CN107870517A

CN107870517A - Chemically amplified positive photosensitive resin composition, method for producing substrate with mold, and method for producing molded article by plating

Info

Publication number: CN107870517A
Application number: CN201710879577.8A
Authority: CN
Inventors: 郭圣扬; 黄伟杰; 刘骐铭; 施俊安
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2016-09-28
Filing date: 2017-09-26
Publication date: 2018-04-03
Also published as: TW201812445A; SG10201707809VA; TWI724029B

Abstract

The present invention relates to a chemically amplified positive photosensitive resin composition having excellent sensitivity and rectangularity, a method for producing a substrate with a mold, and a method for producing an electroplated molded article. The chemically amplified positive photosensitive resin composition comprises a resin (A) which is obtained by copolymerization of a monomer mixture and contains an acid-dissociable protecting group, a photoacid generator (C), a solvent (D), a thiol compound (E), and an anthracene compound (F). The thiol compound (E) has a structure represented by the formula (E-1).

Description

The manufacture of chemical amplification positive photosensitive resin composition, substrate with mold The manufacture method of method and electroplating formation body

Technical field

A kind of manufacture method of substrate the present invention relates to chemical amplification positive photosensitive resin composition, with mold And the manufacture method of electroplating formation body, and a kind of more particularly to chemical amplification that can improve sensitivity and the bad problem of rectangularity Type positive-type photosensitive resin composition, the base as made from the chemical amplification positive photosensitive resin composition with mold The manufacture method of the manufacture method of plate and the electroplating formation body as made from the substrate with mold.

Background technology

Now, photoelectricity processing is into the main flow of precise fine process technology.Alleged " photoelectricity processing ", refers to light resistance composition It is coated on machined object surface and forms photoresist layer, is patterned photoresist layer using photolithographic techniques, then with patterned Photoresist layer (photoresistance pattern) is that shade carries out chemical etching, electrolytic etching or electrical forming to electroplate etc., to manufacture half The general name of the technology of the various precision components such as conductor packaging body.

Also, in recent years, with the miniaturization of electronic equipment, the high density packaging technique progress of semiconductor package body is quick, And seek more stitch film assemblingizations of packaging body, package body sizes miniaturization, adopt flip mode two-dimentional package technique, three Tie up the lifting of the packing density of package technique.In such high density packaging technique, as connection terminal, for example, will be for connection The projected electrode (assembling terminal) of prominent projection etc. on towards packaging body, from the surrounding terminals on wafer the distribution again of extension with Metal column of terminal etc. is assembled to configure to high precision on substrate.

Photoelectricity processing described above uses light resistance composition, and as such light resistance composition, both having known has comprising acid producing agent Chemical amplification type light resistance composition (referring now to patent document 1,2 etc.).Chemical amplification type light resistance composition is to pass through radioactive ray Irradiate (exposure) and acid is produced by acid producing agent, promote sour diffusion by heating, with the matrix resin in constituent etc. Cause acid catalyst to react, and change its alkali-solubility person.

Such chemical amplification positive light resistance composition is to be used in the electricity such as the projection or metal column of adopting coating step Plate formation of formed body etc..Specifically, it is to use chemical amplification type light resistance composition, is formed on the supports such as metal substrate The photoresist layer for the thickness being intended to, it is exposed across set mask pattern, images, forms the photoresistance figure used as template Case, wherein intend being formed projection or metal column partially selectively through removing (stripping).Thereafter, the part to the removal is passed through After (non-photoresistance portion) is embedded to the conductor of copper etc. by plating, then the photoresistance pattern around it is removed, projection or metal column can be formed.

However, afore mentioned chemical amplification positive light resistance composition but have sensitivity it is bad with formed photoresistance pattern rectangularity not The shortcomings that good, and can not be received by industry.Therefore, how a kind of sensitivity and good photoresistance pattern of rectangularity of being formed is provided Chemical amplification positive light resistance composition, actually current those skilled in the art, which desire most ardently, solves the problems, such as.

[patent document]

[patent document 1] Japanese Unexamined Patent Publication 9-176112 publications

[patent document 2] Japanese Unexamined Patent Publication 11-52562 publications

The content of the invention

In view of this, the present invention provides a kind of chemical amplification positive photosensitive resin composition, is increased using the chemistry The problem of width type positive-type photosensitive resin composition can improve sensitivity and bad rectangularity.

The present invention provides a kind of chemical amplification positive photosensitive resin composition, including：By monomer mixture combined polymerization And obtain, and the resin (A) containing acid dissociation protection group, light acid producing agent (C), solvent (D), mercaptan compound (E) and anthracene Class compound (F).Wherein mercaptan compound (E) has the structure shown in following formula (E-1)：

In formula (E-1), R¹、R²It is each independent to represent hydrogen atom or carbon number for 1 to 4 alkyl, R³Represent singly-bound or carbon Atomicity be 1 to 10 alkylidene, R⁴Represent u valency organic groups；U represents 2 to 6 integer.

In one embodiment of this invention, above-mentioned monomer mixture includes monomer (a1), has by following formula (A-1) institute The structure shown：

In formula (A-1), L¹Represent hydrogen atom, the straight-chain that carbon number is 1 to 6 or the alkyl of branch-like, fluorine atom, Or the straight-chain or the fluorinated alkyl of branch-like that carbon number is 1 to 6；L²、L³、L⁴Independently represent carbon number be 1 to 6 the straight-chain either alkyl of branch-like or straight-chain or the fluoroalkyl of branch-like that carbon number is 1 to 6, or L³、L⁴ It is bonded each other and is collectively forming the hydrocarbon ring that carbon number is 5 to 20.

In one embodiment of this invention, above-mentioned monomer mixture includes monomer (a2), and monomer (a2) is sub- containing polyoxy Alkyl chain.

In one embodiment of this invention, it is clear also to include phenolic aldehyde for above-mentioned chemical amplification positive photosensitive resin composition Coating resins (B).

In one embodiment of this invention, total usage amount based on resin (A) is 100 parts by weight, light acid producing agent (C) Content is 0.5 parts by weight to 4.5 parts by weight, and the content of solvent (D) is 60 parts by weight to 600 parts by weight, mercaptan compound (E) Content is 0.3 parts by weight to 3 parts by weight, and the content of anthracene compound (F) is 0.2 parts by weight to 1.5 parts by weight.

In one embodiment of this invention, the total amount based on monomer mixture is 100 parts by weight, the usage amount of monomer (a1) For 20 parts by weight to 80 parts by weight.

In one embodiment of this invention, the total amount based on monomer mixture is 100 parts by weight, the usage amount of monomer (a2) For 10 parts by weight to 60 parts by weight.

In one embodiment of this invention, total usage amount based on resin (A) is 100 parts by weight, novolac resin (B) Content be 20 parts by weight to 180 parts by weight.

The present invention also provides a kind of manufacture method of the substrate with mold, including：Layering steps, with metal surface Substrate metal surface on, photonasty tree that lamination is made up of above-mentioned chemical amplification positive photosensitive resin composition Lipid layer, step of exposure, actinic ray or radioactive ray and development step are irradiated to photo-sensitive resin, to photosensitive after exposure Property resin bed is developed, and is made to form the mold of electroplating formation body.

The present invention also provides a kind of manufacture method of electroplating formation body, including：To by having the base of mold described above Substrate with mold manufactured by the manufacture method of plate implements plating, and in electroplating formation body is formed in mold the step of.

Based on above-mentioned, of the invention chemical amplification positive photosensitive resin composition because containing mercaptan compound (E), with And anthracene compound (F), therefore the problem of sensitivity and bad rectangularity can be improved.

For features described above of the invention and advantage can be become apparent, special embodiment below, and it is detailed to coordinate accompanying drawing to make Carefully it is described as follows.

Brief description of the drawings

Fig. 1 is the schematic diagram for the rectangularity for measuring photoresistance pattern.

Drawing reference numeral explanation：

100：Substrate；

120：Photoresistance pattern；

122：Photoresistance portion；

124：Non- photoresistance portion；

L_b：Bottom width；

L_t：Top width.

Embodiment

The present invention provides a kind of chemical amplification positive photosensitive resin composition, comprising：Resin (A), resin (A) be by Monomer mixture combined polymerization and obtain, and containing acid dissociation protection group, light acid producing agent (C), solvent (D), mercaptan compound And anthracene compound (F) (E).In addition, the chemical amplification positive photosensitive resin composition of the present invention can also include phenolic aldehyde Varnish gum (B), additive (G).

It will be detailed below each composition of the chemical amplification positive photosensitive resin composition for the present invention.

It is described herein to be, it is that acrylic acid and/or methacrylic acid are represented with (methyl) acrylic acid below, and with (methyl) Acrylate represents acrylate and/or methacrylate；Similarly, with (methyl) acryloyl group represent acryloyl group and/ Or methylacryloyl.

Resin (A)

Resin (A) is obtained by monomer mixture combined polymerization, and contains acid dissociation protection group.Specifically, monomer mixes Compound may include with as shown in formula (A-1) monomer (a1) of structure, the monomer (a2) of the chain containing polyoxy alkylidene, with by formula (A-2) or structure shown in formula (A-3) monomer (a3) and other monomers (a4).

Monomer (a1) with the structure as shown in formula (A-1)

It is as follows with the monomer (a1) of structure as shown in formula (A-1)：

In formula (A-1), L¹Represent hydrogen atom, the straight-chain that carbon number is 1 to 6 or the alkyl of branch-like, fluorine atom, Or the straight-chain or the fluorinated alkyl of branch-like that carbon number is 1 to 6；L²、L³、L⁴Independently represent carbon number be 1 to Either the alkyl of branch-like or carbon number are 1 to 6 straight-chain or the fluorinated alkyl of branch-like to 6 straight-chain, or L³、L⁴It is bonded each other and is collectively forming the hydrocarbon ring that carbon number is 5 to 20.

In addition, the alkyl as above-mentioned straight-chain or branch-like, can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, Isobutyl group, three-level butyl, amyl group, isopentyl, neopentyl etc..Also, fluorinated alkyl refers to a part for the hydrogen atom of abovementioned alkyl Or all through fluorine atom substituent.

Work as L³、L⁴When not being bonded each other and forming hydrocarbon ring, L²、L³、L⁴The preferably straight-chain of carbon number 2~4 or branch The alkyl of shape.

Above-mentioned L³、L⁴The carbon atom that can be bonded with both is collectively forming the aliphatic cyclic group of carbon number 5~20.Make For the instantiation of such aliphatic cyclic group, it can enumerate and remove 1 by polynaphthenes such as mononaphthene, two cycloalkanes, three cycloalkanes, tetracycloalkanes The base of hydrogen atom more than individual.Specifically, can enumerate by the mononaphthenes such as pentamethylene, hexamethylene, cycloheptane, cyclooctane or gold The polynaphthenes such as firm alkane, norcamphane, isobornylene, tristane, tetracyclododecane remove the base of the hydrogen atom of more than 1.Especially with The base (can further have substituent) for the hydrogen atom for removing more than 1 by hexamethylene, adamantane is preferred.

Furthermore as above-mentioned L³、L⁴The aliphatic cyclic group formed takes when having substituent in its ring skeleton as this Dai Ji example, the straight-chain of hydroxy, carboxyl, cyano group, oxygen atom (=O) isopolarity base or carbon number 1~4 can be enumerated Or the alkyl of branch-like.As polar group, it is preferred especially with oxygen atom (=O).

As the concrete example with the monomer (a1) of structure as shown in formula (A-1), can enumerate following by formula (A-1-1)~formula (A-1-33) compound shown in：

In formula (A-1-1)~formula (A-1-33), L¹¹Represent hydrogen atom or methyl.

Total amount based on monomer mixture is 100 parts by weight, and the usage amount of monomer (a1) is 20 parts by weight to 80 parts by weight, Preferably 25 parts by weight are to 75 parts by weight, more preferably 30 parts by weight to 70 parts by weight.

If monomer mixture includes having during monomer (a1) of structure, can further improve chemistry as shown in formula (A-1) The rectangularity of amplification positive photosensitive resin composition.

The monomer (a2) of the chain containing polyoxy alkylidene

The monomer (a2) of chain containing polyoxy alkylidene (poly oxyalkylene) can enumerate following concrete example, but be not intended to limit In these concrete examples：The acrylic acid phenyl methylcarbamate ester (trade name of oxirane (hereinafter referred to as EO) modification：ARONIX TO-901)、 Lauryl ester (the trade name of EO modifications：ARONIX TO-950), EO modification acrylic acid tridecane ester (trade name： ARONIX TO-951), acrylic acid (2- ethylhexyls-polyethylene glycol) ester (trade name：ARONIX TO-946~TO-949), with It is upper to be synthesized for East Asia manufactured by limited company；Acrylic acid (ethyl-diethylene glycol) ester (trade name：Light Acrylate EC-A), acrylic acid (methoxy-triethylene glycol) ester (trade name：Light Acrylate MTG-A), acrylic acid (methoxyl group-poly- Ethylene glycol) ester (trade name：Light Acrylate 130A), acrylic acid (phenoxy group-polyethylene glycol) ester (trade name：Light Acrylate P-200A), acrylic acid (nonyl phenyl-polyoxyethanyl chain additives) ester (trade name：Light Acrylate NP-4EA, NP-8EA), the above is manufactured by chemistry limited company of common prosperity society；Polyalkylene glycol acrylate ester (trade name： BLEMMER AE-350), methacrylic acid macrogol ester (trade name：BLEMMER PE-90, PE-200, PE-350), propylene Sour (methoxypolyethylene glycol) ester (trade name：BLEMMER AME-400), methacrylic acid (methoxypolyethylene glycol) ester (trade name：BLEMMER PME-100, PME-200, PME-400), methacrylic acid polypropylene glycol ester (trade name：BLEMMER PP-500, PP-800), methacrylic acid (polyethylene glycol propane diols) ester (trade name：BLEMMER 70PEP-370B), first Base acrylic acid (polyethylene glycol butanediol) ester (trade name：BLEMMER 50PET-800), methacrylic acid (octyloxy-poly- Ethylene glycol-polypropylene glycol) ester (trade name：BLEMMER50POEP-800B, 50AOEP-800B), the above is Japanese grease share Manufactured by Co., Ltd；Methacrylic acid (methoxyl group-diethylene glycol) ester (trade name：NK Ester M-20G、M-40G、M- 90G) and acrylic acid (phenoxy group-diethylene glycol) ester (trade name：NK Ester AMP-20G), the above is Xin Zhong villages chemistry Manufactured by Industries, Inc.

Total amount based on monomer mixture is 100 parts by weight, and the usage amount of monomer (a2) is 10 parts by weight to 60 parts by weight, Preferably 15 parts by weight are to 55 parts by weight, more preferably 20 parts by weight to 50 parts by weight.

If monomer mixture includes monomer (a2) of the chain containing polyoxy alkylidene, it can further improve chemical amplification type just The sensitivity of type photosensitive resin composition.

Monomer (a3) with the structure as shown in formula (A-2) or formula (A-3)

Monomer (a3) with the structure as shown in formula (A-2) or formula (A-3) is as follows：

In formula (A-2), formula (A-3), L⁵~L¹⁰Independently represent hydrogen atom, carbon number be 1 to 6 straight-chain or Alkyl, fluorine atom or the carbon number of branch-like are 1 to 6 straight-chain or the fluorinated alkyl of branch-like；Y represents to have to take Dai Ji alcyl or alkyl, p represent 0 to 4 integer, and q represents 0 or 1.

In addition, in formula (A-2), formula (A-3), L⁵~L¹⁰Straight-chain either the alkyl of branch-like and straight-chain or L in the definition of the fluorinated alkyl of branch-like, with previously described formula (A-1)¹The alkyl of defined straight-chain or branch-like and The fluorinated alkyl of straight-chain or branch-like is identical, is repeated no more in this.

When Y is alcyl or alkyl, it can enumerate and remove 1 by polynaphthenes such as mononaphthene, two cycloalkanes, three cycloalkanes, tetracycloalkanes Base of hydrogen atom above etc..Specifically, can enumerate by the mononaphthenes such as pentamethylene, hexamethylene, cycloheptane, cyclooctane or gold The polynaphthenes such as firm alkane, norcamphane, isobornylene, tristane, tetracyclododecane remove the base of the hydrogen atom of more than 1.Especially with The base (can further have substituent) that the hydrogen atom of more than 1 is removed by adamantane is preferred.

Furthermore when the alcyl represented by Y has substituent in its ring skeleton, as the example of substituent, it can lift Go out hydroxy, carboxyl, cyano group, oxygen atom (=O) isopolarity base or the straight-chain of carbon number 1~4 or the alkyl of branch-like. As polar group, it is preferred especially with oxygen atom (=O).

Also, when Y is alkyl, it is preferred that the alkane of carbon number 1~20, preferably 6~15 straight-chain or branch-like Base.Such alkyl, is preferred with alkoxyalkyl especially, as such alkoxyalkyl, can enumerate 1- methoxy ethyls, 1- ethyoxyls Ethyl, 1- positive propoxies ethyl, 1- isopropoxyethyls, 1- n-butoxyethyls, 1- isobutoxyethies, 1- three-level butoxy Ethyl, 1- methoxy-propyls, 1- ethoxycarbonyl propyls, 1- methoxyl group -1- methyl-ethyls, 1- ethyoxyl -1- Methylethyls etc..

As the concrete example with the monomer (a3) of structure as shown in formula (A-2) or formula (A-3), can enumerate following by formula (A-2-1) compound shown in~formula (A-2-24), formula (A-3-1)~formula (A-3-15)：

In formula (A-2-1)~formula (A-2-24), formula (A-3-1)~formula (A-3-15), L¹¹Represent hydrogen atom or methyl.

Other monomers (a4)

In monomer mixture, as long as not influenceing the effect of the present invention, it may also include and be not belonging to above-mentioned monomer (a1)~mono- The other monomers (a4) of body (a3).Other monomers (a4) are, for example, known free-radical polymerised compound or anionic polymerisation Property compound.

As such polymerizable compound, the monocarboxylic acid class such as acrylic acid, methacrylic acid, crotonic acid can be enumerated；Horse Carry out the omega-dicarboxylic acids such as sour, fumaric acid, itaconic acid；2- methylacryoyloxyethyls butanedioic acid, 2- methylacryoyloxyethyls Malaysia Acid, 2- methylacryoyloxyethyls phthalic acid, 2- methylacryoyloxyethyl hexahydrophthalic acids etc. have carboxyl and ester The methacrylic acid derivative class of key；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (first Base) (methyl) alkyl-acrylates such as cyclohexyl acrylate；(methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid -2- Hydroxy propyl ester etc. (methyl) hydroxyalkyl acrylates class；(methyl) Glycidyl Acrylate, (methyl) acrylic acid -2- methyl rings Oxygen propyl ester, (methyl) acrylic acid -3,4- epoxies butyl ester, (methyl) acrylic acid -6,7- epoxies heptyl ester, (methyl) acrylic acid -3,4- The acrylic acid epoxy base ester class such as epoxy cyclohexyl or (methyl) acrylic acid -3,4- epoxycyclohexanecarboxylates；(methyl) acrylic acid benzene (methyl) the benzyl acrylate classes such as ester, (methyl) benzyl acrylate；The dicarboxylic acids such as diethyl maleate, dibutyl fumarate Two esters；Styrene, α-methylstyrene, chlorostyrene, 1-chloro-4-methyl-benzene, vinyltoluene, hydroxy styrenes, Alpha-Methyl The aromatic compound species containing vinyl such as hydroxy styrenes, α-ethyl hydroxy styrene；Vinyl acetate etc. is containing vinyl Aliphatic compound species；Butadiene, isoprene equiconjugate alkadiene；The polymerization of the nitrile group-containings such as acrylonitrile, methacrylonitrile Property compounds；The chloride polymerizable compound such as vinyl chloride, vinylidene chloride；The amide containings such as acrylamide, Methacrylamide Polymerizable compound class of key etc..

Also, as polymerizable compound, (methyl) acrylic acid of the aliphatic polycycle base of the non-dissociative of tool acid can be enumerated Esters, aromatic compound species containing vinyl etc..As the aliphatic polycycle base of the non-dissociative of acid, particularly tricyclodecyl, Adamantyl, Fourth Ring dodecyl, isobornyl, norcamphanyl etc., so that industrially easily the viewpoint such as acquirement is preferable.These aliphatic The straight-chain or the alkyl of branch's chain state that polycycle base also can be with carbon number 1~5 are as substituent.

As (methyl) esters of acrylic acid of the aliphatic polycycle base of the non-dissociative of tool acid, specifically, can illustrate down Row are as the compound shown in formula (A-4-1)~formula (A-4-5)：

In formula (A-4-1)~formula (A-4-5), L¹¹Represent hydrogen atom or methyl.

Total amount based on monomer mixture is 100 parts by weight, and the usage amount of other monomers (a4) is 5 parts by weight to 40 weight Part, preferably 8 parts by weight to 35 parts by weight, more preferably 10 parts by weight to 30 parts by weight.

Prepare solvent used during resin (A) and include but is not limited to (1) alcohol compound：Methanol, ethanol, phenmethylol, 2- Benzyl carbinol, or 3- phenyl-1-propanols etc.；(2) ether compound：Tetrahydrofuran etc.；(3) glycol ethers compound：Ethylene glycol list Propyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether etc.；(4) ethylene glycol alkyl ether acetate：2-Butoxyethyl acetate, second two Alcohol ethyl ether acetate ester, glycol methyl ether acetate etc.；(5) diethylene glycol class compound：Diethylene glycol monomethyl ether, diethylene glycol list Ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), diethylene glycol Diethyl ether, diethylene glycol ethylmethyl ether etc.；(6) DPG class compound：Dipropylene glycol monomethyl ether, DPE, two Propylene Glycol Dimethyl Ether, dipropylene glycol diethyl ether, DPG ethyl methyl ether etc.；(7) propylene-glycol monoalky lether class compound：Propane diols Monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.；(8) propylene glycol alkyl ether acetate class chemical combination Thing：Propylene glycol methyl ether acetate (Propylene glycol monomethyl ether acetate), propylene-glycol ethyl ether acetic acid Ester, propylene glycol propyl ether acetate, propandiol butyl ether acetate etc.；(9) propylene glycol alkyl ether propionic acid ester compound：Propane diols first Ether propionic ester, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether propionic ester etc.；(10) arene Compound：Toluene, dimethylbenzene etc.；(11) ketone compounds：MEK, cyclohexanone, DAA etc.；(12) ester type compound：Second Sour methyl esters, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyls methyl propionate, 2- hydroxyls Base -2 Methylpropionic acid ethyl ester, glycolic methyl esters, ethyl glycolate, butyl glycolate, methyl lactate, propyl lactate, lactic acid fourth Ester, 3- hydroxy methyl propionates, 3- hydroxypropionates, 3- hydracrylic acids propyl ester, 3- hydracrylic acids butyl ester, 2- hydroxy-3-methyls Methyl butyrate, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethyoxyl second Acetoacetic ester, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group acetic acid Propyl ester, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid fourth Ester, 3- methoxybutyls acetic acid esters, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- first Epoxide butyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- ethoxy-cs propyl propionate, 2- ethoxy-propionic acids Butyl ester, 2- butoxy methyl propionate, 2- butoxy ethyl propionate, 2- butoxy propyl propionate, 2- butoxy butyl propionate, 3- first Epoxide methyl propionate, 3- methoxypropionates, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, 3- ethoxy-propionic acids Methyl esters, 3- ethoxyl ethyl propionates, 3- ethoxy-cs propyl propionate, 3- ethoxy-cs acid butyl ester, 3- propoxyl group methyl propionate, 3- third Epoxide ethyl propionate, 3- propoxyl group propyl propionate, 3- propoxyl group butyl propionate, 3- butoxy methyl propionate, 3- butoxy propionic acid Ethyl ester, 3- butoxy propyl propionate, 3- butoxy butyl propionates etc., this solvent can be used alone or as a mixture.

Used polymerization initiators, can be single including but not limited to azo-compound or peroxide when preparing resin (A) Solely or it is used in mixed way.

Azo-compound is such as, but not limited to：2,2 '-azobis isobutyronitrile, 2,2 '-azo are double (2,4- methyl pentane nitriles) Double (4- methoxyl group -2,4- the dimethyl-pentens of [2,2'-Azobis (2,4-dimethylvaleronitrile)], 2,2 '-azo Nitrile), the double -2- methylbutyronitriles [2,2'-azobis-2-methyl butyronitrile] of 2,2 '-azo, the double (4- of 4,4 '-azo Cyanopentanoic acid), dimethyl 2,2 '-azo double (2 Methylpropionic acid ester), the double (4- methoxyl group -2,4- dimethyl-pentens of 2,2 '-azo Nitrile) etc..

Peroxide is such as, but not limited to：Dibenzoyl peroxide, dilauroyl peroxide, tert-butyl hydroperoxide trimethylacetic acid Ester, 1,1- double (tert-butyl hydroperoxide) hexamethylene, hydrogen peroxide etc..

Reaction temperature when preparing resin (A) is 40~120 degree, and polymerization time is 3~12 hours.

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

Novolac resin (B)

Novolac resin (B) is by aldehyde compound and aromatic hydroxy compound, in the presence of acidic catalyst Obtained through polycondensation reaction.

The concrete example of foregoing aldehyde compound, such as：Formaldehyde, paraformaldehyde (paraformaldehyde), metaformaldehyde (trioxane), acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, methacrylaldehyde (acrolein), crotonaldehyde (crotonaldehyde), Hexamethylene aldehyde (cyclo hexanealdehyde), furtural (furfural), furylacrolein (furylacrolein), Benzaldehyde, terephthalaldehyde (terephthal aldehyde), phenylacetaldehyde, α-hydrocinnamicaldehyde, beta-phenyl propionic aldehyde, ortho-methyl benzene Formaldehyde, m- tolyl aldehyde, p-tolualdehyde, o- chlorobenzaldehyde, m- chlorobenzaldehyde, p- chlorobenzaldehyde, cinnamic acid Deng.Foregoing aldehyde compound can be used alone or mixing plural kinds of use.It is preferred that aldehyde compound can be formaldehyde or benzene Formaldehyde.

The concrete example of aforementioned fragrance race hydroxy compounds, such as：Phenol (phenol)；M-cresol (m-cresol), p- first Phenol (p-cresol), o-cresol (o-cresol) etc. cresols (cresol) class compound；2,3 xylidine phenol, 2,5- dimethylbenzene Phenol, 3,5- xylenols, 3,4- xylenols etc. xylenol (xylenol) class compound；M- ethyl -phenol, p- ethylo benzene Phenol, o- ethyl -phenol, 2,3,5- pseudocuminols, 2,3,5- triethyl groups phenol, 4- tributyl phenols, 3- tributyl benzene Phenol, 2- tributyl phenols, 2- tributyl -4- methylphenols, 2- tributyl -5- methylphenols, 6- tributyl -3- first The alkylphenols such as base phenol (alkyl phenol) class compound；P-methoxyphenol, m- metoxyphenol, p- ethyoxyl Phenol, m- thanatol, to propoxyl group phenol, m- propoxyl group phenol etc. alkoxy phenol (alkoxy phenol) class Compound；O- isopropenyl phenol, p- isopropenyl phenol, 2- methyl -4- isopropenyl phenols, 2- ethyl -4- isopropenyls The isopropenyl phenols such as phenol (isopropenyl phenol) class compound；The aryl of phenylphenol (phenyl phenol) Phenol (aryl phenol) class compound；4,4' dihydroxy diphenyl, bisphenol-A, m- benzenediol (resorcinol), p- benzene two Phenol (hydroquinone), pyrogaelol (pyrogallol) etc. polyhydroxy benzenes (polyhydroxyphenol) class chemical combination Thing.Aromatic hydroxy compound can be used alone or mixing plural kinds of use.

It is preferred that aromatic hydroxy compound can be 3,5- xylenols, it is DMP, 2,5- xylenols, o- Cresols, m-cresol or p-Cresol.

The concrete example of aforementioned acid catalyst, such as：Hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-methyl benzenesulfonic acid etc..

Novolac resin (B) can be used alone or mixing plural kinds of use.Total usage amount based on resin (A) is 100 parts by weight, the content of novolac resin (B) are 20 parts by weight to 180 parts by weight, preferably 25 parts by weight to 160 weight Part, more preferably 30 parts by weight to 140 parts by weight.

The weight average molecular weight of novolac resin (B) is 5,000 to 50,000；Preferably 6,000 to 45,000；More Good is 7,000 to 40,000.

When including novolac resin (B) in chemical amplification positive photosensitive resin composition, can further improve Rectangularity.

Light acid producing agent (C)

Light acid producing agent (C) produces the compound of acid by the irradiation of actinic ray or radioactive ray, as long as that can pass through Light directly or indirectly produces the compound of acid, is not particularly limited.It is preferably following described as light acid producing agent (C) The acid producing agent of the embodiment of bright first~the 5th.Hereinafter, the light acid producing agent to being adapted to use in photosensitive resin composition (C) preferably among, it is illustrated in the form of first to the 5th.

As the first form of light acid producing agent (C), the compound shown in following formula (C-1) can be enumerated：

In formula (C-1), X¹The sulphur atom or iodine atom of g valencys are represented, g is 1 or 2.H represents the repetition list of the structure in parantheses First number.W¹For with X¹The organic group of bond, represent heterocyclic radical, carbon that aryl, carbon number that carbon number is 6 to 30 are 4 to 30 The alkynyl that the alkenyl or carbon number that alkyl that atomicity is 1 to 30, carbon number are 2 to 30 are 2 to 30, W¹Alkane can be passed through Base, hydroxyl, alkoxy, alkyl carbonyl, aromatic carbonyl, alkoxy carbonyl group, aryloxy carbonyl, fragrant thiocarbonyl group, acyloxy, arylthio, alkylthio group, Aryl, heterocycle, aryloxy group, alkyl sulfinyl, fragrant sulfinyl, alkane sulfonyl, arylsulfonyl, alkylene oxide group, amido, cyano group, At least one kind of substitution selected in group formed by nitro and halogen.W¹Number be g+h (g-1)+1, W¹Can distinguish it is mutually the same or It is different.Also, the W of more than 2¹It can be bonded directly with one another or by-O- ,-S- ,-SO- ,-SO₂-、-NH-、-NW²-、-CO-、- COO- ,-CONH-, carbon number form for 1 to 3 alkylidene or phenylene bond and include X¹Ring structure.W²It is former for carbon The aryl that the alkyl or carbon number that subnumber is 1 to 5 are 6 to 10.

X²For the structure shown in following formula (C-1a)：

In formula (C-1a), X⁴Represent the arlydene or carbon that alkylidene, carbon number that carbon number is 1 to 8 are 6 to 20 Atomicity be 8 to 20 the miscellaneous base of divalent, X⁴Alkoxy that the alkyl that can be 1 to 8 by carbon number, carbon number are 1 to 8, carbon At least one kind of substitution selected in group formed by aryl, hydroxyl, cyano group, nitro and the halogen that atomicity is 6 to 10.X⁵Represent- O-、-S-、-SO-、-SO₂-、-NH-、-NW²- ,-CO- ,-COO- ,-CONH-, carbon number be 1 to 3 alkylidene or sub- benzene Base.H represents the number of repeat unit of the structure in parantheses.H+1 X⁴And h X⁵It can distinguish identical or different.W²It is and aforementioned definitions It is identical.

(X³)^-For to ion (counter ion), the fluoroalkyl fluorophosphoric acid that can be enumerated shown in following formula (C-1b) is cloudy Borate anion shown in ion or following formula (C-1c)：

[(W³)_jPF_6-j]^-Formula (C-1b)

In formula (C-1b), W³The alkyl that the hydrogen atom of expression more than 80% substitutes through fluorine atom.J represents its number, be 1 to 5 integer.J W³It can distinguish identical or different.

In formula (C-1c), W⁴~W⁷Independently represent fluorine atom or phenyl, a part or complete for the hydrogen atom in the phenyl Portion can be by least one kind of substitution for being selected in group formed by fluorine atom and trifluoromethyl.

As the ion in the compound shown in formula (C-1), triphenylsulfonium, three-p-methylphenyl sulfonium, 4- (benzene can be enumerated Sulfenyl) phenyl diphenyl sulfonium, double [4- (diphenyl sulfonium base) phenyl] thioethers, double [4- { double [4- (2- hydroxy ethoxies) phenyl] sulfoniums Base } phenyl] thioether, double { 4- [double (4- fluorophenyls) sulfonium bases] phenyl } thioethers, 4- (4- benzoyl -2- chlorophenylsulfanyls) phenyl be double (4- fluorophenyls) sulfonium, 7- isopropyl -9- Oxy-1 0- thia -9,10- dihydroanthracene -2- two-p-methylphenyls of base sulfonium, 7- isopropyls - 9- Oxy-1 0- thia -9,10- dihydroanthracene -2- base diphenyl sulfonium, 2- [(diphenyl) sulfonium base] thioxanthone, 4- [4- (4- three-levels Butylbenzoyl) thiophenyl] two-p-methylphenyl of phenyl sulfonium, 4- (4- benzoylphenylsulfanyls) phenyl diphenyl sulfonium, diphenyl Phenylacetyl group sulfonium, 4- hydroxyphenylmethyl benzyls sulfonium, 2- naphthyl methyls (1- carbethoxyl groups) ethyl sulfonium, 4- hydroxyphenylmethyl benzene second Acyl group sulfonium, phenyl [4- (4- biphenyl sulfenyl) phenyl] 4- biphenyl sulfonium, phenyl [4- (4- biphenyl sulfenyl) phenyl] 3- biphenyl sulfonium, [4- (4- acetyl thiophenyl) phenyl] diphenyl sulfonium, octadecyl methyl phenylacetyl group sulfonium, two benzene base Iodonium, two-to first benzene base Iodonium, double (4- Dodecyl phenyl) Iodonium, double (4- methoxyphenyls) Iodonium, (4- octyloxyphenyls) benzene base Iodonium, double (epoxides of 4- 12) benzene base Iodonium, 4- (epoxide of 2- hydroxyls 14) phenyl Ben Ji Iodonium, 4- cumenyls (p-methylphenyl) Iodonium or 4- isobutylphenyl (p-methylphenyl) Iodonium etc..

Among the ion in compound shown in above-mentioned formula (C-1), following formula (C- can be enumerated as preferable ion Sulfonium cation shown in 1d)：

In formula (C-1d), W⁸Independently represent by hydrogen atom, alkyl, hydroxyl, alkoxy, alkyl carbonyl, alkane carbonyloxy group, alkane The base selected in oxygen carbonyl, halogen atom, the aryl that can have substituent, group formed by aromatic carbonyl.X²Represent and above-mentioned formula (C-1) In X²Identical meaning.

As the instantiation of the sulfonium cation shown in above-mentioned formula (C-1d), can enumerate 4- (thiophenyl) phenyl diphenyl sulfonium, Double (4- fluorophenyls) sulfonium of 4- (4- benzoyl -2- chlorophenylsulfanyls) phenyl, 4- (4- benzoylphenylsulfanyls) phenyl diphenyl sulfonium, Phenyl [4- (4- biphenyl sulfenyl) phenyl] 4- biphenyl sulfonium, phenyl [4- (4- biphenyl sulfenyl) phenyl] 3- biphenyl sulfonium, [4- (4- acetyl Thiophenyl) phenyl] diphenyl sulfonium, diphenyl [4- (to three thiophenyls) phenyl] diphenyl sulfonium.

In fluoroalkyl fluorophosphoric acid anion shown in above-mentioned formula (C-1b), W³The alkyl substituted through fluorine atom is represented, preferably Carbon number be 1~8, more preferably carbon number be 1~4.As the instantiation of alkyl, methyl, ethyl, third can be enumerated The straight chained alkyls such as base, butyl, amyl group, octyl group；The branched alkyl groups such as isopropyl, isobutyl group, secondary butyl, three-level butyl；Even ring Cycloalkyl such as propyl group, cyclobutyl, cyclopenta, cyclohexyl etc., the hydrogen atom of alkyl is substituted is usually for the ratio of fluorine atom More than 80%, preferably more than 90%, more preferably 100%.If the Replacement rate of fluorine atom is not up to 80%, above-mentioned formula (C-1) institute The acid strength of the fluoroalkyl fluorophosphate shown can reduce.

Particularly good W³Be 1~4 for carbon number, and the Replacement rate of fluorine atom be 100% straight-chain or branch-like it is complete Fluoroalkyl, as instantiation, CF can be enumerated₃、CF₃CF₂、(CF₃)₂CF、CF₃CF₂CF₂、CF₃CF₂CF₂CF₂、(CF₃)₂CFCF₂、 CF₃CF₂(CF₃)CF、(CF₃)₃C。W³Number j be 1~5 integer, preferably 2~4, particularly good is 2 or 3.

As the instantiation of preferable fluoroalkyl fluorophosphoric acid anion, [(CF can be enumerated₃CF₂)₂PF₄]^-、[(CF₃CF₂)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CF)₃PF₃]^-、[(CF₃CF₂CF₂)₂PF₄]^-、[(CF₃CF₂CF₂)₃PF₃]^-、 [((CF₃)₂CFCF₂)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-、[(CF₃CF₂CF₂CF₂)₂PF₄]^-Or [(CF₃CF₂CF₂)₃PF₃]^-, Among these, particularly good is [(CF₃CF₂)₃PF₃]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CF)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-Or [((CF₃)₂CFCF₂)₂PF₄]^-。

As the preferred embodiments of the borate anion shown in above-mentioned formula (C-1c), wantonly (pentafluorophenyl group) boron can be enumerated Acid group ([B (C₆F₅)₄]^-), wantonly [(trifluoromethyl) phenyl] borate ([B (C₆H₄CF₃)₄]^-), double (pentafluorophenyl group) boric acid of difluoro Root ([(C₆F₅)₂BF₂]^-), trifluoro (pentafluorophenyl group) borate ([(C₆F₅)BF₃]^-), wantonly (difluorophenyl) borate ([B (C₆H₃F₂)₄]^-) etc..It is particularly good for wantonly (pentafluorophenyl group) borate ([B (C among these₆F₅)₄]^-)。

As the second form of acid producing agent (A), can enumerate double (the trichloromethyl) -6- piperonyls -1,3,5-triazines of 2,4-, The symmetrical triazines of double (the trichloromethyl) -6- [2- (2- furyls) vinyl] of 2,4-, double (trichloromethyl) -6- [2- (the 5- first of 2,4- Base -2- furyls) vinyl] symmetrical triazine, double (the trichloromethyl) -6- [2- (5- ethyl -2- furyls) vinyl] of 2,4- are right Claim the symmetrical triazines of double (the trichloromethyl) -6- [2- (5- propyl group -2- furyls) vinyl] of triazine, 2,4-, double (three chloromethanes of 2,4- Base) the symmetrical triazines of -6- [2- (3,5- Dimethoxyphenyls) vinyl], double (trichloromethyl) -6- [2- (the 3,5- diethoxies of 2,4- Base phenyl) vinyl] symmetrical triazine, double (the trichloromethyl) -6- [2- (3,5- dipropoxies phenyl) vinyl] symmetrical three of 2,4- The symmetrical triazines of double (the trichloromethyl) -6- [2- (3- methoxyl group -5- ethoxyl phenenyls) vinyl] of piperazine, 2,4-, double (three chloromethanes of 2,4- Base) symmetrically [(3,4- is sub- by 2- by double (the trichloromethyl) -6- of triazine, 2,4- by -6- [2- (3- methoxyl group -5- propoxyphenyls) vinyl] Methylenedioxy group phenyl) vinyl] symmetrical triazine, the symmetrical triazines of double (the trichloromethyl) -6- (3,4- methylenedioxyphenyls) of 2,4-, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) symmetrical triazine of phenyl, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxies of 2- Base) the symmetrical triazine of phenyl, 2,4- be double-and trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) symmetrical triazine of styryl phenyl, 2,4- be double - Double (three chloromethanes of trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) symmetrical triazine of styryl phenyl, 2- (4- methoxyphenyls) -4,6- Base) -1,3,5- triazines, double (the trichloromethyl) -1,3,5- triazines of 2- (4- methoxyl groups naphthyl) -4,6-, 2- [2- (2- furyls) second Alkenyl] double (the trichloromethyl) -1,3,5- triazines of -4,6-, double (three chloromethanes of 2- [2- (5- methyl -2- furyls) vinyl] -4,6- Base) -1,3,5- triazines, double (the trichloromethyl) -1,3,5- triazines of 2- [2- (3,5- Dimethoxyphenyls) vinyl] -4,6-, 2- Double (the trichloromethyl) -1,3,5- triazines of [2- (3,4- Dimethoxyphenyls) vinyl] -4,6-, 2- (3,4- methylenedioxybenzenes Base) double (the trichloromethyl) -1,3,5- triazines of -4,6-, ginseng (1,3- dibromopropyls) -1,3,5- triazines, ginseng (2,3- dibromopropyls) - The following formula (C-2) such as the halogen-containing triaizine compounds such as 1,3,5- triazines and ginseng (2,3- dibromopropyls) isocyanuric acid ester Shown halogen-containing triaizine compounds.

In formula (C-2), W⁹~W¹¹Independently it is expressed as alkylhalide group.

Also, the 3rd form as light acid producing agent (C), can enumerate α-(tolysulfonyl epoxide imido grpup)-phenyl second Nitrile, α-(phenylsulfonyloxy imido grpup) -2,4 dichloro benzene base acetonitrile, α-(phenylsulfonyloxy imido grpup) -2,6- dichlorophenyl second Nitrile, α-(2- chloro benzenesulfonyloxies imido grpup) -4- methoxyphenylacetonitriles, α-(ethylsulfonyloxy imido grpup) -1- chlorine amylenes Compound shown in base acetonitrile and following formula (C-3) containing sulfonic acid oximido.

In formula (C-3), W¹²Represent 1 valency, divalent or trivalent organic group, W¹³Expression is substituted or unsubstituted saturated hydrocarbons Base, unsaturated alkyl or aromatic series compound base, n represent the number of repeat unit of the structure in parantheses.

In above-mentioned formula (C-3), aromatic series compound basis representation makes aromatic compound show distinctive physics, chemically The base of the compound of matter, the heteroaryl such as aryl or furyl, thienyl such as phenyl, naphthyl can be enumerated.These also can be in ring The upper appropriate substituent with more than 1, such as halogen atom, alkyl, alkoxy, nitro etc..Also, W¹³Particularly good is carbon atom Number is 1 to 6 alkyl, can enumerate methyl, ethyl, propyl group, butyl.Especially with W¹²For aromatic series compound base, W¹³For carbon atom The compound for the alkyl that number is 1 to 4 is preferable.

As the acid producing agent shown in above-mentioned formula (C-3), as n=1, W can be enumerated¹²For phenyl, aminomethyl phenyl, methoxyl group Phenyl is any, W¹³For the compound of methyl, can specifically enumerate α-(mesyloxy imido grpup) -1- phenylacetonitriles, α - (mesyloxy imido grpup) -1- (p-methylphenyl) acetonitrile, α-(mesyloxy imido grpup) -1- (p- methoxyphenyls) second Nitrile, [2- (the third sulfonyloxy imido grpup) -2,3- dihydroxy thiophene -3- subunits] (o-tolyl) acetonitrile etc..As n=2, as Acid producing agent shown in above-mentioned formula (C-3), it can specifically enumerate the acid generation shown in following formula (C-3-1)~formula (C-3-8) Agent：

In addition, the 4th form as light acid producing agent (C), can enumerate cationic moiety has the salt of naphthalene nucleus.Should " tool Have naphthalene nucleus " refer to structure derived from naphthalene, it is intended that the structure of at least two ring, and the meaning of the armaticity of they can be maintained.The naphthalene Ring can also have the straight-chain that alkyl, hydroxy, the carbon number of the straight-chain that carbon number is 1 to 6 or branch-like are 1 to 6 Or the substituent of alkoxy of branch-like etc..Structure derived from naphthalene nucleus can be 1 valency base (free valence be 1), or divalent More than base (free valence is 2), more satisfactory is that 1 valency base (is only, now, to deduct the part closed with above-mentioned substituent bond to come Calculate free valence).Naphthalene nucleus number is preferably 1~3.

There is the cationic moiety of the salt of naphthalene nucleus as such cationic moiety, preferably shown in following formula (C-4) Structure：

In formula (C-4), W¹⁴~W¹⁶In at least 1 represent base shown in following formula (C-4a), remaining represents that carbon number is 1 to 6 straight-chain or the straight-chain that the alkyl of branch-like, the phenyl that can have substituent, hydroxy or carbon number are 1 to 6 Or the alkoxy of branch-like.Or W¹⁴~W¹⁶One of for the base shown in following formula (C-4a), remaining both only respectively Stand as carbon number W¹⁴~W¹⁶The alkylidene of straight-chain or branch-like, these end can be bonded and annular in shape.

In formula (C-4a), W¹⁷、W¹⁸Independently represent hydroxy, the straight-chain or branch-like that carbon number is 1 to 6 Alkoxy or carbon number be 1 to 6 straight-chain or branch-like alkyl, W¹⁸Represent singly-bound or can have the carbon of substituent Atomicity is 1 to 6 straight-chain or the alkylidene of branch-like.L and m independently represents 0~2 integer, and l+m is less than 3. Work as W¹⁷When having a plurality of, they can be mutually the same or different.Work as W¹⁸When having a plurality of, they can be mutually the same or different.

Above-mentioned W¹⁴~W¹⁶The number of base shown in central above-mentioned formula (C-4a), the stability viewpoint based on compound are preferable For 1, remaining is the alkylidene of the straight-chain that carbon number is 1 to 6 or branch-like, and these end can be bonded and annular in shape. Now, above-mentioned 2 alkylidenes can include sulphur atom and form 3~9 yuan of rings.The number for forming the atom (sulfur atom-containing) of ring is preferable For 5~6.

Also, the substituent that can have as above-mentioned alkylidene, it is (now, former with the carbon of composition alkylidene can to enumerate oxygen atom Son is collectively forming carbonyl), hydroxy etc..

Also, the substituent that can have as phenyl, can enumerate hydroxy, the straight-chain of carbon number 1~6 or branch-like Alkyl of alkoxy, the straight-chain of carbon number 1~6 or branch-like etc..

Category is suitable as these cationic moieties person, following formula (C-4b), (C-4c) those shown can be enumerated, especially with following formula (C-4c) structure shown in is preferred.

As such cationic moiety, Ke Wei Iodonium salt or sulfonium salt；More satisfactory based on viewpoints such as sour generation efficiencies is sulfonium salt.

It is more satisfactory for can shape so as to, the anionicsite person that there is the salt of naphthalene nucleus for being suitable as cationic moiety Into the anion of sulfonium salt.

It is part or all of perfluorinated fluoroalkyl sulfonic acids of hydrogen atom as the anionicsite of such acid producing agent Ion or aryl sulfonic acid ion.

Alkyl in fluoroalkyl sulfonic acids ion can be straight-chain, branch-like or the ring-type that carbon number is 1 to 20, based on production Raw sour volume size and its diffusion length, preferably carbon number are 1 to 10.Particularly in branch-like or ring-type person because of diffusion Apart from short and preferable.Also, for by can inexpensively synthesize, methyl, ethyl, propyl group, butyl, octyl group etc. can be enumerated as preferable Person.

Aryl in aryl sulfonic acid ion is the aryl that carbon number is 6 to 20, and can enumerate can take through alkyl, halogen atom Phenyl, the naphthyl in generation.Particularly, for by can inexpensively synthesize, preferably carbon number is 6 to 10 aryl.As preferable The instantiation of person, phenyl, tosyl, ethylphenyl, naphthyl, methyl naphthyl etc. can be enumerated.

In above-mentioned fluoroalkyl sulfonic acids ion or aryl sulfonic acid ion, hydrogen atom part or all it is perfluorinated when fluorination Rate is preferably 10~100%, more preferably 50~100%, the winner particularly with fluorine atom substitution whole hydrogen atoms, because of the intensity of acid Enhancing and it is preferable.Belong to such person, can specifically enumerate triflate, perfluor butanesulfonate, perfluorooctane sulfonate ester, perfluor Benzene sulfonate etc..

Among these, as preferable anionicsite, following formula (C-4d) those shown can be enumerated：

W²⁰SO₃ ^-Formula (C-4d)

In formula (C-4d), W²⁰For the base shown in following formula (C-4e), (C-4f) and (C-4g).

-C_xF_2x+1Formula (C-4e)

In formula (C-4e), x represents 1~4 integer.In formula (C-4f), W²¹Represent hydrogen atom, hydroxy, carbon atom be 1 to Either the alkyl of branch-like or carbon number are 1 to 6 straight-chain or the alkoxy of branch-like to 6 straight-chain, y represents 1~ 3 integer.Among these, triflate, perfluor butanesulfonate are preferably based on safety point.

Also, as anionicsite, it is possible to use the nitrogenous person shown in following formula (C-4h), formula (C-4i).

In formula (C-4h), formula (C-4i), X^aRepresent the straight-chain that substitutes through fluorine atom of at least one hydrogen atom or branch-like Alkylidene, the carbon number of the alkylidene is 2~6, preferably 3~5, and most preferably carbon number is 3.Also, Y^a、Z^aIndependently The straight-chain or the alkyl of branch-like that expression at least one hydrogen atom substitutes through fluorine atom, the carbon number of the alkyl is 1~10, Preferably 1~7, more preferably 1~3.

X^aAlkylidene carbon number or Y^a、Z^aAlkyl carbon number it is smaller, the dissolubility of organic solvent is cured Well, therefore preferably.

Also, X^aAlkylidene or Y^a、Z^aAlkyl in, through fluorine atom substitution hydrogen atom number the more, sour intensity is cured By force, therefore preferably.The ratio of fluorine atom in the alkylidene or alkyl, namely fluorination rate are preferably 70~100%, more preferably 90 ~100%, the perfluorinated alkylidene or perfluoroalkyl that most preferably all hydrogen atoms substitute through fluorine atom.

Category, which is suitable as such cationic moiety, has the salt person of naphthalene nucleus, can enumerate following formula (C-4j), formula (C-4k) Shown compound：

Furthermore as the 5th form of light acid producing agent (C), can enumerate double (p-toluenesulfonyl) diazomethanes, it is double (1, 1- dimethylethylsulfonyls) diazomethane, double (cyclohexylsulfonyl) diazomethanes, double (2,4- 3,5-dimethylphenyls sulfonyls) Double sulfonyidiazomethanes classes such as diazomethane；P-methyl benzenesulfonic acid 2- nitrobenzene methyl esters, p-methyl benzenesulfonic acid 2,6- dinitro benzene first Ester, toluenesulfonic acid nitrobenzene methyl esters, toluenesulfonic acid dinitro benzene methyl esters, sulfonic acid nitrobenzene methyl esters, nitrophenylcarbonates methyl esters, carbonic acid The nitrobenzoyl radical derivative such as dinitro benzene methyl esters；1,2,3,-thrihydroxy-benzene triflate, 1,2,3,-thrihydroxy-benzene front three benzene sulfonate, toluene Sulfonic acid benzene methyl, sulfonic acid benzene methyl, N- mesyloxies succinimide, N- trichloromethyl sulfonyloxies succinimide, N- The sulfonic acid esterses such as phenylsulfonyloxy group maleimide, N- mesyloxy phthalimides；N- hydroxyl phthalyls The trifluoromethanesulfonic acid esters such as imines, N- hydroxynaphthylimides；Er Ben Ji Iodonium hexafluorophosphates, (4- methoxyphenyl) Ben Ji Iodonium tri- It is fluorine mesylate, double (to three-level butyl phenyl) Iodonium fluoroform sulphonates, triphenylsulfonium hexafluorophosphate, (4- methoxyphenyls) The salts such as diphenyl sulfonium fluoroform sulphonate, (to three-level butyl phenyl) diphenyl sulfonium fluoroform sulphonate；Styrax toluene The styrax toluenesulfonic acid esters such as sulphonic acid ester, Alpha-Methyl styrax tosylate；Other Er Ben Ji Iodonium salt, triphenylsulfonium Salt, Arenediazonium salts, methyl phenyl carbonate etc..

Light acid producing agent (C) can be used alone, and two or more use also can be combined.Also, total usage amount based on resin (A) For 100 parts by weight, the content of light acid producing agent (C) is 0.5 parts by weight to 4.5 parts by weight, preferably 0.6 parts by weight to 4 weight Part, more preferably 0.7 parts by weight to 3.5 parts by weight.By the way that the dosage of light acid producing agent (C) is taken as into above range, then easily adjust The good sensitivity of fixture, in uniform solution, and the photosensitive resin composition that storage stability is excellent.

Solvent (D)

The species of solvent (D), is not particularly limited in the range of without prejudice to the object of the invention, can be by being used in eurymeric in the past Suitably select and use in the organic solvent of photosensitive resin composition.

As solvent (D) instantiation, acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2- heptan can be enumerated The ketones such as ketone；Ethylene glycol, ethylene glycol acetate, diethylene glycol, diethylene glycol monoacetate, propane diols, propane diols list acetic acid The polyalcohols such as ester, DPG, the monomethyl ether of dipropylene glycol monoacetate, single ether, single propyl ether, monobutyl ether, monophenyl ether and Its derivative；The cyclic ethers class such as dioxanes；Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid fourth Ester, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethoxy ethyl acetate, methoxypropionic acid Methyl esters, ethoxyl ethyl propionate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyls ethyl propionate, 2- hydroxyls The esters such as base -3 Methylbutanoic acid methyl esters, 3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters；Toluene, two Toluene etc. is aromatic hydrocarbon；Deng.These can be used alone, and can also mix two or more use.

Total usage amount based on resin (A) is 100 parts by weight, and the content of solvent (D) is 60 parts by weight to 600 parts by weight, Preferably 70 parts by weight are to 500 parts by weight, more preferably 80 parts by weight to 400 parts by weight.

Mercaptan compound (E)

Mercaptan compound (E) has the structure shown in following formula (E-1)：

Work as R¹、R²For alkyl when, the alkyl can be straight-chain or branch's chain state, preferably straight-chain.Work as R¹、R²For alkyl When, as the carbon number of the alkyl, preferably 1~4, particularly good is 1 or 2, most preferably 1.As R¹、R²Combination, preferably one Person is hydrogen atom, another one is alkyl, it is particularly good be one be hydrogen atom, another one be methyl.

Work as R³For alkylidene when, the alkylidene can be straight-chain or branch's chain state, preferably straight-chain.Work as R³For alkylidene When, as the carbon number of the alkylidene, preferably 1~10, more preferably 1~5, particularly good is 1 or 2, most preferably 1.

R⁴Defined u valencys organic group, specifically for 2~6 valency fatty groups of the atom beyond carbon can be included.Make For R⁴Atom beyond the carbon that can be included, nitrogen-atoms, oxygen atom, sulphur atom, fluorine atom, chlorine atom, bromine atoms and iodine can be enumerated Atom etc..R⁴The structure of affiliated fatty group can be straight-chain, branch's chain state or ring-type, or these structures combine Structure.

As in the mercaptan compound (E) shown in formula (E-1), more preferably as the compound shown in following formula (E-2)：

In formula (E-2), R⁴, u definition it is identical with formula (E-1), R⁵The alkyl for being 1 to 4 for hydrogen atom or carbon number.

The concrete example of mercaptan compound (E) can enumerate the concrete example of following formula (E-3)~formula (E-16), but be not limited to this A little concrete examples：

Total usage amount based on resin (A) is 100 parts by weight, and the content of mercaptan compound (E) is 0.3 parts by weight to 3 weights Measure part, preferably 0.4 parts by weight to 2.8 parts by weight, more preferably 0.5 parts by weight to 2.5 parts by weight.

When not contained in chemical amplification positive photosensitive resin composition as the mercaptan compound (E) shown in formula (E-1) When, the rectangularity of its photoresistance pattern formed is bad.

Anthracene compound (F)

Anthracene compound (F) can enumerate following concrete example, but be not restricted to these concrete examples：Anthracene (anthracene), 9,10- dibutoxies anthracene, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxys anthracene, 2- tributyl -9,10- dimethoxies Base anthracene, 2,3- dimethyl -9,10- dimethoxys anthracene, 9- methoxyl group -10- methyl anthracene, 9,10- diethoxies anthracene, 2- ethyl -9, 10- diethoxies anthracene, 2- tributyl -9,10- diethoxies anthracene, 2,3- dimethyl -9,10- diethoxies anthracene, 9- ethyoxyls - 10- methyl anthracene, 9,10- dipropoxies anthracene, 9,10- diisopropoxies anthracene, 2- ethyl -9,10- dipropoxies anthracene, the fourths of 2- the 3rd Base -9,10- dipropoxies anthracene, 2,3- dimethyl -9,10- dipropoxies anthracene, 9- isopropoxy -10- methyl anthracene, 9,10- diformazans Phenoxy group anthracene, 2- ethyl -9,10- xylyloxies anthracene, 2- tributyl -9,10- xylyloxies anthracene, 2,3- dimethyl -9, 10- xylyloxies anthracene, 9- toloxyl -10- methyl anthracene, 9,10- bis--Alpha-Methyl toloxyls anthracene, 2- ethyls -9,10- two - Alpha-Methyl toloxyl anthracene, 2- tributyl -9,10- two-Alpha-Methyl toloxyls anthracene,-α of 2,3- dimethyl -9,10- two-first Base toloxyl anthracene, 9- (Alpha-Methyl toloxyl) -10- methyl anthracene, 9,10- diphenylanthrancenes, 9- methoxyl groups anthracene, 9- ethyoxyls The compounds such as anthracene, 9- methyl anthracene, 9- bromines anthracene, 9- methyl mercaptos anthracene, 9- ethylmercapto group anthracenes.

Total usage amount based on resin (A) is 100 parts by weight, and the content of anthracene compound (F) is 0.2 parts by weight to 1.5 Parts by weight, preferably 0.25 parts by weight are to 1.3 parts by weight, more preferably 0.3 parts by weight to 1.1 parts by weight.

When not including anthracene compound (F) in chemical amplification positive photosensitive resin composition, chemical amplification type is just The sensitivity of type photosensitive resin composition is bad.

Additive (G)

In chemical amplification positive photosensitive resin composition, as long as not influenceing the effect of the present invention, more can further it wrap Containing additive (G), additive (G) can be used alone it is a kind of or mixed a variety of, end is seen be actually needed depending on.Illustrate additive below (G) particular content.

In chemical amplification positive photosensitive resin composition, to lift plasticity, it also can further contain polyethylene tree Fat is as additive (G).As the instantiation of polyvinyl resin, polyvinyl chloride, polystyrene, poly- hydroxy benzenes second can be enumerated It is alkene, polyvinyl acetate, polystyrene formic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, PVP, poly- Vinylphenol and these copolymer etc..Polyvinyl resin, based on glass transition temperature it is relatively low for, preferably polyvinyl methyl ether.

Also, in chemical amplification positive photosensitive resin composition, formed to be lifted using photosensitive resin composition Template and metal substrate adherence, also can further contain then auxiliary agent as additive (G).

Furthermore in chemical amplification positive photosensitive resin composition, to lift coating, defoaming, equal levelling etc., Interfacial agent can further be contained as additive (G).As the instantiation of interfacial agent, can enumerate BM-1000, BM-1100 (being BM Chmie company systems), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (being DIC company systems), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (being Sumitomo 3M company systems), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (being Asahi Glass company system), SH-28PA, SH-190, SH-193, SZ-6032, The commercially available fluorine system interfacial agents such as SF-8428 (being Toray Silicone company systems), it is only non-limiting in these.

In addition, in chemical amplification positive photosensitive resin composition, to carry out the deliquescent fine setting to imaging liquid, Acid, acid anhydrides or higher boiling solvent can further be contained as additive (G).

As acid and the instantiation of acid anhydrides, acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid, benzene can be enumerated The monocarboxylic acid class such as formic acid, cinnamic acid；Lactic acid, 2- hydroxybutyric acids, 3-hydroxybutyrate, salicylic acid, m-hydroxybenzoic acid, para hydroxybenzene The hydroxyl list carboxylics such as formic acid, 2- hydroxyls cinnamic acid, 3- hydroxyls cinnamic acid, 4-Hydroxycinnamic Acid, 5- Hydroxy M Phthalic Acids, syringic acid Acids；Oxalic acid, butanedioic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic two Formic acid, terephthalic acid (TPA), 1,2- cyclohexane dicarboxylic acids, 1,2,4- cyclohexanetricarboxylic acids, BTCA, trimellitic acid, benzene The polybasic carboxylic acid classes such as equal tetracid, pentamethylene tetrabasic carboxylic acid, BTCA, 1,2,5,8- naphthalene tetracarboxylic acids；Itaconic anhydride, butanedioic acid Acid anhydride, citraconic anhydride, laurylene succinic anhydride, tricarballylic acid's acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrochysene are adjacent Phthalate anhydride, humic acid acid anhydride, 1,2,3,4- butane tetracarboxylics acid anhydrides, pentamethylene tetracarboxylic dianhydride, phthalic anhydride, benzene equal four The double trimellitic anhydrides of acid anhydrides, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol, glycerine ginseng trimellitic anhydride Deng acid anhydrides；Deng.

Also, the instantiation as higher boiling solvent, can enumerate N-METHYLFORMAMIDE, DMF, N- first Yl carboxylic acid anilides, N- methylacetamides, DMAC N,N' dimethyl acetamide, N- methylpyrrole pyridines ketone, dimethyl sulfoxide (DMSO), benzyl second Ether, two hexyl ethers, pentanedione, different Buddhist ketone, caproic acid, octanoic acid, 1- octanols, 1 nonyl alcohol, phenmethylol, phenylmethyl acetate, benzoic acid Ethyl ester, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propene carbonate, phenyl Sai Lusu acetic acid esters Deng.

Also, in chemical amplification positive photosensitive resin composition, to lift sensitivity, further can also make containing sensitizer For additive (G).

There is no particular restriction for the manufacture method of chemical amplification positive photosensitive resin composition, can by it is above-mentioned it is each into Divide and mixed with common method, stir and be made.As workable device when above-mentioned each composition is mixed, is stirred, can enumerate Dissolving machine, homogenizer, three-roll mill etc..After above-mentioned each composition uniformly mixing, also gained mixture can further be utilized Screen cloth, molecular filter etc. are filtered.

Using above-mentioned chemical amplification positive photosensitive resin composition, in the metal watch of the substrate with metal surface Formed on face and be not particularly limited as to form the method for the photoresistance pattern of the mold of electroplating formation body.

As preferable method, it can enumerate and include：Layering steps, on the metal surface of the substrate with metal surface, The photo-sensitive resin that lamination is made up of above-mentioned chemical amplification positive photosensitive resin composition；Step of exposure, to sense Photosensitive resin layer irradiates actinic ray or radioactive ray；And development step, the photo-sensitive resin after exposure is imaged, and make Into forming the manufacture method of the substrate with mold of the mold of electroplating formation body.

As the substrate for lamination photo-sensitive resin, it is not particularly limited, always known person can be used, can illustrates for example electric The substrate of sub- part or thereon formed with set Wiring pattern person.It is to use that there is metal surface for the substrate Person；As the metal species for forming metal surface, preferably copper, gold, aluminium, more preferably copper.

Photo-sensitive resin be with such as in the following manner on substrate.That is, the chemical amplification positive by liquid Photosensitive resin composition is coated on substrate, then removes solvent by heating to form the photoresist of desired thickness Layer.The thickness of photo-sensitive resin, as long as can be then not particularly limited using the photoresistance pattern that desired thickness is formed as template.Sense The thickness of photosensitive resin layer is not particularly limited, preferably more than 10 μm, more preferably 10~150 μm, and particularly good is 20~120 μm, most Good is 20~100 μm.

As coating method of the photosensitive resin composition on substrate, method of spin coating, slot coated method, roller can be used The methods of rubbing method, screen painting method, scattering method.Prebake conditions preferably are carried out to photo-sensitive resin.Prebake conditions are because of sense The species of each composition in photosensitiveness resin combination, mix proportionses, coating film thickness etc. and it is different, only generally at 70~150 DEG C, preferably For 80~140 DEG C and 2~60 minutes or so.

To the photo-sensitive resin being formed as above, across the shade of predetermined pattern, it is photochemical optionally to irradiate (exposure) Ray or radioactive ray, such as the ultraviolet or luminous ray that wavelength is 300~500nm.

As the line source of radioactive ray, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide can be used Lamp, argon laser etc..Also, radioactive ray include microwave, infrared ray, luminous ray, ultraviolet, X ray, gamma-rays, electron beam, matter Beamlet, neutron beam, ion beam etc..Radioactive ray exposure is the film of the composition or photo-sensitive resin because of photosensitive resin composition Thickness waits and different, such as is 100~10000mJ/cm during using extra-high-pressure mercury vapour lamp².Also, radioactive ray, which include, makes light acid producing agent (C) light of activation is to produce acid.

After exposure, the diffusion of acid is promoted to photo-sensitive resin heating by using known method, in photonasty tree Exposed part in adipose membrane, makes the alkali-solubility of photo-sensitive resin change.

Secondly, by by the photo-sensitive resin after exposure, following existing method to be imaged, and solvable part is molten Solution, remove, and form set photoresistance pattern.Now, it is to use alkaline aqueous solution as imaging liquid.

As imaging liquid, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammoniacal liquor, second can be used Amine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl-diethyl-amine, dimethylethanolamine, triethanolamine, tetramethylphosphonihydroxide hydroxide Ammonium, tetraethylammonium hydroxide, pyrroles, piperidines, 1,8- diazabicyclos [5,4,0] -7- hendecenes, 1,5- diazabicyclos [4,3, 0] aqueous solution of the bases such as -5- nonanes.Also, also the water solubilitys such as methanol, ethanol will can be in right amount added to the aqueous solution of above-mentioned bases The aqueous solution that organic solvent or interfacial agent form uses as imaging liquid.

Time of developing be it is different because of thickness of the composition of photosensitive resin composition or photo-sensitive resin etc., usually 1 ~30 minutes.Developing method can be that covering liquid method, infusion process, paddle method, injection visualization method etc. are any.

After imaging, the flowing water cleaning of 30~90 seconds is carried out, and is subject to drying using air gun or baking oven etc..In this way, i.e. The substrate with mold for possessing the photoresistance pattern as mold on the metal surface of the substrate with metal surface can be manufactured.

(removed by the non-photoresistance portion in the mold of the substrate with mold to being formed according to the above method with imaging liquid Part), by electroplating the embedment conductor such as metal, the electroplating formation of the class of connection terminal such as projection or metal column can be formed Body.In addition, plating process is not particularly limited, always known various methods can be used.As electroplate liquid, it is especially suitable for making With plating solder, copper are electroplated, gold is electroplated, nickel plating solution.Remaining mold, finally follows common method to be gone using stripper etc. Remove.

According to the above method, that is, undercutting can be suppressed by being formed, while as the photoresistance pattern of mold.By using being so made The substrate for possessing the mold that can suppress undercutting, the electroplating formation body excellent with the adhesion of substrate can be manufactured.

Embodiment will be enumerated below and describes the present invention in detail, but the invention is not limited in disclosed in these embodiments Hold.

The synthesis example of resin (A)

Illustrate the synthesis example A-1 to A-10 of resin (A) below：

Synthesis example A-1

Nitrogen inlet, agitator, heater, condenser pipe and temperature are set on four cervical vertebra bottles of 1000 milliliters of a volume Meter.Then, the diethylene glycol dimethyl ether of 50 parts by weight is added, and oil bath temperature is warming up to 70 DEG C.Then, by 20 parts by weight As the compound (referred to as (a11)) shown in formula (A-1-26), 20 parts by weight as the compound shown in formula (A-2-2) (referred to as For (a31)), 20 parts by weight as the compound (referred to as (a33)) shown in formula (A-3-1), the methacrylic acid of 10 parts by weight Methacrylic acid -2- the hydroxy methacrylates (referred to as (a43)) of (referred to as (a41)), 30 parts by weight and the 2 of 3.5 parts by weight, Double -2- the methylbutyronitriles of 2 '-azo (referred to as AMBN) are added in four cervical vertebra bottles, and are slowly stirred above-mentioned mixed solution.It is whole poly- The reaction temperature of conjunction process maintains 70 DEG C, and polymerization time continues 6 hours, after the completion of polymerization, by polymerizate from four cervical vertebra bottles Middle taking-up, and solvent is sloughed, resin (A-1) can be obtained.

Synthesis example A-2 to A-10

Synthesis example A-2 to A-10 is to prepare resin (A-2) to (A-10) with the step identical with synthesis example A-1, different Place be：Change reaction temperature, reaction time, the species and usage amount of composition, and state in detail in table 1.

In addition, the compound corresponding to abbreviation in following synthesis example A-1 to A-10 is as follows.

[table 1]

The synthesis example of novolac resin (B)

Illustrate the synthesis example B-1 to B-6 of novolac resin (B) below：

Synthesis example B-1

Nitrogen inlet, agitator, heater, condenser pipe and temperature are set on four cervical vertebra bottles of 1000 milliliters of a volume Count, m-cresol (referred to as (b12)), 0.50 mole of the p-Cresol of 0.40 mole of addition after importing nitrogen (are referred to as (b13)), 0.10 mole of 3,5- xylenols (referred to as (b14)), 0.65 mole of formaldehyde (referred to as (b21)) and 0.02 mole of oxalic acid.Being slowly stirred makes reaction solution be warming up to 100 DEG C, and polycondensation 6 hours at a temperature of this.Then, will Reaction solution is warming up to 180 DEG C, and is dried under reduced pressure with 10mmHg pressure, will can obtain novolaks tree after solvent devolatilization Fat (B-1).

Synthesis example B-2 to B-6

Synthesis example B-2 to B-6 is to prepare novolac resin (B-2) to (B- with the step identical with synthesis example B-1 6), different places is：Change reaction temperature, reaction time, the species and usage amount of composition, and state in detail in table 2.

In addition, the compound corresponding to abbreviation in following synthesis example B-1 to B-6 is as follows.

Referred to as	Chinese
		b11	O-cresol (o-cresol)
b12	M-cresol (m-cresol)
		b13	P-Cresol (p-cresol)
b14	2,5- xylenols (2,5-xylenol)
		b15	3,5- xylenols (3,5-xylenol)
b16	3,4- xylenols (3,4-xylenol)
		b21	Formaldehyde (formaldehyde)
b22	Benzaldehyde (benzaldehyde)

[table 2]

The embodiment of chemical amplification positive photosensitive resin composition

Illustrate the embodiment 1 of chemical amplification positive photosensitive resin composition to embodiment 14 and comparative example 1 below To comparative example 6：

Embodiment 1

By the resin (A-1) of 100 parts by weight obtained by foregoing synthesis example, 0.5 parts by weight light acid producing agent C-1 (following letters Claim C-1), 3.0 parts by weight as the compound (hereinafter referred to as E-1) and the fourths of 9,10- bis- of 0.2 parts by weight shown in formula (E-6) Epoxide anthracene (hereinafter referred to as F-1), after adding the propylene glycol methyl ether acetate (hereinafter referred to as D-1) of 60 parts by weight, stirred with rock type Device is mixed, is dissolved mixing, you can modulates and obtains chemical amplification positive photosensitive resin composition, the chemical amplification type is just Type photosensitive resin composition is evaluated in a manner of following each evaluation of measuring, and acquired results are as shown in table 3.

Embodiment 2 is to embodiment 14

Embodiment 2 to embodiment 14 is to use to make with the chemical amplification positive photosensitive resin composition of embodiment 1 Method identical operating method, difference are that embodiment 2 to embodiment 14 is to change chemical amplification positive photonasty tree The species and usage amount of raw material in fat composition, it is formulated and following evaluation result is as shown in table 3 and table 4.

Comparative example 1 is to comparative example 6

Comparative example 1 to comparative example 6 is using the chemical amplification positive photosensitive resin composition making side with embodiment 1 Method identical operating method, difference are that comparative example 1 to comparative example 6 is to change chemical amplification positive photoresist group The species and usage amount of raw material into thing, it is formulated and following evaluation result is as shown in table 4.

Compound in table 3 and table 4 corresponding to label is as follows.

[table 3]

[table 4]

Evaluation method

A. sensitivity

By embodiment and the chemical amplification positive photosensitive resin composition of comparative example, it is coated on using spin coater On the copper base of 6 inch, the photo-sensitive resin of 50 μm of thickness is formed.Thereafter, the photo-sensitive resin is carried out at 110 DEG C 6 minutes prebake conditions.After prebake conditions, shade and (the Ultratech companies of exposure device Titan 2 using the sectional hole patterns in 60 μm of footpaths System), pattern exposure is carried out with g lines, h lines and i lines and periodically changes light exposure.Then, by substrate-placing in heating plate On, heat (PEB) after the exposure of 3 minutes is carried out at 100 DEG C.Thereafter, drip 2.38% hydroxide four to photo-sensitive resin First ammonium (TMAH) aqueous solution, placed 60 seconds at 23 DEG C, be repeated 4 times and imaged.Thereafter, flowing water cleaning is carried out, then is blown Spill nitrogen and obtain the thick film photoresistance pattern of the contact hole pattern with 50 μm of footpaths.

Then, ask for not being seen that there is the light exposure of pattern residue, namely for forming the minimum exposure needed for thick film photoresistance pattern Light quantity, the index as sensitivity.Evaluation criterion is as follows：

◎：Light exposure ＜ 100mJ/cm²

○：100mJ/cm²≤ light exposure ＜ 150mJ/cm²

Δ：150mJ/cm²≤ light exposure ＜ 200mJ/cm²

╳：Bao Guang Liang≤200mJ/cm²

B. rectangularity

Fig. 1 is refer to, Fig. 1 is the schematic diagram for the rectangularity for measuring photoresistance pattern.It is coated on the photoresist of substrate 100 Layer forms the photoresistance pattern 120 with non-photoresistance portion 124 with photoresistance portion 122 after above-mentioned exposure, development step.For upper The section configuration for stating the photoresistance pattern of optimum exposure is observed, and measures bottom width L_bAnd top width L_tValue, and count Calculate L_t/L_bIt is worth the index as rectangularity.Evaluation criterion is 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

Δ：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 result

Learnt by table 3, table 4, it is (real with the chemical amplification positive photosensitive resin composition containing mercaptan compound (E) Example 1 is applied to embodiment 14) to compare, the chemical amplification positive photosensitive resin composition not containing mercaptan compound (E) (compares Example 1,3,4, rectangularity 6) it is bad；It is (real with the chemical amplification positive photosensitive resin composition containing anthracene compound (F) Example 1 is applied to embodiment 14) to compare, the chemical amplification positive photosensitive resin composition not containing anthracene compound (F) (compares Example 2,3,5, sensitivity 6) it is bad.

Meanwhile when in the monomer mixture for the combined polymerization of resin (A), containing with the structure as shown in formula (A-1) During monomer (a1) (embodiment 1-5,9,11,14), its rectangularity performs better.In addition, when poly- also including containing in monomer mixture During monomer (a2) (embodiment 2-6,10,11) of oxyalkylene chain, its sensitivity performs better.

In addition, in the chemical amplification positive photosensitive resin composition containing novolac resin (B) (embodiment 3-5, When the 13rd, 14), its rectangle sex expression is also more preferably.

In summary, chemical amplification positive photosensitive resin composition of the invention because containing mercaptan compound (E), with And anthracene compound (F), therefore the problem of sensitivity and bad rectangularity can be improved.

On the other hand, if the resin (A) in the chemical amplification positive photosensitive resin composition of the present invention is by including spy The monomer mixture combined polymerization of order body (a1) and or the present invention chemical amplification positive photosensitive resin composition in When also containing novolac resin (B), obtained photoresistance pattern can further obtain more preferably rectangularity.

In addition, if the resin (A) in the chemical amplification positive photosensitive resin composition of the present invention is by including specific list The monomer mixture combined polymerization of body (a2) and when, obtained photoresistance pattern can further obtain more preferably sensitivity.

Although the present invention is disclosed above with embodiment, so it is not limited to the present invention, any art Middle tool usually intellectual, without departing from the spirit and scope of the present invention, when a little change and retouching can be made, thus it is of the invention Protection domain when being defined depending on appended claims institute defender.

Claims

1. a kind of chemical amplification positive photosensitive resin composition, including：

Resin (A), the resin (A) is obtained by monomer mixture combined polymerization, and contains acid dissociation protection group；

Light acid producing agent (C)；

Solvent (D)；

Mercaptan compound (E)；And

Anthracene compound (F)；

Wherein described mercaptan compound (E) has the structure shown in following formula (E-1)：

In formula (E-1), R¹、R²It is each independent to represent hydrogen atom or carbon number for 1 to 4 alkyl, R³Represent singly-bound or carbon atom Count the alkylidene for 1 to 10, R⁴Represent u valency organic groups；U represents 2 to 6 integer.

2. chemical amplification positive photosensitive resin composition according to claim 1, wherein the monomer mixture bag Monomer (a1) is included, the monomer (a1) has as the structure shown in following formula (A-1)：

In formula (A-1), L¹It is 1 to 6 straight-chain or alkyl, fluorine atom or the carbon of branch-like to represent hydrogen atom, carbon number Atomicity is 1 to 6 straight-chain or the fluorinated alkyl of branch-like；L²、L³、L⁴It is 1 to 6 independently to represent carbon number The straight-chain either alkyl of branch-like or straight-chain or the fluoroalkyl of branch-like that carbon number is 1 to 6, or L³、L⁴That This is bonded and is collectively forming the hydrocarbon ring that carbon number is 5 to 20.

3. chemical amplification positive photosensitive resin composition according to claim 1, wherein the monomer mixture bag Monomer (a2) is included, the monomer (a2) contains polyoxy alkylidene chain.

4. chemical amplification positive photosensitive resin composition according to claim 1, wherein also including novolaks tree Fat (B).

5. chemical amplification positive photosensitive resin composition according to claim 1, wherein based on the resin (A) Total usage amount is 100 parts by weight, and the content of the smooth acid producing agent (C) is 0.5 parts by weight to 4.5 parts by weight, the solvent (D) Content be 60 parts by weight to 600 parts by weight, the content of the mercaptan compound (E) is 0.3 parts by weight to 3 parts by weight, described The content of anthracene compound (F) is 0.2 parts by weight to 1.5 parts by weight.

6. chemical amplification positive photosensitive resin composition according to claim 2, wherein being mixed based on the monomer The total amount of thing is 100 parts by weight, and the usage amount of the monomer (a1) is 20 parts by weight to 80 parts by weight.

7. chemical amplification positive photosensitive resin composition according to claim 3, wherein being mixed based on the monomer The total amount of thing is 100 parts by weight, and the usage amount of the monomer (a2) is 10 parts by weight to 60 parts by weight.

8. chemical amplification positive photosensitive resin composition according to claim 4, wherein based on the resin (A) Total usage amount is 100 parts by weight, and the content of the novolac resin (B) is 20 parts by weight to 180 parts by weight.

9. a kind of manufacture method of substrate with mold, including：

Layering steps, on the metal surface of the substrate with metal surface, lamination according in claim 1 to 8 by appointing The photo-sensitive resin that chemical amplification positive photosensitive resin composition described in one is formed；

Step of exposure, actinic ray or radioactive ray are irradiated to the photo-sensitive resin；And

Development step, the photo-sensitive resin after exposure is developed, and be made to form the casting of electroplating formation body Mould.

10. a kind of manufacture method of electroplating formation body, including：

It is real to the substrate with mold manufactured by the manufacture method by the substrate according to claim 9 with mold Apply plating, and in electroplating formation body is formed in the mold the step of.