity.

<Manufacturing method of chemically amplified positive photosensitive resin composition>

The method for producing the chemically amplified positive photosensitive resin composition is not particularly limited, and the above-mentioned components can be mixed and stirred by a usual method. As a device that can be used when mixing and stirring the above-mentioned components, a dissolution machine, Quality machine, three-roll mill, etc. After the above components are uniformly mixed, the resulting mixture may be further filtered using a screen, membrane filter, or the like.

<Manufacturing method of substrate with mold>

Using the above-mentioned chemically amplified positive photosensitive resin composition, a method of forming a photoresist pattern as a mold for forming a plated molded body on the metal surface of a substrate having a metal surface is not particularly limited.

As a preferred method, there may be mentioned a laminating step of laminating a photosensitive resin layer composed of the above-mentioned chemically amplified positive photosensitive resin composition on the metal surface of a substrate having a metal surface; The photosensitive resin layer is irradiated with active light or radiation; and a development step is to develop the photosensitive resin layer after exposure to produce a mold-attached substrate for forming a mold for an electroplated molded body.

The substrate on which the photosensitive resin layer is deposited is not particularly limited, and a conventionally known one can be used. Examples thereof include a substrate for electronic parts or a predetermined wiring pattern formed thereon. For this substrate, a metal surface is used; as the metal species constituting the metal surface, copper, gold, aluminum, and more preferably copper.

The photosensitive resin layer is laminated on the substrate in the following manner, for example. That is, the liquid chemically amplified positive photosensitive resin composition is applied on the substrate, and then the solvent is removed by heating to form a photosensitive resin layer of a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited as long as it can form a photoresist pattern as a template with a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited, but is preferably 10 μm or more, It is more preferably 10 to 150 μm, particularly preferably 20 to 120 μm, and most preferably 20 to 100 μm.

As a coating method of the photosensitive resin composition on the substrate, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and a spreading method can be used. Preferably, the photosensitive resin layer is prebaked. The pre-baking conditions vary depending on the types of components in the photosensitive resin composition, blending ratio, coating film thickness, etc., but are usually 70 to 150°C, preferably 80 to 140°C and 2 to 60 minutes about.

The photosensitive resin layer formed as described above is selectively irradiated (exposed) with active light or radiation such as ultraviolet or visible light with a wavelength of 300 to 500 nm through a mask of a predetermined pattern.

As a radiation source, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc. can be used. In addition, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ rays, electron beams, proton beams, neutron beams, ion beams, and the like. The amount of radiation exposure varies depending on the composition of the photosensitive resin composition or the thickness of the photosensitive resin layer. For example, when an ultra-high pressure mercury lamp is used, it is 100 to 10000 mJ/cm ² . In addition, the radiation contains light that activates the photoacid generator (C) to generate acid.

After exposure, the photosensitive resin layer is heated by a well-known method to promote the diffusion of acid, and the exposed portion of the photosensitive resin film changes the alkali solubility of the photosensitive resin layer.

Next, by developing the photosensitive resin layer after exposure according to a conventional method, and dissolving and removing the soluble portion, a predetermined photoresist pattern is formed. At this time, as the developer, an alkaline aqueous solution is used.

As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiamine Ethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, Aqueous solutions of bases such as 1,5-diazabicyclo[4,3,0]-5-nonane. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the alkali may be used as a developing solution.

The development time varies depending on the composition of the photosensitive resin composition or the thickness of the photosensitive resin layer, etc., and is usually 1 to 30 minutes. The development method may be any of a coating method, a dipping method, a paddle method, and a jet development method.

After development, rinse with running water for 30 to 90 seconds, and dry it with an air spray gun or oven. In this way, a substrate with a mold having a photoresist pattern as a mold on the metal surface of the substrate with a metal surface can be manufactured.

<Manufacturing method of electroplated molded body>

By plating the non-photoresist portion (the portion removed with the developer) in the mold of the substrate with the mold formed by the above method, by plating and embedding a conductor such as metal, a connection terminal such as a bump or a metal post can be formed And the like. In addition, the plating treatment method is not particularly limited, and various conventionally known methods can be used. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solutions are particularly suitable. The residual casting mold is finally removed using a stripping solution or the like in accordance with common methods.

According to the above method, the light that can suppress the undercutting and be used as the mold at the same time is formed Resistance pattern. By using the substrate provided with a casting mold capable of suppressing undercutting in this way, it is possible to produce a plated molded body having excellent adhesion to the substrate.

The present invention will be described in detail with examples below, but the present invention is not limited to the contents disclosed in these examples.

<Example> Synthetic example of resin (A)

The following describes Synthesis Examples A-1 to A-10 of Resin (A):

Synthesis Example A-1

A four-necked conical flask with a volume of 1000 ml is provided with a nitrogen gas inlet, agitator, heater, condenser tube and thermometer. Then, 50 parts by weight of diethylene glycol dimethyl ether was added, and the temperature of the oil bath was raised to 70°C. Next, 15 parts by weight of the compound represented by formula (A-1-26) (abbreviated as (a11)), 10 parts by weight of methacrylic acid (abbreviated as (a41)), and 10 parts by weight of methacrylic acid 2-hydroxyethyl (abbreviated as (a43)), 35 parts by weight of isobornyl methacrylate (abbreviated as (a44)), 30 parts by weight of benzyl methacrylate (abbreviated as (a46)) and 3.5 Weight parts of 2,2'-azobis-2-methylbutyronitrile (abbreviated as AMBN) was added to the four-necked conical flask, and the above mixed solution was slowly stirred. The reaction temperature of the entire polymerization process was maintained at 70°C, and the polymerization time continued for 6 hours. After the polymerization was completed, the polymerization product was taken out from the four-necked conical flask and the solvent was removed to obtain resin (A-1).

Synthesis Examples A-2 to A-10

Synthetic Examples A-2 to A-10 use the same steps as Synthetic Example A-1 to prepare resins (A-2) to (A-10), except that the reaction temperature, reaction time, and type of ingredients are changed And the amount of use, and detailed in Table 1.

In addition, the compounds corresponding to the abbreviations in Synthesis Examples A-1 to A-10 below are shown below.

Synthetic example of novolak resin (B)

The following describes Synthesis Examples B-1-1 to B-1-3 and B-2-1 to B-2-2 of novolak resin (B):

Synthesis Example B-1-1

A nitrogen inlet, agitator, and Heater, condenser and thermometer. After introducing nitrogen, add 64.89g (0.6 mol) of m-cresol, 43.26g (0.4 mol) of p-cresol, 0.5g (0.0028 mol) of manganese acetate and 37% by weight. 48.70 g (0.6 mole) of formaldehyde aqueous solution was slowly stirred and polymerized for 3 hours. Then, 1.38 g (0.01 mol) of salicylic acid was added to adjust the pH to 3.5, and dried under reduced pressure at a pressure of 300 mmHg for 30 minutes. Next, the reaction solution was slowly heated to 150° C. to remove the solvent, and the high ortho-position novolak resin (B-1-1) was prepared.

The obtained high ortho-position novolak resin (B-1-1) was measured by carbon nuclear magnetic resonance ( ¹³ C-NMR) for the number of methyl-extended bonds, and was bonded to the ortho position by the following methyl novolak resin -The evaluation method for the ratio of neighbors is calculated to be 18%.

Synthesis Example B-1-2

A nitrogen inlet, stirrer, heater, condenser, and thermometer are set on a four-necked conical flask with a volume of 1000 ml. After introducing nitrogen, add o-cresol 5.40g (0.05 mol) and m-cresol 64.89g (0.6 Mol), p-cresol 37.86 g (0.35 mol), manganese acetate 0.5 g (0.0028 mol) and 37% by weight aqueous formaldehyde solution 52.75 g (0.65 mol), slowly stirred and polymerized for 3 hours. Then, 1.10 g (0.008 mol) of salicylic acid was added to adjust the pH to 4.0, and dried under reduced pressure under a pressure of 300 mmHg for 30 minutes. Next, the reaction solution was slowly heated to 150°C to remove the solvent, and the high ortho-position novolak resin (B-1-2) was prepared.

The obtained high ortho-position novolak resin (B-1-2) was measured by carbon nuclear magnetic resonance ( ¹³ C-NMR) for the number of methyl-extended bonds, and was bonded to the ortho position by the following methyl-extended methyl novolak resin -The evaluation method for the ratio of neighbors is calculated to be 20%.

Synthesis Example B-1-3

A nitrogen inlet, stirrer, heater, condenser, and thermometer are installed on a four-necked conical flask with a volume of 1000 ml. After introducing nitrogen, m-cresol 64.89g (0.6 mole) and p-cresol 43.26g (0.4 Mol), manganese acetate 0.5g (0.0028 mol) and 37% by weight aqueous formaldehyde solution 56.82g (0.7 mol), slowly stirred and polymerized for 3 hours. Then, 0.37 g (0.003 mol) of benzoic acid was added to adjust the pH to 4.8, and dried under reduced pressure at a pressure of 300 mmHg for 30 minutes, then 0.03 g (0.0002 mol) of dimethyl sulfate was added. Next, the reaction solution is slowly heated to 150° C. to remove the solvent, and the high ortho-position novolak resin (B-1-3) can be prepared.

The obtained high ortho-position novolak resin (B-1-3) was measured by carbon nuclear magnetic resonance ( ¹³ C-NMR) for the number of methyl-extended bonds, and was bonded to the ortho position by the following methyl-extended methyl novolak resin -The evaluation method for the ratio of neighbors is 25%.

Synthesis Example B-2-1

A nitrogen inlet, stirrer, heater, condenser, and thermometer are installed on a four-necked conical flask with a volume of 1000 ml. After introducing nitrogen, m-cresol 64.89g (0.6 mole) and p-cresol 43.26g (0.4 Mol), 1.80 g (0.02 mol) of oxalic acid and 48.70 g (0.6 mol) of 37% by weight aqueous formaldehyde solution, slowly stirred and polymerized for 3 hours. Then, the reaction solution was heated to 150°C to remove the solvent, and the novolak resin (B-2-1) was prepared.

The obtained novolak resin (B-2-1) was measured by carbon nuclear magnetic resonance ( ¹³ C-NMR) for the number of methyl-bonded groups, and was bonded to the ortho-ortho position by the methyl-bonded of the following novolak resin The proportion of the evaluation method is calculated to be 16%.

Synthesis Example B-2-2

A nitrogen inlet, stirrer, heater, condenser, and thermometer were installed on a four-necked conical flask with a volume of 1000 ml. After introducing nitrogen, m-cresol 64.89g (0.6 mole) and p-cresol 32.45g (0.3 Mol), 2,5-xylenol 12.22 g (0.1 mol), oxalic acid 0.90 g (0.01 mol) and 37% by weight aqueous formaldehyde solution 44.64 g (0.55 mol), slowly stirred and polymerized for 3 hours. Then, the reaction solution was heated to 150°C to remove the solvent, and the novolak resin (B-2-2) was prepared.

The obtained novolak resin (B-2-2) was measured by carbon nuclear magnetic resonance ( ^13C -NMR) for the number of methyl-bonded groups, and was bonded to the ortho-ortho position by the methyl-bonded of the following novolak resin The ratio of the evaluation method is calculated to be 14%.

Examples of chemically amplified positive photosensitive resin compositions

The following describes Examples 1 to 14 and Comparative Examples 1 to 4 of the chemically amplified positive photosensitive resin composition:

Example 1

100 parts by weight of the resin (A-1) obtained in the above Synthesis Example A-1, 35 parts by weight of the high ortho novolak resin (B-1-1) obtained in Synthesis Example B-1-1, 0.2 parts by weight Photoacid generator C-1 (hereinafter referred to as C-1) and 0.3 parts by weight of 2,4-bis(trichloro Methyl)-6-piperyl-1,3,5-triazine (hereinafter referred to as C-2), after adding 30 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as D-1), using a shaking mixer, By dissolving and mixing, a chemically amplified positive photosensitive resin composition can be prepared. The chemically amplified positive photosensitive resin composition is evaluated by each measurement evaluation method described below. The results are shown in Table 2.

Example 2 to Example 14

Examples 2 to 14 use the same operation method as the manufacturing method of the chemically amplified positive photosensitive resin composition of Example 1, except that Examples 2 to 14 change the chemically amplified positive photosensitive The types and amounts of raw materials in the resin composition, their formulations and the following evaluation results are shown in Table 2 and Table 3.

Comparative Example 1 to Comparative Example 6

Comparative Examples 1 to 4 use the same method of production as the chemical amplification positive photosensitive resin composition of Example 1, except that Comparative Examples 1 to 4 change the chemical amplification positive photosensitive The types and amounts of raw materials in the resin composition, their formulations and the following evaluation results are shown in Table 3.

The compounds corresponding to the symbols in Table 2 and Table 3 are as follows.

Evaluation method

a. Novolac resin's ortho-to-ortho-methyl bonding ratio

A carbon nuclear magnetic resonance ( ¹³ C-NMR) (manufactured by Bruker, model AV400) was used to measure the amount of methylated bonds of the novolak resin, and the ortho-ortho bonding ratio in the novolak resin was calculated according to the following formula.

Proximity-proximity bonding ratio (%)={(proximity-proximity bond)/[(proximity-proximity bond)+(proximity-para-position bond)+(para-position-para-position bond)] }×100%

The ortho-ortho bond: the number of bonds between the methyl group and the ortho-ortho position.

The ortho-para bond: the number of bonding of the methyl group to the ortho-para position.

Para-to-para bond: the number of bonds between the methyl group and the para-to-para bond.

b. Sensitivity

The chemically amplified positive photosensitive resin compositions of Examples and Comparative Examples were coated on a 6-inch copper substrate using a spin coater to form a photosensitive resin layer with a film thickness of 50 μm. Thereafter, the photosensitive resin layer was prebaked at 110°C for 6 minutes. After pre-baking, the mask was exposed with a hole pattern with a diameter of 60 μm, and the exposure device Titan 2 (manufactured by Ultratech) was used to expose the pattern with g-line, h-line, and i-line, and the exposure amount was changed stepwise. Next, the substrate was placed on a hot plate and subjected to post-exposure heating (PEB) at 100°C for 3 minutes. Thereafter, a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution was dropped on the photosensitive resin layer, and it was left at 23°C for 60 seconds, and was repeated 4 times. 行Development. After that, washing with running water and blowing nitrogen gas were performed to obtain a thick film photoresist pattern having a contact hole pattern with a diameter of 50 μm.

Then, the exposure amount where no pattern residue is recognized, that is, the minimum exposure amount required for forming a thick film photoresist pattern is obtained as an index of sensitivity. The evaluation criteria are as follows:

◎: Exposure <100mJ/cm ²

○: 100mJ/cm ² ≦exposure amount<150mJ/cm ²

△: 150mJ/cm ² ≦exposure amount<200mJ/cm ²

×: Exposure ≧200mJ/cm ²

c. rectangle

Please refer to FIG. 1, which is a schematic diagram of measuring the rectangularity of the photoresist pattern. After the photosensitive resin layer coated on the substrate 100 undergoes the above-mentioned exposure and development steps, a photoresist pattern 120 having a photoresist 122 and a non-photoresist 124 is formed. Observe the cross-sectional shape of the photoresist pattern with the optimal exposure amount described above, measure the values of the bottom width L _b and the top width L _t , and calculate the L _t /L _b value as an index of rectangularity. The evaluation criteria are as follows:

◎: 0.9<L _t /L _b <1.1

○: 0.85<L _t /L _b ≦0.9; 1.1≦L _t /L _b <1.15

△: 0.75<L _t /L _b ≦0.85; 1.15≦L _t /L _b <1.25

×: L _t /L _b <0.75; L _t /L _b >1.25

Evaluation results

It is known from Tables 2 and 3 that the resin containing high ortho-position novolak resin (B-1) Compared to the chemically amplified positive photosensitive resin composition (Examples 1-14), the chemically amplified positive photosensitive resin composition that does not contain the high ortho novolak resin (B-1) (Comparative Example 2- 4) Poor rectangularity; compared to the chemically amplified positive photosensitive resin composition containing the resin (A) (Examples 1-14), the chemically amplified positive photosensitive resin not containing the resin (A) The composition (Comparative Examples 1 and 4) had poor sensitivity.

Meanwhile, when the monomer mixture used for the copolymerization of the resin (A) contains the monomer (a1) (Example 1-7) having the structure represented by the formula (A-1), its rectangularity performance is more good. In addition, when the monomer mixture further includes a cyclic ether group-containing monomer (a2) (Examples 2-8), the sensitivity performance is better.

In addition, when the chemically amplified positive photosensitive resin composition contains a thiol compound (E) (Examples 2-4, 6, 8, 12, 13), its rectangularity performance is also better.

In addition, when the chemically amplified positive photosensitive resin composition contains an anthracene compound (F) (Examples 2, 3, 6-8, 13, 14), its sensitivity performance is also better.

In summary, the chemically amplified positive photosensitive resin composition of the present invention contains a high ortho-position novolak resin (B-1) having 18% to 25% of methyl groups bonded to the ortho-ortho position ), it can improve the problem of poor rectangularity.

On the other hand, if the resin (A) in the chemically amplified positive photosensitive resin composition of the present invention is obtained by copolymerization of a monomer mixture containing a specific monomer, or the chemically amplified positive photosensitive resin of the present invention When the composition further contains a thiol compound (E), the resulting photoresist pattern can further achieve better rectangularity.

In addition, if the chemically amplified positive photosensitive resin composition of the present invention The resin (A) is obtained by copolymerizing a monomer mixture containing a specific monomer (a2), or when the chemically amplified positive photosensitive resin composition of the present invention further contains an anthracene compound (F) The photoresist pattern will be able to further obtain better sensitivity.

Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the appended patent application.

Claims (12)

A chemically amplified positive photosensitive resin composition, comprising: resin (A), which is obtained by copolymerization of a monomer mixture and contains an acid dissociative protective group; novolak resin (B); A photoacid generator (C); and a solvent (D), the novolak resin (B) includes a high ortho-position novolak resin (B-1), and the high-ortho-position novolak resin (B-1) has 18% to 25% of the methyl group is bonded to the ortho-ortho position, wherein based on the total usage of the resin (A) is 100 parts by weight, the high ortho-position novolak resin (B-1) The amount used is from 20 parts by weight to 120 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 1 of the patent application range, wherein the monomer mixture includes a monomer (a1), and the monomer (a1) has the following formula (A-1) ) The structure shown:

In formula (A-1), L ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched group having 1 to 6 carbon atoms Fluorinated alkyl groups; L ² , L ³ , and L ⁴ independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms Fluoroalkyl group, or L ³ and L ⁴ are bonded to each other to form a hydrocarbon ring having 5 to 20 carbon atoms. The chemically amplified positive photosensitive resin composition as described in item 1 of the patent application range, wherein the monomer mixture includes a monomer (a2), and the monomer (a2) contains a cyclic ether group. The chemically amplified positive photosensitive resin composition as described in item 1 of the patent application scope, which further includes a thiol compound (E), the thiol compound (E) having the following formula (E-1) Structure:

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents a single bond or an alkylene group having 1 to 10 carbon atoms, R ⁴ Represents an u-valent organic group; u represents an integer from 2 to 6. The chemically amplified positive photosensitive resin composition as described in item 1 of the patent application scope further includes an anthracene compound (F). The chemically amplified positive photosensitive resin composition as described in item 1 of the patent application scope, wherein the total usage amount based on the resin (A) is 100 parts by weight, and the usage amount of the novolak resin (B) is From 20 parts by weight to 150 parts by weight, the photoacid generator (C) is used in an amount of 0.5 to 5 parts by weight, and the solvent (D) is used in an amount of 30 to 360 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 2 of the patent application range, wherein the total usage amount based on the monomer mixture is 100 parts by weight, and the usage amount of the monomer (a1) is 10 parts by weight Parts to 60 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 3 of the patent application scope, wherein the total usage amount based on the monomer mixture is 100 parts by weight, and the usage amount of the monomer (a2) is 5 parts by weight Parts to 30 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 4 of the patent application scope, wherein the total usage amount based on the resin (A) is 100 parts by weight, and the usage amount of the thiol compound (E) is 0.3 parts by weight to 3 parts by weight. The chemically amplified positive photosensitive resin composition as described in item 5 of the patent application range, wherein the total usage amount based on the resin (A) is 100 parts by weight, and the usage amount of the anthracene compound (F) is 0.2 parts by weight to 1.5 parts by weight. A method for manufacturing a substrate with a casting mold, comprising: a lamination step, on the metal surface of a substrate having a metal surface, the lamination is chemically amplified as described in any one of claims 1 to 10 A photosensitive resin layer composed of a positive photosensitive resin composition; an exposure step that irradiates the photosensitive resin layer with active light or radiation; and a development step that develops the photosensitive resin layer after exposure, and A casting mold for forming an electroplated shaped body is prepared. A manufacturing method of electroplated shaped body, including: The step of forming a plated molded body in the mold by performing electroplating on the mold-attached substrate manufactured by the method of manufacturing a mold-attached substrate as described in item 11 of the scope of patent applications.

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