CN102540726B - Positive-type photosensitive resin composition, cured film and forming method thereof, interlayer dielectric and display device - Google Patents

Positive-type photosensitive resin composition, cured film and forming method thereof, interlayer dielectric and display device Download PDF

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Publication number
CN102540726B
CN102540726B CN201110415283.2A CN201110415283A CN102540726B CN 102540726 B CN102540726 B CN 102540726B CN 201110415283 A CN201110415283 A CN 201110415283A CN 102540726 B CN102540726 B CN 102540726B
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Prior art keywords
resin composition
formula
photosensitive resin
acid
construction unit
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CN102540726A (en
Inventor
山田悟
山﨑健太
杉原幸一
柏木大助
川岛敬史
霜山达也
真崎庆央
下野胜弘
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from JP2011271238A external-priority patent/JP5417422B2/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides a kind of positive-type photosensitive resin composition, cured film and forming method thereof, interlayer dielectric and display device, and the various performance synthesis of described positive-type photosensitive resin composition is excellent.The positive-type photosensitive resin composition of the present invention is characterised by: comprise the alkali soluble resin containing butoxy methyl acrylamide etc. and radiation acid producing agent.

Description

Positive-type photosensitive resin composition, cured film and forming method thereof, interlayer dielectric and display device
Technical field
The present invention relates to a kind of photosensitive resin composition, the forming method of cured film, cured film, organic electric-excitation luminescent (electroluminescence, EL) display device and liquid crystal indicator.More specifically, the present invention relates to a kind of positive-type photosensitive resin composition being suitable for forming the planarization film of electronic component, protecting film or the interlayer dielectrics such as liquid crystal indicator, organic EL display, integrated circuit component, solid-state imager and use the forming method of cured film of this positive-type photosensitive resin composition.
Background technology
Thin film transistor (TFT) (thinfilmtransistor, below it is denoted as " TFT ") in the electronic component such as type liquid crystal display cells or magnetic head element, integrated circuit component, solid-state imager, interlayer dielectric is set generally for making to be configured to insulation between the distribution of stratiform.Forming the material of interlayer dielectric, to be preferably number of steps in order to obtain desirable pattern shape few and have the material of substantially flat property, therefore widely uses photosensitive resin composition (with reference to Japanese Patent Laid-Open 2001-354822 publication and Japanese Patent Laid-Open 2001-343743 publication).
In described electronic component, such as TFT type liquid crystal display cells is through forming ELD on described interlayer dielectric, then the step forming liquid crystal orienting film on this ELD manufactures, therefore interlayer dielectric can be exposed under hot conditions in the forming step of ELD, or in the stripper of the resist that the pattern being exposed to electrode uses when being formed, therefore must have the abundant patience to them.
On the other hand, the photosensitive resin composition of high sensitivity is known acrylic acid series resist or alicyclic alkene hydrocarbon system resist (Japanese Patent Laid-Open 2010-181730 publication, Japanese Patent Laid-Open 2009-235414 publication).It addition, negative photosensitive resin constituent is known Japanese Patent Laid-Open 2002-40649 publication.
In recent years, there is the trend of large screen, high brightness, high-precision refinement, high-speed response, slimming etc. in TFT type liquid crystal display cells, the interlayer dielectric formation constituent wherein used is high sensitivity, for the interlayer dielectric formed, in low-k, high penetration etc., it is desirable to performance higher than ever.
As mentioned above, when being formed interlayer dielectric by photosensitive resin composition, requirement constituent is high sensitivity, and the interlayer dielectric formed by this constituent to be required the various performance synthesis excellence such as low-k, high penetration, but in the past but without finding to meet the photosensitive resin composition of this requirement.
Summary of the invention
The present invention is based on case above and is formed.Therefore, it is an object of the invention to provide the photosensitive resin composition of a kind of cured film obtaining various excellent performance and sensitivity excellence, the cured film hardening of described photosensitive resin composition obtained and forming method thereof and include organic EL display and the liquid crystal indicator of described cured film.
Based on described situation, inventor actively studies, it was found that by using the alkali soluble resin containing specific structure unit as resinous principle, it is possible to provide the positive-type photosensitive resin composition that various performance synthesises are excellent, thus completing the present invention.
Specifically, the present invention is by following means<1>, it is preferred to solve described problem by means<2>～means<26>.
<1>a kind of positive-type photosensitive resin composition, it is characterised in that: comprise (A) alkali soluble resin containing the construction unit represented by formula (1) and (C) radiation acid producing agent:
Formula (1)
(in formula, R1Represent hydrogen atom or methyl, R2Represent the alkyl of carbon number 1～9).
<2>according to the positive-type photosensitive resin composition described in<1>, following (1) and/or (2) is wherein also met:
(1) (A) alkali soluble resin containing the construction unit represented by formula (1) has acid labile group；
(2) this positive-type photosensitive resin composition comprises (B) and has the resin of acid labile group.
<3>according to the positive-type photosensitive resin composition described in<2>, the wherein said alkali soluble resin containing acid labile group is the resin containing acidic group and crosslinking group.
<4>according to the positive-type photosensitive resin composition according to any one of<1>～<3>, wherein (C) radiation acid producing agent is oxime sulfonate compounds.
<5>according to the positive-type photosensitive resin composition according to any one of<2>～<4>, the wherein said alkali soluble resin containing acid labile group is the resin containing the acid labile group as acid dissociation base, and described acid dissociation base utilizes the effect of acid to produce carboxyl or phenolic hydroxyl group.
<6>according to the positive-type photosensitive resin composition according to any one of<2>～<5>, the wherein said alkali soluble resin containing acid labile group is the resin containing the acidic group as carboxyl and the acid labile group as acid dissociation base, and described acid dissociation base utilizes the effect of acid to produce carboxyl or phenolic hydroxyl group.
<7>according to the positive-type photosensitive resin composition according to any one of<2>～<6>, the wherein said alkali soluble resin containing acid labile group contains at least one of following represented construction unit:
(in described formula, R1Represent the alkyl of hydrogen atom or carbon number 1～4, L respectively1Represent carbonyl or phenylene, R2Represent the alkyl of carbon number 1～4 respectively.N1 and n2 respectively 1～5 integer, n3 is the integer of 1～4, and n4 is the integer of 1～3).
<8>according to the positive-type photosensitive resin composition according to any one of<2>～<7>, the wherein said alkali soluble resin containing acid labile group contains the construction unit represented by following formula (2) or formula (3):
Formula (2) formula (3)
<9>according to the positive-type photosensitive resin composition described in<8>, the wherein said alkali soluble resin containing acid labile group contains the construction unit represented by formula (2).
<10>according to the positive-type photosensitive resin composition according to any one of<2>～<9>, the wherein said alkali soluble resin containing acid labile group is the resin containing the crosslinking group comprising oxetanyl and/or epoxy radicals.
<11>according to the positive-type photosensitive resin composition according to any one of<2>～<10>, (A) alkali soluble resin containing the construction unit represented by formula (1) and (B) alkali soluble resin containing acid labile group are wherein comprised.
<12>according to positive-type photosensitive resin composition described in<11>, wherein said (B) alkali soluble resin containing acid labile group is the resin that free-radical polymerised compound containing oxetanes or epoxy radicals of (a) unsaturated carboxylic acid, (b) and (c) free-radical polymerised compound containing acid labile group carry out combined polymerization.
<13>according to positive-type photosensitive resin composition described in<11>, wherein said (B) alkali soluble resin containing acid labile group is the resin that free-radical polymerised compound containing oxetanyl of (a) unsaturated carboxylic acid, (b) and (c) free-radical polymerised compound containing acid labile group carry out combined polymerization.
<14>according to the positive-type photosensitive resin composition according to any one of<1>～<13>, wherein (A) alkali soluble resin is the polymer also comprising the construction unit containing acidic group.
<15>according to the positive-type photosensitive resin composition according to any one of<1>～<14>, wherein (A) alkali soluble resin is possibly together with the polymer from cinnamic construction unit.
<16>according to the positive-type photosensitive resin composition according to any one of<2>～<15>, wherein the main constituent of solid constituent is resinous principle, and comprise (A) alkali soluble resin containing the construction unit represented by formula (1) and (B) alkali soluble resin containing acid labile group as this resinous principle, and comprise (C) radiation acid producing agent relative to total solid composition with the scope of 0.1%～10%.
<17>according to the positive-type photosensitive resin composition according to any one of<1>～<16>, (D) cross-linking agent is wherein also comprised.
<18>according to the positive-type photosensitive resin composition described in<17>, wherein the main constituent of solid constituent is resinous principle, and comprise (A) alkali soluble resin containing the construction unit represented by formula (1) and (B) alkali soluble resin containing acid labile group as this resinous principle, and relative to total solid composition to comprise (C) radiation acid producing agent in the scope of 0.1%～10%, comprise (D) cross-linking agent with the scope of 1%～40%.
<19>according to the positive-type photosensitive resin composition according to any one of<2>～<18>, wherein (B) alkali soluble resin containing acid labile group is comprised with the ratio of 10 weight %～97 weight % in total resinous principle.
<20>according to the positive-type photosensitive resin composition according to any one of<2>～<18>, wherein also comprise (B ') resin beyond (B) alkali soluble resin containing acid labile group, and comprise this (B ') resin with the ratio of 3 weight %～70 weight % in total resinous principle.
<21>a kind of cured film, is applied on substrate by the positive-type photosensitive resin composition according to any one of<1>～<20>, utilizes light and/or heat to make it harden and form.
<22>a kind of cured film, is applied on substrate by the positive-type photosensitive resin composition according to any one of<1>～<20>, and the step being undertaken developing and then heating by not including heat treated after exposure is formed.
<23>a kind of interlayer dielectric, uses according to the cured film described in<21>or<22>.
<24>a kind of liquid crystal indicator or organic EL display, including the interlayer dielectric according to<23>.
<25>forming method of a kind of cured film, comprises the following steps:
(1) photosensitive resin composition according to any one of<1>～<20>is applied to the step on substrate；
(2) from the photosensitive resin composition applied, remove the step of solvent；
(3) step that activity lonizing radiation are exposed is utilized；
(4) aqueous developer solution is utilized to carry out the step developed；And
(5) step of thermmohardening is carried out.
<26>forming method according to cured film described in<25>, wherein after the described step carrying out and developing, carry out the step of thermmohardening before include the step of blanket exposure.
(invention effect)
By the present invention, the positive-type photosensitive resin composition that various performance synthesis is excellent can be obtained.
Accompanying drawing explanation
Fig. 1 represents the composition concept map of an example of organic EL display.The constructed profile of the substrate in expression bottom emission type organic EL display, has planarization film 4.
Fig. 2 represents the composition concept map of an example of liquid crystal indicator.The constructed profile of the active matrix substrate in expression liquid crystal indicator, has the cured film 17 as interlayer dielectric.
The explanation of symbol
1,16:TFT
2: distribution
3,8: dielectric film
4: planarization layer
5: the first electrodes
6: glass substrate
7,18: contact hole
10: liquid crystal indicator
12: backlight unit
14,15: glass substrate
17: cured film
19: indium tin oxide transparency electrode
20: liquid crystal
22:RGB chromatic filter
Detailed description of the invention
Hereinafter, present disclosure is described in detail.Additionally, in this case description "～" it is so that numerical value described before and after it is used as the implication of lower limit and higher limit.
It addition, the so-called organic EL element in the present invention, refer to organic electroluminescent element.
And then, so-called (methyl) acrylic acid refers to acrylic acid and/or methacrylic acid.
Additionally, in the present invention so-called " alkali-soluble ", refer to by the solution of compound (resin) is applied on substrate, film (the thickness 3 μm) dissolution velocity in 0.4% tetramethylammonium hydroxide aqueous solution at 23 DEG C of the compound (resin) heated 2 minutes at 90 DEG C and formed is 0.01 μm/more than sec, so-called " alkali-insoluble ", refer to by the solution of compound (resin) is applied on substrate, the film (thickness 3 μm) of compound (resin) heated 2 minutes at 90 DEG C and formed at 23 DEG C the dissolution velocity in 0.4% tetramethylammonium hydroxide aqueous solution less than 0.01 μm/sec.
The positive-type photosensitive resin composition of the present invention is characterised by: comprise (A) alkali soluble resin containing the construction unit represented by formula (1) and (C) radiation acid producing agent.By being set to this composition, can the various performances of tremendous raising positive-type photosensitive resin composition.
Formula (1)
(in formula, R1Represent hydrogen atom or methyl, R2Represent the alkyl of carbon number 1～9.)
Resin used in the present invention is characterised by containing the construction unit represented by formula (1), but is preferably and also has acid labile group in addition.Acid labile group can be included in the alkali soluble resin containing the construction unit represented by formula (1), it is also possible to is included in the alkali soluble resin different from this alkali soluble resin.And then, more preferably there is acidic group and/or bridging property base.Alternatively, it is also possible to containing other construction units.In the present invention, these groups or construction unit can be only contained in a kind of resin, it is also possible to be included in two or more resin wantonly a kind or two or more in.Hereinafter, the embodiment of resin used in the present invention is shown in following.But, resin used in the present invention is not limited to these resins certainly.
(embodiment 1)
(A) alkali soluble resin (hereinafter sometimes referred to " (A) resin ") containing the construction unit represented by formula (1) is possibly together with the aspect of acid labile group.
(embodiment 2)
(A) resin also comprises the aspect of acid labile group and crosslinking group.
(embodiment 3)
(A) resin is possibly together with the aspect of acid labile group and acidic group.
(embodiment 4)
(A) resin is possibly together with the aspect of acid labile group, crosslinking group and acidic group.
(embodiment 5)
In arbitrary form of described embodiment 1～embodiment 4, (A) resin is possibly together with the aspect of other construction units.
(embodiment 6)
(A) alkali soluble resin containing the construction unit represented by formula (1) and the resin different from this (A) resin contain the aspect of acid labile group.Hereinafter, sometimes the resin containing acid labile group now is expressed as " (B) resin ".
(embodiment 7)
Comprise (A) resin and (B) resin, and (B) resin contains the aspect of acid labile group and crosslinking group.
(embodiment 8)
Comprise (A) resin and (B) resin, and (B) resin contains the aspect of acid labile group and acidic group.
(embodiment 9)
Comprise (A) resin and (B) resin, and (B) resin contains the aspect of acid labile group, bridging property base and acidic group.
(embodiment 10)
In arbitrary form of described embodiment 6～embodiment 9, (A) resin is possibly together with the aspect of acidic group.
(embodiment 11)
In arbitrary form of described embodiment 6～embodiment 10, (A) resin or (B) resin are possibly together with the aspect of other construction units.
(embodiment 12)
In described embodiment 11, (A) resin contains from cinnamic construction unit, and (B) resin contains the aspect from (methyl) acrylic acid construction unit.
In described embodiment, (A) resin and (B) resin can simply be a kind respectively, it is also possible to comprise two or more.
Construction unit represented by formula (1)
In formula (1), R1Represent hydrogen atom or methyl, it is preferred to hydrogen atom.
R2Represent the alkyl of carbon number 1～9, it is preferred to the alkyl of carbon number 1～7, it is particularly preferred that for the alkyl of carbon number 2～6.Alkyl can be any one in straight chain or branched alkyl groups.
Construction unit represented by formula (1) is preferably and contains with the ratio of 1 mole of %～50 mole % of (A) resin, more preferably contain with the ratio of 10 moles of %～40 mole %, it is particularly preferred that be 30 moles of %.
Acid labile group
The resin of the present invention is preferably containing acid labile group.By containing acid labile group, alkali-soluble being made to increase.The acid labile group comprised in the present invention refers to decomposable functional group in the presence of acid, it is preferred to utilize the effect of acid to produce the acid dissociation base of carboxyl or phenolic hydroxyl group.
More specifically, resin used in the present invention is preferably containing the construction unit from the monomer containing acid labile group.This construction unit typically uses the construction unit of the monomer from the acid dissociation base with effect generation carboxyl or the phenolic hydroxyl group utilizing acid.
(a1-1) from the construction unit that there is the effect utilizing acid and produce the monomer of the acid dissociation base of carboxyl
(a1-1-1) from the construction unit of the monomer with carboxyl
The monomer with carboxyl include, for example the monomer of the unsaturated carboxylic acid etc. in unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular with at least 1 carboxyl.
It is use the carboxylic acid being exemplified below to obtain the unsaturated carboxylic acid used from the construction unit of the monomer with carboxyl.That is, unsaturated monocarboxylic include, for example acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, cinnamic acid etc..It addition, unsaturated dicarboxylic include, for example maleic acid, fumaric acid, methylene-succinic acid, methyl maleic succinic acid, mesaconic acid etc..It addition, can also be its anhydride to obtain the unsaturated polybasic carboxylic acid used from the construction unit of the monomer with carboxyl.Specifically, maleic anhydride, itaconic anhydride, methyl maleic succinic anhydride etc. can be enumerated.Additionally, unsaturated polybasic carboxylic acid can be list (2-methacryloxyalkyl) ester of polybasic carboxylic acid, for instance can enumerate succinic acid list (2-acryloxy second) ester, succinic acid list (2-methacryloxy second) ester, phthalic acid list (2-acryloxy second) ester, phthalic acid list (2-methacryloxy second) ester etc..
And then, unsaturated polybasic carboxylic acid can be list (methyl) acrylate of its two ends dicarboxyl polymer, for instance can enumerate ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc..
It addition, unsaturated carboxylic acid can also use acrylic acid-2-carboxyethyl, methacrylic acid-2-carboxyethyl, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, 4-carboxyl styrene etc..Wherein, for the viewpoint of developability, in order to form the construction unit from the monomer with carboxyl, it is preferable to use the anhydride etc. of acrylic acid, methacrylic acid or unsaturated polybasic carboxylic acid, more preferably use acrylic acid or methacrylic acid.
Construction unit (a1-1-1) from the monomer with carboxyl can comprise independent a kind, it is also possible to comprises two or more.
(a1-1-2) from the construction unit of the monomer with ethylene unsaturated group and anhydride residue
Construction unit (a1-2) from the monomer with ethylene unsaturated group and anhydride residue is preferably the unit from following monomer, and this monomer is to make hydroxyl existing in the construction unit of the monomer with ethylene unsaturated group and anhydride react and obtain.
Anhydride can use known anhydride, specifically can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride；The anhydride such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid anhydride, biphenyl tetracarboxylic anhydride.In these anhydride, for the viewpoint of developability, it is preferred to phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.
For the viewpoint of developability, anhydride is preferably 10 moles of %～100 mole % for the response rate of hydroxyl, more preferably 30 moles of %～100 mole %.
(a1-1-3) from the construction unit that there is the effect utilizing acid and produce the monomer of the acid dissociation base of carboxyl
So-called from the construction unit that there is the effect utilizing acid and produce the monomer of the acid dissociation base of carboxyl, it is preferred to the construction unit of the monomer of the residue being protected by by sour decomposability base described further below from the carboxyl that there is described (a1-1-1), described (a1-1-2) records.
Acid decomposability base can use the known group as the sour decomposability base in KrF eurymeric resist, ArF eurymeric resist up to now, is not particularly limited.In the past, acid decomposability base was known has utilization acid be easier the group (the acetal system functional groups of such as THP trtrahydropyranyl etc.) of decomposition or utilize acid and be relatively difficult to the group (such as the tert-butyl group system functional group of tert-butyl ester base, t-butyl carbonate base etc.) of decomposition.
In these acid decomposability bases; basic physical properties with regard to resist; the particularly viewpoint of the storage stability of sensitivity or pattern form, the formative of contact hole, photosensitive resin composition, it is preferred to from the construction unit of the monomer with residue that carboxyl is protected by by acetal or the residue that carboxyl is protected by by ketal.And then in acid decomposability base, for the viewpoint of sensitivity, more preferably the residue that carboxyl acetal represented by following formula (a1-1) or ketal are protected by.Additionally, when the residue that carboxyl acetal represented by following formula (a1-1) or ketal are protected by, residue generally form-(C=O)-O-CR1R2(OR3) structure.
(in formula (a1-1), R1And R2Separately represent hydrogen atom or alkyl, wherein, R1With R2It is except the situation of hydrogen atom；R3Represent alkyl；R1Or R2Can with R3Link and form cyclic ether.)
In formula (a1-1), R1～R3Separately representing hydrogen atom or alkyl, this alkyl can be any one in straight-chain, branch's chain, ring-type.Herein, it is absent from R1And R2The situation of both expression hydrogen atoms, but R1And R2At least one represent alkyl.
In formula (a1-1), at R1、R2And R3When representing alkyl, this alkyl can be any one in straight-chain, branch's chain or ring-type.
The alkyl of straight-chain or branch's chain is preferably carbon number 1～12, more preferably carbon number 1～6, it is particularly preferred that for carbon number 1～4.Specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, 2,3-dimethylbutane-2-base (thexyl) (2,3-dimethyl-2-butyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc..
Cyclic alkyl is preferably carbon number 3～12, more preferably carbon number 4～8, it is particularly preferred that for carbon number 4～6.Cyclic alkyl include, for example: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc..
Described alkyl can have substituent group, and substituent group can illustrate halogen atom, aryl, alkoxyl.When having halogen atom alternatively base, R1、R2、R3Become alkylhalide group, when having aryl alternatively base, R1、R2、R3Become aralkyl.
Halogen atom can illustrate fluorine atom, chlorine atom, bromine atoms, atomic iodine, in these halogen atoms, it is preferred to fluorine atom or chlorine atom.
Additionally, described aryl is preferably the aryl of carbon number 6～20, be more preferably carbon number 6～12, specifically can illustrate phenyl, Alpha-Methyl phenyl, naphthyl etc., through aryl replace alkyl totally, namely aralkyl can illustrate benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc..
Described alkoxyl is preferably the alkoxyl of carbon number 1～6, more preferably carbon number 1～4, more preferably methoxyl group or ethyoxyl.
Additionally, when alkyl is cycloalkyl, this cycloalkyl can have the straight-chain of carbon number 1～10 or the alkyl alternatively base of branch's chain, when the alkyl that alkyl is straight-chain or branch's chain, it is possible to has the cycloalkyl alternatively base of carbon number 3～12.These substituent groups can be further substituted with through described substituent group.
In formula (a1-1), at R1、R2And R3When representing aryl, this aryl is preferably carbon number 6～12, more preferably carbon number 6～10.This aryl can have substituent group, and this substituent group can preferably illustrate the alkyl of carbon number 1～6.Aryl such as can illustrate phenyl, tolyl, silylation, cumenyl, 1-naphthyl etc..
It addition, R1、R2And R3Can be combineding with each other, the carbon atom combined with them collectively forms ring.R1With R2、R1With R3Or R2With R3In conjunction with the ring structure of situation include, for example cyclobutyl, cyclopenta, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc..
Additionally, in formula (a1-1), R1And R2Any one be preferably hydrogen atom or methyl.
The free radical polymerization monomer used to form the construction unit of the monomer from the residue having represented by formula (a1-1) can use commercially available monomer, it is possible to use utilizes the monomer that known method synthesizes.Such as can be as described below, pass through to make (methyl) acrylic acid and vinyl Ether react in the presence of acid catalyst and synthesize.
R11Representing hydrogen atom or alkyl, this alkyl is in formula (a1-1), and as R1～R3The alkyl represented is identical.R11It is preferably hydrogen atom or methyl.
R12And R13As-CH (R12)(R13), with the R in formula (a1-1)2Implication is identical, R14With the R in formula (a)1Implication is identical, R15With the R in formula (a1-1)3Implication is identical, it addition, they preferable range are also identical.
Described synthesis can make (methyl) acrylic acid and other monomers carry out combined polymerization in advance, then reacts with vinyl Ether in the presence of acid catalyst.
Used in the present invention produce the construction unit of the acid dissociation base of carboxyl can enumerate using lower unit as preferred example containing the effect utilizing acid.
(in described formula, R1Represent the alkyl of hydrogen atom or carbon number 1～4, L respectively1Represent carbonyl or phenylene, R2Represent the alkyl of carbon number 1～4 respectively；N1 and n2 respectively 1～5 integer, n3 is the integer of 1～4, and n4 is the integer of 1～3.)
R1Represent the alkyl of hydrogen atom or carbon number 1～4 respectively, it is preferred to hydrogen atom or methyl, it is particularly preferred that for methyl.
L1Represent carbonyl or phenylene, more preferably carbonyl.R2Represent the alkyl of hydrogen atom or carbon number 1～4 respectively, it is preferred to hydrogen atom or methyl, more preferably any one is hydrogen atom.
N1, n2, n3 and n4 are respectively preferably 0.
In described, it is particularly preferred to for (1), (2), (5) or (7), it is particularly preferred that for (2) or (7), it is most preferred that for (7).
Produce the preferred concrete example of the construction unit (a1-1) of the monomer of the acid dissociation base of carboxyl and can illustrate the construction unit from following monomer from having the effect utilizing acid.Additionally, R represents hydrogen atom or methyl, more preferably methyl.
The present invention is particularly preferably the alkali soluble resin containing acid labile group and contains the construction unit represented by following formula (2) or formula (3).
Formula (2) formula (3)
(a1-2) from the construction unit that there is the effect utilizing acid and produce the monomer of the acid dissociation base of phenolic hydroxyl group
(a1-2-1) from the construction unit of the monomer with phenolic hydroxyl group
Construction unit from the monomer with phenolic hydroxyl group can enumerate the construction unit from hydroxy styrenes system monomer or the construction unit from the monomer in novolaks system resin, in these construction units, for the viewpoint of the transparency, it is preferred to from the construction unit of the monomer coming from Alpha-Methyl hydroxy styrenes.In the construction unit of monomer with phenolic hydroxyl group, the just viewpoint of the transparency, sensitivity, it is preferred to from the construction unit of the monomer represented by formula (a1-2).
(in formula (a1-2), R20Represent hydrogen atom or methyl, R21Represent singly-bound or concatenating group, R22Representing halogen atom or alkyl, a represents the integer of 1～5, and b represents the integer of 0～4, and a+b is less than 5；Additionally, at R22When having more than 2, these R22Can be mutually different, it is also possible to identical.)
In formula (a1-2), R20Represent hydrogen atom or methyl, it is preferred to methyl.
It addition, R21Represent singly-bound or bivalence linking base.At R21When for singly-bound, sensitivity can be made to improve, and then the transparency raising of cured film can be made, it is thus preferred to.R21Bivalence linking base can illustrate alkylidene, R21Concrete example for alkylidene can be enumerated: methylene, ethylidene, propylidene, isopropylidene, positive butylidene, isobutylene, tertiary butylidene, pentylidene, isopentylidene, neopentylidene, hexylidene etc..Wherein, R21It is preferably singly-bound, methylene, ethylidene.It addition, described bivalence linking base can have substituent group, substituent group can enumerate halogen atom, hydroxyl, alkoxyl etc..
It addition, a represents the integer of 1～5, for the viewpoint of effect of the present invention or the aspect that easily manufactures, it is preferred to a is 1 or 2, and more preferably a is 1.
Will with R it addition, work as21In conjunction with carbon atom as benchmark (1) time, the binding site of the hydroxyl in phenyl ring be preferably be incorporated into 4.
R22Alkyl for the straight chain of halogen atom or carbon number 1～5 or branch's chain.Specifically can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl etc..Wherein, the aspect manufactured it is easy for, it is preferred to chlorine atom, bromine atoms, methyl or ethyl.
It addition, b represents the integer of 0 or 1～4.
In the construction unit of monomer with phenolic hydroxyl group, in described formula (a1-2), at R21It is not the situation of alkylidene, for the viewpoint of the transparency and sensitivity, it is particularly preferred that for the construction unit from the monomer represented by formula (a1-2 ').R21Concatenating group except alkylidene, it may be preferable to illustrate (from the main chain side of copolymer) alkylene oxide group carbonyl etc., be now preferably the construction unit from the monomer with phenolic hydroxyl group represented by following formula (a1-2 ').
(in formula (a1-2 '), R30With the R in formula (a1-2)20Implication is identical, R32With the R in formula (a1-2)22Implication is identical, a and b is identical with a and the b implication in formula (a1-2) respectively；Additionally, it is preferred that scope also identical.)
In formula (a1-2 '), R33Represent bivalence linking base, it may be preferable to illustrate alkylidene.This alkylidene can be any one of straight-chain or branch's chain, it is preferred to carbon number 2～6, can enumerate ethylidene, propylidene, isopropylidene, positive butylidene, tertiary butylidene, pentylidene, isopentylidene, neopentylidene, hexylidene etc..It addition, bivalence linking base also can have substituent group, substituent group can enumerate halogen atom, hydroxyl, alkoxyl etc..In these groups, for the viewpoint of sensitivity, R33It is preferably ethylidene, propylidene, 2-hydroxy propylidene.
(a1-2-2) from the construction unit that there is the effect utilizing acid and produce the monomer of the acid dissociation base of phenolic hydroxyl group
From there is the effect utilizing acid and producing the construction unit that the construction unit of the monomer of the acid dissociation base of phenolic hydroxyl group originates from having the monomer of following residue, the residue that this residue is (a1-2-1) to be protected by from the phenolic hydroxyl group of the construction unit of the monomer with phenolic hydroxyl group by sour decomposability base explained in detail below.Acid decomposability base can use known acid decomposability base as mentioned above, is not particularly limited.In acid decomposability base; basic physical properties with regard to resist; the particularly viewpoint of the formative of sensitivity or pattern form, the storage stability of photosensitive resin composition, contact hole, it is preferred to from the construction unit of the monomer with residue that phenolic hydroxyl group is protected by by acetal or the residue that phenolic hydroxyl group is protected by by ketal.And then, in acid decomposability base, for the viewpoint of sensitivity, more preferably the residue that phenolic hydroxyl group acetal represented by formula (a1-1) or ketal are protected by.Additionally, when the residue that phenolic hydroxyl group acetal represented by formula (a1-1) or ketal are protected by, residue totally become-Ar-O-CR1R2(OR3) structure.Additionally, Ar represents arlydene.
The preferred example of the acetal ester structure of phenolic hydroxyl group can illustrate R1=R2=R3=methyl or R1=R2=methyl and R3The combination of=benzyl.
nullAdditionally，In order to form the free radical polymerization monomer used from the construction unit of the monomer with the residue that phenolic hydroxyl group is protected by by acetal or ketal，Include, for example: the 1-alkoxyalkyl protective of hydroxy styrenes、The THP trtrahydropyranyl protective of hydroxy styrenes、The 1-alkoxyalkyl protective of Alpha-Methyl-hydroxy styrenes、The THP trtrahydropyranyl protective of Alpha-Methyl-hydroxy styrenes、The 1-alkoxyalkyl protective of methacrylic acid 4-hydroxylphenyl ester、The THP trtrahydropyranyl protective of methacrylic acid 4-hydroxylphenyl ester、The 1-alkoxyalkyl protective of 4-HBA (1-methacryloxy first) ester、The THP trtrahydropyranyl protective of 4-HBA (1-methacryloxy first) ester、The 1-alkoxyalkyl protective of 4-HBA (2-methacryloxy second) ester、The THP trtrahydropyranyl protective of 4-HBA (2-methacryloxy second) ester、The 1-alkoxyalkyl protective of 4-HBA (3-methacryloxy third) ester、The THP trtrahydropyranyl protective of 4-HBA (3-methacryloxy third) ester、The 1-alkoxyalkyl protective of 4-HBA (3-methacryloxy-2-hydroxyl third) ester、The THP trtrahydropyranyl protective etc. of 4-HBA (3-methacryloxy-2-hydroxyl third) ester.
nullIn these monomers，For the viewpoint of the transparency，It is preferably: the 1-alkoxyalkyl protective of methacrylic acid 4-hydroxylphenyl ester、The THP trtrahydropyranyl protective of methacrylic acid 4-hydroxylphenyl ester、The 1-alkoxyalkyl protective of 4-HBA (1-methacryloxy first) ester、The THP trtrahydropyranyl protective of 4-HBA (1-methacryloxy first) ester、The 1-alkoxyalkyl protective of 4-HBA (2-methacryloxy second) ester、The THP trtrahydropyranyl protective of 4-HBA (2-methacryloxy second) ester、The 1-alkoxyalkyl protective of 4-HBA (3-methacryloxy third) ester、The THP trtrahydropyranyl protective of 4--hydroxy benzoic acid (3-methacryloxy third) ester、The 1-alkoxyalkyl protective of 4-HBA (3-methacryloxy-2-hydroxyl third) ester、The THP trtrahydropyranyl protective of 4-HBA (3-methacryloxy-2-hydroxyl third) ester.
Acetal protecting group and the ketal protected concrete example of phenolic hydroxyl group can enumerate 1-alkoxyalkyl; include, for example: 1-ethoxyethyl group, 1-methoxy ethyl, 1-n-butoxyethyl, 1-isobutoxyethy, 1-(2-chloroethoxy) ethyl, 1-(2-ethyl hexyl oxy) ethyl, 1-positive propoxy ethyl, 1-cyclohexyloxy ethyl, 1-(2-cyclohexylethoxy radical) ethyl, 1-Benzyloxyethyl etc., these groups can be used alone or two or more combination be used.
The free radical polymerization monomer used for the construction unit (a1) that formed from monomer can use commercially available monomer, it is possible to use utilizes the monomer that known method synthesizes.Such as can react with vinyl Ether and synthesize by making to have the compound of phenolic hydroxyl group in the presence of acid catalyst.The monomer with phenolic hydroxyl group can also be carried out combined polymerization with other monomers by described synthesis in advance, then reacts with vinyl Ether in the presence of acid catalyst.
Preferred concrete example from the construction unit (a1-2) of monomer can illustrate the construction unit from following monomer, but the present invention is not limited to these construction units.
When (A) used in the present invention resin contains acid labile group, content from the construction unit of these monomers is preferably 3 moles of %～70 mole % of the construction unit of total resinous principle, it is more preferably 5 moles of %～60 mole %, it is particularly preferred that be 10 moles of %～50 mole %.
And then when (B) used in the present invention resin contains acid labile group, 3 moles of %～90 mole % of the construction unit that the content with the construction unit of acid labile group is preferably in (B) resin, it is more preferably 20 moles of %～90 mole %, it is particularly preferred that be 30 moles of %～85 mole %.
The acid labile group producing the acid dissociation base of carboxyl or phenolic hydroxyl group as the effect utilizing acid is preferably at least the effect as utilization acid and produces the acid labile group of the acid dissociation base of carboxyl.It addition, particularly produce the acid labile group of the acid dissociation base of carboxyl according to the effect as utilization acid, and use carboxyl as acidic group described later, then more effectively play the effect of the present invention, it is thus preferred to.
Bridging property base
Alkali soluble resin used in the present invention is preferably containing bridging property base.By containing bridging property base, existing for the cured film formed, the tendency that resistance to indium tin oxide (ITO) sputtering or the patience to the treatment fluid such as stripper and etching solution improve.Bridging property base can illustrate oxetanyl, epoxy radicals, methylacryloyl, acryloyl group, it is preferred to oxetanyl and/or epoxy radicals.
In the present invention, it is common to use there is the monomer of this bridging property base, the construction unit group containing crosslinking group is entered in resin.
Construction unit containing bridging property base is preferably 10 moles of %～70 mole % of the construction unit adding up to composition of total resinous principle, more preferably 20 moles of %～60 mole %, it is particularly preferred that be 30 moles of %～55 mole %.
The construction unit containing bridging property base used in the present invention is more preferably the construction unit from (methyl) acrylic acid and/or its ester.In addition it is also possible to have from the construction unit beyond the construction unit of (methyl) acrylic acid and/or its ester, for instance from cinnamic construction unit or from the construction unit etc. of vinyl compound.
It is more preferably the construction unit represented by following formula.
(in described formula, R1Represent hydrogen atom or methyl, L1For singly-bound or bivalence linking base, C is bridging property base)
R1Represent hydrogen atom or methyl, it is preferred to methyl.L1For singly-bound or bivalence linking base, it is preferred to phenylene, ester group, amide groups, more preferably ester group.C is bridging property base, it is preferred to oxetanyl or epoxy radicals.
Acidic group
Alkali soluble resin used in the present invention is preferably containing acidic group.By containing acidic group, becoming easily to be dissolved in alkaline-based developer, more effectively play the effect of the present invention.So-called acidic group in the present invention, refers to the pKa proton dissociation base less than 7.Acidic group typically uses the monomer that can form acidic group, is set in resin as the construction unit containing acidic group.By making the construction unit containing this acidic group be included in resin, there is the tendency that alkali-soluble becomes big.Particularly at the positive-type photosensitive resin composition of the present invention except comprising (A) resin, also additionally comprise the situation of (B) alkali soluble resin containing acid labile group, it is preferred to (A) resin and (B) alkali soluble resin containing acid labile group contain the construction unit comprising acidic group respectively.By becoming this composition, become easy uniform dissolution in alkaline-based developer.
The acidic group used in the present invention can illustrate the acidic group from carboxylic acid group, the acidic group from hydroxyl, the acidic group from sulfoamido, the acidic group etc. from 1,3-diketo, it is preferred to the acidic group from carboxylic acid group and/or the acidic group from hydroxyl.
The construction unit containing acidic group used in the present invention is more preferably the construction unit from (methyl) acrylic acid and/or its ester.In addition it is also possible to have from the construction unit beyond the construction unit of (methyl) acrylic acid and/or its ester, for instance from cinnamic construction unit or from the construction unit etc. of vinyl compound.
It is more preferably the construction unit represented by following formula.
(in described formula, R1Represent hydrogen atom or methyl, L1For singly-bound or bivalence linking base, A is acidic group)
R1Represent hydrogen atom or methyl, it is preferred to methyl.L1For singly-bound or bivalence linking base, it is preferred to singly-bound, alkylidene, arlydene, more preferably singly-bound, the alkylidene of carbon number 1～3, phenylene.A is acidic group, it is preferred to hydroxyl, carboxylic acid group, it is particularly preferred that for carboxylic acid group.
The concrete example of the monomer containing acidic group can be enumerated: acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, methyl maleic succinic acid, mesaconic acid, methylene-succinic acid.Wherein it is preferably acrylic acid, methacrylic acid.
Construction unit containing acidic group is preferably 1 mole of %～50 mole % of the construction unit constituting total resinous principle, more preferably 5 moles of %～40 mole %, it is particularly preferred that be 5 moles of %～30 mole %.
And then, there is the situation of acid labile group at (A) resin, the construction unit containing acidic group is more preferably 1 mole of %～20 mole % in (A) resin, it is particularly preferred that be 5 moles of %～10 mole %.On the other hand, it is the aspect without acid labile group at (A) resin, namely the situation of the aspect of (B) resin is comprised, (A) content of the construction unit containing acidic group in resin is preferably 1 mole of %～50 mole %, it is particularly preferred that be 10 moles of %～30 mole %.(B) content of the construction unit containing acidic group in resin is preferably 1 mole of %～30 mole %, it is particularly preferred that be 5 moles of %～10 mole %.
Other construction units
Composition A can also have other construction units in the scope not interfering with effect of the present invention.
Other construction units are preferably the construction unit from least one monomer selected in free 4-Vinyl phenol, Alpha-Methyl-4-Vinyl phenol, styrene and the formed group of α-methyl styrene.
It addition, the preferred example of construction unit also can enumerate the construction unit from least one monomer selected in the esters of unsaturated carboxylic acids of free hydroxyl, esters of unsaturated carboxylic acids containing alicyclic structure, styrene and N replacement the formed group of maleimide.
In these construction units, for the viewpoint that electrical characteristic improves, it is preferred to such as (methyl) acrylic acid three ring [5.2.1.02,6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid three ring [5.2.1.02,6] decane-8-oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl etc (methyl) esters of acrylic acid containing alicyclic structure, or such as the hydrophobic monomer of styrene etc.For the viewpoint of sensitivity, it is preferred to (methyl) acrylic acid 2-hydroxy methacrylate, N replace maleimide.In these construction units, more preferably there is (methyl) esters of acrylic acid of alicyclic structure.It addition, for the viewpoint of elching resistant, it is preferred to the phenylethylene such as styrene or α-methyl styrene.
These other construction units can be used alone a kind or by two or more combination use.
(A) resin and (B) resin are respectively preferably addition polymerization type resin, it is preferred to containing selected from the construction unit from (methyl) acrylic acid and/or its ester, from cinnamic construction unit and from least one in the construction unit of vinyl compound.
By containing the construction unit from (methyl) acrylic acid and/or its ester, can further improve sensitivity, it addition, can further improve the transparency.By containing from cinnamic construction unit, dry-etching speed can be reduced further, reduce relative dielectric constant (K value) further.
When (A) resin contains the aspect of acid labile group, the construction unit from (methyl) acrylic acid and/or its ester is preferably and accounts for overall 50 mole %～100 mole %, more preferably account for 60 moles of %～95 mole %.
On the other hand, in (A) resin aspect without acid labile group, when namely comprising the aspect of (B) resin, (A) in resin, it is preferably from cinnamic construction unit and accounts for 70 moles of %～20 mole %, being more preferably and account for 60 moles of %～30 mole %, the construction unit from (methyl) acrylic acid and/or its ester is preferably and accounts for overall 30 mole %～80 mole %, more preferably account for 40 moles of %～70 mole %.Now, in (B) resin, the construction unit from (methyl) acrylic acid and/or its ester is preferably and accounts for overall 50 mole %～100 mole %, more preferably account for 80 moles of %～95 mole %.
Particularly (B) resin is preferably the resin that (a) unsaturated carboxylic acid, (b) carry out combined polymerization containing oxetanes or the free-radical polymerised compound of epoxy radicals, (c) free-radical polymerised compound containing acid labile group, it is particularly preferred that for (a) unsaturated carboxylic acid, (b) carry out the resin of combined polymerization containing the free-radical polymerised compound of oxetanyl, (c) free-radical polymerised compound containing acid labile group.Particularly the composition beyond these compositions is more preferably 2 overall mass %.
(A) molecular weight of resin and (B) resin can suitably determine, when (A) resin contains the aspect of acid labile group, is preferably 3000～30000 with weight average molecular weight, more preferably 6000～20000.On the other hand, in (A) resin aspect without acid labile group, when namely comprising the aspect of (B) resin, (A) weight average molecular weight of resin is preferably 5000～20000, it is more preferably 6000～15000, (B) weight average molecular weight of resin is preferably 5000～30000, more preferably 6000～20000.
(A) resin (B ') beyond resin and (B) resin
The positive-type photosensitive resin composition of the present invention can comprise the resin (B ') beyond described (A) resin and (B) resin.This resin (B ') is preferably has any structure unit cited in bridging property base, acidic group or other construction units, it is preferred at least have acidic group.
This resin (B ') is preferably the resin on side chain with carboxyl.Include, for example: such as Japanese Patent Laid-Open No. Sho 59-44615, Japan Patent examined patent publication 54-34327, Japan Patent examined patent publication 58-12577, Japan Patent examined patent publication 54-25957, Japanese Patent Laid-Open No. Sho 59-53836, methacrylic acid copolymer described in each publication of Japanese Patent Laid-Open No. Sho 59-71048, acrylic copolymer, methylene-succinic acid copolymer, crotonic acid copolymers, acid/maleic acid copolymers, partial esterification acid/maleic acid copolymers etc., and side chain has the acid cellulose derivant of carboxyl, the resin etc. of addition anhydride in the polymer have hydroxyl, and then the high molecular polymer with (methyl) acryloyl group can also be enumerated on side chain as preferred example.
Except described, can also enumerate: the huge monomer/benzyl methacrylate/methacrylic acid copolymer of (methyl) acrylic acid 2-hydroxy propyl ester/polystyrene recorded in Japanese Patent Laid-Open 7-140654 publication, acrylic acid 2-hydroxyl-3-phenoxy-propyl/huge monomer/benzyl methacrylate/methacrylic acid copolymer of polymethyl methacrylate, huge monomer/methyl methacrylate/the methacrylic acid copolymer of 2-hydroxyethyl methacrylate/polystyrene, huge monomer/benzyl methacrylate/the methacrylic acid copolymer of 2-hydroxyethyl methacrylate/polystyrene, styrene/methacrylic acid/methacrylic acid bicyclo-pentyl ester/the glycidyl methacrylate copolymer etc. recorded in Japanese Patent Laid-Open 5-165214 publication.
In addition, it is also possible to use the known macromolecular compound recorded in Japanese Patent Laid-Open 7-207211 publication, Japanese Patent Laid-Open 8-259876 publication, Japanese Patent Laid-Open 10-300922 publication, Japanese Patent Laid-Open 11-140144 publication, Japanese Patent Laid-Open 11-174224 publication, Japanese Patent Laid-Open 2000-56118 publication, Japanese Patent Laid-Open 2003-233179 publication, Japanese Patent Laid-Open 2009-52020 publication etc..
These other resins (B ') can only comprise a kind, it is also possible to comprises two or more.
It is resinous principle that the positive-type photosensitive resin composition of the present invention is usually the main constituent of solid constituent.Herein, so-called main constituent, refer to the composition that allotment amount is maximum, in the present invention, more than the 70 weight % being preferably solid constituent are resinous principle, more preferably more than the 80 weight % of solid constituent are resinous principle, it is preferred to more than the 90 weight % of solid constituent are resinous principle.
In the present invention, when the alkali soluble resin using (B) containing acid labile group, it is preferably and comprises this (B) resin with the ratio of 10 weight %～97 weight % in total resinous principle, it is more preferably and comprises 15 weight %～95 weight %, it is particularly preferred that for comprising 20 weight %～90 weight %.
In the present invention, when (B ') resin is somebody's turn to do in use, preferably comprise this (B ') resin with the ratio of 3 weight %～70 weight % in total resinous principle, more preferably comprise 5 weight %～65 weight %, it is particularly preferred that for comprising 10 weight %～60 weight %.
(C) radiation acid producing agent
The photosensitive resin composition of the present invention contains (C) radiation acid producing agent.The radiation acid producing agent used in the present invention is preferably sensing more than wavelength 300nm, be preferably the active ray of wavelength 300nm～450nm and produce the compound of acid, but its chemical constitution there is no particular restriction.Additionally, about the radiation acid producing agent that the active ray of more than wavelength 300nm is not directly sensed, as long as by with sensitizer and with and sense the active ray of more than wavelength 300nm and produce the compound of acid, then can also be preferably used with sensitizer combination.The radiation acid producing agent used in the present invention is preferably the radiation acid producing agent producing the acid that pKa is less than 4, more preferably produce the radiation acid producing agent of the acid that pKa is less than 3.
The example of radiation acid producing agent can be enumerated: trichloromethyl-s-triazine, sulfonium salt or iodine salt, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds, naphthalene quinone di-azido compound etc..In these examples, for the viewpoint of insulating properties, it is preferable to use oxime sulfonate compounds.These radiation acid producing agents can be used alone a kind or by two or more combination use.
These concrete examples can illustrate example below.
nullTrichloromethyl-s-triazine can illustrate: 2-(3-chlorphenyl)-bis-(4，6-trichloromethyl)-s-triazine、2-(4-methoxyphenyl)-bis-(4，6-trichloromethyl)-s-triazine、2-(4-methyl mercapto phenyl)-bis-(4，6-trichloromethyl)-s-triazine、2-(4-methoxyl group-β-styryl)-bis-(4，6-trichloromethyl)-s-triazine、2-piperonyl-bis-(4，6-trichloromethyl)-s-triazine、2-[2-(furan-2-base) vinyl]-bis-(4，6-trichloromethyl)-s-triazine、2-[2-(5-methylfuran-2-base) vinyl]-bis-(4，6-trichloromethyl)-s-triazine、2-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-bis-(4，6-trichloromethyl)-s-triazine or 2-(4-methoxyl group naphthyl)-bis-(4，6-trichloromethyl)-s-triazine etc.；
Diaryl iodonium salt can illustrate: trifluoroacetic acid diphenyl iodine, trifluoromethanesulfonic acid diphenyl iodine, trifluoromethanesulfonic acid 4-methoxyphenyl phenyl-iodide, trifluoroacetic acid 4-methoxyphenyl phenyl-iodide, trifluoromethanesulfonic acid phenyl-4-(2 '-hydroxyl-1 '-ten four oxygen) phenyl-iodide, hexafluoro-antimonic acid 4-(2 '-hydroxyl-1 '-ten four oxygen) phenyl-iodide, p-methyl benzenesulfonic acid phenyl-4-(2 '-hydroxyl-1 '-ten four oxygen) phenyl-iodide etc.；
Triaryl matte salt can illustrate: trifluoromethanesulfonic acid triphenylsulfonium, trifluoroacetic acid triphenylsulfonium, trifluoromethanesulfonic acid 4-methoxyphenyl diphenyl sulfonium, trifluoroacetic acid 4-methoxyphenyl diphenyl sulfonium, trifluoromethanesulfonic acid 4-Phenylsulfanylphenyl diphenyl sulfonium or trifluoroacetic acid 4-Phenylsulfanylphenyl diphenyl sulfonium etc.；
Quarternary ammonium salt class can illustrate: butyl three (2,6-difluorophenyl) boric acid tetramethyl-ammonium, hexyl three (rubigan) boric acid tetramethyl-ammonium, hexyl three (3-trifluoromethyl) boric acid tetramethyl-ammonium, butyl three (2,6-difluorophenyl) boric acid benzyl dimethyl phenyl ammonium, hexyl three (rubigan) boric acid benzyl dimethyl phenyl ammonium, hexyl three (3-trifluoromethyl) boric acid benzyl dimethyl phenyl ammonium etc.；
Diazomethane derivative can illustrate: double; two (cyclohexylsulfonyl) Azimethylene., double; two (tert. butylsulfonyl) Azimethylene., double; two (p-toluenesulfonyl) Azimethylene. etc.；
Acid imide sulfonate derivatives can illustrate: trimethyl fluoride sulfonyl oxygen base dicyclo [2.2.1]-5-in heptan alkene dicarboximide, succimide trifluoromethane sulfonic acid ester, phthalimide trifluoromethane sulfonic acid ester, N-hydroxyl naphthalimide methanesulfonates, N-hydroxyl-5-norborene-2,3-dicarboximide propane sulfonic acid ester etc.；
Oxime sulfonate compounds can illustrate compound shown below.
Namely oxime sulfonate compounds has the compound of oxime sulfonates residue can preferably illustrate the compound containing the oxime sulfonates residue represented by formula (b1).
(in formula (b1), R5Represent alkyl or aryl.)
Arbitrary group all can be replaced, R5In alkyl can be straight-chain, it is also possible to be branch-like, it is also possible to be ring-type.Hereinafter the substituent group allowed is illustrated.
R5Alkyl be preferably straight-chain or the branch-like alkyl of carbon number 1～10.R5Alkyl can be replaced through the aryl of carbon number 6～11, the alkoxyl of carbon number 1～10 or cycloalkyl (what comprise 7,7-dimethyl-2-side oxygen norbornies etc. has bridge-type alcyl, it is preferred to bicyclic alkyl etc.).
R5Aryl be preferably the aryl of carbon number 6～11, more preferably phenyl or naphthyl.R5Aryl can be replaced through low alkyl group, alkoxyl or halogen atom.
Compound containing the oxime sulfonates residue represented by described formula (b1) is particularly preferably the oxime sulfonate compounds represented by formula (OS-3), formula (OS-4) or formula (OS-5).
(in formula (OS-3)～formula (OS-5), R1Represent alkyl, aryl or heteroaryl, R2Separately represent hydrogen atom, alkyl, aryl or halogen atom, R6Separately representing halogen atom, alkyl, alkoxyl, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X represents that O or S, n represent that 1 or 2, m represent the integer of 0～6.)
In described formula (OS-3)～formula (OS-5), R1In alkyl, aryl or heteroaryl can have substituent group.
In described formula (OS-3)～formula (OS-5), R1In alkyl preferably can have the alkyl of total carbon number 1～30 of substituent group.
R1In the substituent group that can have of alkyl can enumerate: halogen atom, alkoxyl, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl.
R1In alkyl can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, trifluoromethyl, perfluoro propyl, perfluoro hexyl, benzyl.
It addition, in described formula (OS-3)～formula (OS-5), R1In aryl preferably can have the aryl of total carbon number 6～30 of substituent group.
R1In the substituent group that can have of aryl can enumerate: halogen atom, alkyl, alkoxyl, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl, sulfonic group, amino-sulfonyl, alkyloxysulfonyl.
R1In aryl can enumerate: phenyl, p-methylphenyl, rubigan, penta chlorphenyl, pentafluorophenyl group, o-methoxyphenyl, to Phenoxyphenyl.
It addition, in described formula (OS-3)～formula (OS-5), R1In heteroaryl preferably can have the heteroaryl of total carbon number 4～30 of substituent group.
R1In the substituent group that can have of heteroaryl can enumerate: halogen atom, alkyl, alkoxyl, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl, sulfonic group, amino-sulfonyl, alkyloxysulfonyl.
In described formula (OS-3)～formula (OS-5), R1As long as at least 1 ring of heteroaryl be assorted aromatic rings, for instance assorted aromatic rings and phenyl ring can contracting rings.
R1In heteroaryl can enumerate the group that freely can have 1 hydrogen atom of removal on the ring the thiphene ring of substituent group, pyrrole ring, thiazole ring, imidazole ring, furan nucleus, benzothiophene ring, benzothiazole ring and the formed group of benzimidazole ring from choosing and obtain.
In described formula (OS-3)～formula (OS-5), R2It is preferably hydrogen atom, alkyl or aryl, more preferably hydrogen atom or alkyl.
In described formula (OS-3)～formula (OS-5), compound exists the R of more than 22In, it is preferred to 1 or 2 is alkyl, aryl or halogen atom, more preferably 1 is alkyl, aryl or halogen atom, it is particularly preferred that be 1 for alkyl, and all the other are hydrogen atom.
In described formula (OS-3)～formula (OS-5), R2In alkyl or aryl can have substituent group.R2In alkyl or the substituent group that can have of aryl can illustrate and described R1In alkyl or the identical group of the substituent group that can have of aryl.
R2In alkyl preferably can have the alkyl of total carbon number 1～12 of substituent group, more preferably can have the alkyl of total carbon number 1～6 of substituent group.
R2In alkyl be preferably: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-hexyl, pi-allyl, chloromethyl, bromomethyl, methoxy, benzyl, it is more preferably: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-hexyl, it is especially preferably: methyl, ethyl, n-pro-pyl, normal-butyl, n-hexyl, it is particularly preferred to for methyl.
R2In aryl preferably can have the aryl of total carbon number 6～30 of substituent group.
R2In aryl be specifically preferably: phenyl, p-methylphenyl, Chloro-O-Phenyl, rubigan, o-methoxyphenyl, to Phenoxyphenyl.
R2In halogen atom can enumerate: fluorine atom, chlorine atom, bromine atoms, atomic iodine.
In these halogen atoms, it is preferred to chlorine atom, bromine atoms.
In described formula (OS-3)～formula (OS-5), X represents O or S, it is preferred to O.
In formula (OS-3)～formula (OS-5), it is 5 Yuans rings or 6 Yuans rings containing X as the ring of ring person.
In described formula (OS-3)～formula (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, it addition, be the situation of S at X, n is preferably 2.
In described formula (OS-3)～formula (OS-5), R6In alkyl and alkoxyl can have substituent group.
In described formula (OS-3)～formula (OS-5), R6In alkyl preferably can have the alkyl of total carbon number 1～30 of substituent group.
R6In the substituent group that can have of alkyl can enumerate: halogen atom, alkoxyl, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl.
R6In alkyl be preferably: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, trifluoromethyl, perfluoro propyl, perfluoro hexyl, benzyl.
In described formula (OS-3)～formula (OS-5), R6In alkoxyl preferably can have the alkoxyl of total carbon number 1～30 of substituent group.
R6In the substituent group that can have of alkoxyl can enumerate: halogen atom, alkoxyl, aryloxy group, alkylthio group, arylthio, alkoxy carbonyl, aryloxycarbonyl, amino carbonyl.
R6In alkoxyl be preferably: methoxyl group, ethyoxyl, butoxy, hexyloxy, phenoxy group, trichloromethoxy or ethoxy ethoxy.
In described formula (OS-3)～formula (OS-5), R6In amino-sulfonyl can enumerate: aminosulfonyl, dimethylaminosulfonyl, phenylsulfamoyl, methylphenylamino sulfonyl, amino-sulfonyl.
In described formula (OS-3)～formula (OS-5), R6In alkyloxysulfonyl can enumerate: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, butoxy sulfonyl.
It addition, in described formula (OS-3)～formula (OS-5), m represents the integer of 0～6, it is preferred to the integer of 0～2, more preferably 0 or 1, it is particularly preferred to be 0.
It addition, the compound containing the oxime sulfonates residue represented by described formula (b1) is particularly preferably any one represented oxime sulfonate compounds in following formula (OS-6)～formula (OS-11).
(in formula (OS-6)～formula (OS-11), R1Represent alkyl, aryl or heteroaryl, R7Represent hydrogen atom or bromine atoms, R8Represent hydrogen atom, the alkyl of carbon number 1～8, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, R9Represent hydrogen atom, halogen atom, methyl or methoxyl group, R10Represent hydrogen atom or methyl.)
R in formula (OS-6)～formula (OS-11)1With the R in described formula (OS-3)～formula (OS-5)1Implication is identical, it is preferable that aspect is also identical.
R in formula (OS-6)7Represent hydrogen atom or bromine atoms, it is preferred to hydrogen atom.
R in formula (OS-6)～formula (OS-11)8Represent hydrogen atom, the alkyl of carbon number 1～8, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxy, phenyl or chlorphenyl, it is preferably the alkyl of carbon number 1～8, halogen atom or phenyl, it is more preferably the alkyl of carbon number 1～8, it is especially preferably the alkyl of carbon number 1～6, it is particularly preferred to for methyl.R in formula (OS-8) and formula (OS-9)9Represent hydrogen atom, halogen atom, methyl or methoxyl group, it is preferred to hydrogen atom.
R in formula (OS-8)～formula (OS-11)10Represent hydrogen atom or methyl, it is preferred to hydrogen atom.
It addition, in described oxime sulfonate compounds, about the stereochemical structure (E, Z) of oxime, it is possible to be any of which, it is also possible to be mixture.
The concrete example of the oxime sulfonate compounds represented by described formula (OS-3)～formula (OS-5) can enumerate following exemplary compounds, but the present invention is not limited to these compounds.
Described compound containing the oxime sulfonates residue represented by formula (b1) is it is also preferred that compound represented by formula (OS-1).
(in formula (OS-1), R1Represent hydrogen atom, alkyl, thiazolinyl, alkoxyl, alkoxy carbonyl, acyl group, carbamyl, sulfamoyl, sulfo group, cyano group, aryl or heteroaryl；R2Represent alkyl or aryl.)
X represents-O-,-S-,-NH-,-NR5-、-CH2-、-CR6H-or-CR6R7-, R5～R7Represent alkyl or aryl.
R21～R24Separately represent hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxyl, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide groups, sulfo group, cyano group or aryl.R21～R24In 2 can be combined with each other respectively and form ring.
R21～R24It is preferably hydrogen atom, halogen atom and alkyl, it is also preferable to enumerate R21～R24In at least 2 be combined with each other and form the aspect of aryl.Wherein, for the viewpoint of sensitivity, it is preferred to R21～R24It is the aspect of hydrogen atom.
Described functional group all can also have substituent group.
Compound represented by described formula (OS-1) is more preferably the compound represented by following formula (OS-2).
In described formula (OS-2), R1、R2、R21～R24Identical with the implication in formula (OS-1) respectively, it is additionally preferred example is also identical.
In these compounds, more preferably formula (OS-1) and the R in formula (OS-2)1Aspect for cyano group or aryl, it is most preferred that represented by formula (OS-2), and R1Aspect for cyano group, phenyl or naphthyl.
It addition, in described oxime sulfonate compounds, about the stereochemical structure (E, Z etc.) of oxime or benzothiazole ring, can be any of which respectively, it is also possible to be mixture.
Hereinafter, represent the concrete example (exemplary compounds b-1～exemplary compounds b-34) of the compound represented by formula (OS-1) that can be suitable for use in the present invention, but the present invention is not limited to this concrete example.Additionally, Me represents that methyl, Et represent that ethyl, Bn represent benzyl, Ph represents phenyl.
In described compound, with regard to sensitivity and stability and for the viewpoint deposited, it is preferred to b-9, b-16, b-31, b-33.
Described compound containing the oxime sulfonates residue represented by formula (b1) can be the oxime sulfonate compounds represented by following formula (b2).
(in formula (b2), R5Representing alkyl or aryl, X represents alkyl, alkoxyl or halogen atom, and m represents the integer of 0～3, and when m is 2 or 3, multiple X can be identical, it is also possible to different.)
Straight-chain or the branch-like alkyl of carbon number 1～4 it is preferably as the alkyl of X.
Straight-chain or the branch-like alkoxyl of carbon number 1～4 it is preferably as the alkoxyl of X.
Halogen atom as X is preferably chlorine atom or fluorine atom.
M is preferably 0 or 1.
In formula (b2), it is particularly preferred to be 1, X for m be methyl, the position of substitution of X is ortho position, R5For the straight-chain alkyl of carbon number 1～10,7,7-dimethyl-2-side oxygen norbornylmethyl or the compounds to toluyl groups.
Compound containing the oxime sulfonates residue represented by formula (b1) can be the oxime sulfonate compounds represented by formula (b3).
(in formula (b3), R5With the R in formula (b1)5Implication is identical, and X ' represents halogen atom, hydroxyl, the alkyl of carbon number 1～4, the alkoxyl of carbon number 1～4, cyano group or nitro, and L represents the integer of 0～5.)
R in formula (b3)5It is preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor-n-pro-pyl, perfluor-normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, it is particularly preferred to for n-octyl.
X ' is preferably the alkoxyl of carbon number 1～5, more preferably methoxyl group.
L is preferably 0～2, it is particularly preferred to be 0～1.
The concrete example of the compound represented by formula (b3) can be enumerated: α-(methylsulfonyloxyimino) benzyl cyanide, α-(ethylsulfonyloxy imino group) benzyl cyanide, α-(n-pro-pyl sulfonyloxyimino) benzyl cyanide, α-(normal-butyl sulfonyloxyimino) benzyl cyanide, α-(4-tosyloxy imino group) benzyl cyanide, α-[(methylsulfonyloxyimino)-4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxy imino group)-4-methoxyphenyl] acetonitrile, α-[(n-pro-pyl sulfonyloxyimino)-4-methoxyphenyl] acetonitrile, α-[(normal-butyl sulfonyloxyimino)-4-methoxyphenyl] acetonitrile, α-[(4-tosyloxy imino group)-4-methoxyphenyl] acetonitrile.
The concrete example of preferred oxime sulfonate compounds can enumerate following compound (i)～compound (viii) etc., it is possible to is used alone a kind, or and uses two or more.Compound (i)～compound (viii) can obtain as commercially available product.Alternatively, it is also possible to use with the combination of other kinds of (C) radiation acid producing agent.
Quinone di-azido compound can enumerate adjacent quinone di-azido compound (1,2-quinone di-azido compound) or to quinone di-azido compound (Isosorbide-5-Nitrae-quinone di-azido compound).Wherein, for the viewpoint of sensitivity or developability, it is preferred to 1,2-quinone di-azido compound, it is particularly preferred to be 1,2-naphthalene quinone di-azido compound.
1,2-quinone di-azido compound is such as by making 1,2-quinone two nitrine sulfonic acid chloride class and hydroxy compounds, amino-compound etc., carrying out condensation reaction and obtain under the existence of desalination acid agent.
1,2-quinone di-azido compound include, for example 1,2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinone two nitrine sulfonic acid amides, 1,2-naphthoquinone two nitrine sulfonic acid amides etc..nullSpecifically can enumerate: J.Kosar work " photosensitive system (Light-SensitiveSystems) " pp.339～352 (1965)，John wiley & sons, inc (NewYork) or W.S.DeForest work " photoresistance (Photoresist) " 50 (1975)，McGraw-Hill，Inc，(NewYork) 1 recorded in，2-quinone di-azido compound，Japanese Patent Laid-Open 2004-170566 publication、Japanese Patent Laid-Open 2002-40653 publication、Japanese Patent Laid-Open 2002-351068 publication、Japanese Patent Laid-Open 2004-4233 publication、1 recorded in Japanese Patent Laid-Open 2004-271975 publication etc.，2-quinone di-azido compound.In the paragraph 0066～0081 of Japanese Patent Laid-Open 2008-224970 publication record 1,2-quinone di-azido compound it is also preferred that.
Having in the compound of 1,2-naphthoquinone diazido, the sensitivity of the compound with following structure is high especially, therefore can be preferably used.
And then, it is most preferred that the compound with 1,2-naphthoquinone diazido be following compound.For the viewpoint of sensitivity and the transparency, H and 1 in D, the ratio (mol ratio) of 2-naphthoquinone diazido is preferably 50: 50～1: 99.
In the photosensitive resin composition of the present invention, relative to resinous principle 100 weight portion, (C) radiation acid producing agent is preferably with 0.1 weight portion～10 weight portion, more preferably use 0.5 weight portion～10 weight portion.It is particularly preferably and comprises (C) radiation acid producing agent relative to total solid composition with the scope of 0.1%～10%.
(D) cross-linking agent
The photosensitive resin composition of the present invention is preferably and optionally contains (D) cross-linking agent.(D) cross-linking agent such as can add there is in the molecule of the following stated more than 2 epoxy radicals or oxetanylmethoxy compound, cross-linking agent containing alkoxy methyl, there is the compound of at least 1 ethylene unsaturated double-bond.In the photosensitive resin composition of the present invention, relative to resinous principle 100 weight portion, (D) cross-linking agent is preferably with 1 weight portion～40 weight portion.It is particularly preferably and comprises (D) cross-linking agent relative to total solid composition with the scope of 1%～40%.
By adding (D) cross-linking agent, cured film can be made to become more firmly film.Cross-linking agent can add following compound.
<there is in molecule the compound of more than 2 epoxy radicals>
The concrete example of the compound in molecule with more than 2 epoxy radicals can be enumerated: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, aliphatic epoxy resin etc..
These compounds can obtain as commercially available product.Such as, bisphenol A type epoxy resin can be enumerated: JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (are manufactured by Mitsubishi Chemical's (stock)) above, and EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (are manufactured by DIC (stock)) above；Bisphenol f type epoxy resin can be enumerated: JER806, JER807, JER4004, JER4005, JER4007, JER4010 (are manufactured by Mitsubishi Chemical's (stock)) above, EPICLON830, EPICLON835 (are manufactured by DIC (stock)) above, and LCE-21, RE-602S (are manufactured by Japan's chemical medicine (stock)) above；Phenol novolak type epoxy resin can be enumerated: JER152, JER154, JER157S65, JER157S70 (are manufactured by Mitsubishi Chemical's (stock)) above, and EPICLONN-740, EPICLONN-740, EPICLONN-770, EPICLONN-775 (are manufactured by DIC (stock)) above；Cresol novolak type epoxy resin can be enumerated: EPICLONN-660, EPICLONN-665, EPICLONN-670, EPICLONN-673, EPICLONN-680, EPICLONN-690, EPICLONN-695 (are manufactured by DIC (stock)) above, and EOCN-1020 (is manufactured by Japan's chemical medicine (stock)) above；Biphenyl type epoxy resin can be enumerated: JERYX4000, JERYX4000H, JERYX4000HK, JERYL6121H (are manufactured by Mitsubishi Chemical's (stock)) above；nullAliphatic epoxy resin can be enumerated: ADEKARESINEP-4080S、ADEKARESINEP-4085S、ADEKARESINEP-4088S (is manufactured by (stock) Ai Dike (ADEKA)) above，Celloxide2021P、Celloxide2081、Celloxide2083、Celloxide2085、EHPE3150、EPOLEADPB3600、EPOLEADPB4700 (is manufactured by Daicel (Daicel) chemical industry (stock)) above，DenacolEX-211、Denacol212、Denacol212L、Denacol214L、Denacol216L、Denacol313、Denacol314、Denacol321、Denacol321L、Denacol411、Denacol421、Denacol512、Denacol521、Denacol611、Denacol612、Denacol614、Denacol614B、Denacol622、Denacol810、Denacol811、Denacol850、Denacol850L、Denacol851、Denacol821、Denacol830、Denacol832、Denacol841、Denacol911、Denacol941、Denacol920、Denacol931、DenacolDLC-201、DenacolDLC-203、DenacolDLC-204、DenacolDLC-205、DenacolDLC-206、DenacolDLC-301、DenacolDLC-402 (is manufactured by long rapids chemical technology (NagaseChemteX)) above，YH-300、YH-301、YH-302、YH-315、YH-324、YH-325 (is manufactured by Nippon Steel's chemistry) above.In addition, can also enumerate: ADEKARESINEP-4000S, ADEKARESINEP-4003S, ADEKARESINEP-4010S, ADEKARESINEP-4011S (are manufactured by (stock) ADEKA) above, NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (are manufactured by (stock) ADEKA) above, JER1031S, JER1032H60, JER604, JER630 etc..These compounds can be used alone a kind or by two or more combination use.
In these compounds, preferred compound can be enumerated: bisphenol A type epoxy resin, bisphenol f type epoxy resin, aliphatic epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin.It is particularly preferably bisphenol A type epoxy resin, phenol novolak type epoxy resin, aliphatic epoxy resin, biphenyl type epoxy resin.
<there is in molecule the compound of more than 2 oxetanylmethoxy>
The concrete example in molecule with the compound of more than 2 oxetanylmethoxy can use OXT-121, OXT-221, OX-SQ, PNOX (being synthesized (stock) by East Asia above to manufacture).
When the total amount of resinous principle is set to 100 weight portion, there is the compound of epoxy radicals or the oxetanylmethoxy addition in photosensitive resin composition and be preferably 1 weight portion～50 weight portion, more preferably 3 weight portion～30 weight portions.
<cross-linking agent containing alkoxy methyl>
Cross-linking agent containing alkoxy methyl is preferably alkoxymethylated melamine, aikoxymethytated benzoguanamine, aikoxymethytated glycolurils and aikoxymethytated urea etc..These cross-linking agent are obtain by the methylol of methylolated melamine, methylolation benzoguanamine, methylolation glycoluril or methylolation urea is changed into alkoxy methyl respectively.Kind for this alkoxy methyl is not particularly limited, for instance can enumerate methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl etc., for the viewpoint of the generation amount of emergent gas, it is particularly preferred to for methoxy.In these cross-linked compounds, alkoxymethylated melamine, aikoxymethytated benzoguanamine, aikoxymethytated glycolurils can be enumerated as preferred cross-linked compound, for the viewpoint of the transparency, it is particularly preferred to for aikoxymethytated glycolurils.
nullThese cross-linking agent containing alkoxy methyl can obtain as commercially available product，Such as can be preferably used: Cymel300、Cymel301、Cymel303、Cymel370、Cymel325、Cymel327、Cymel701、Cymel266、Cymel267、Cymel238、Cymel1141、Cymel272、Cymel202、Cymel1156、Cymel1158、Cymel1123、Cymel1170、Cymel1174、CymelUFR65、Cymel300 (is manufactured by three well cyanamides (stock)) above，NikalacMX-750、NikalacMX-032、NikalacMX-706、NikalacMX-708、NikalacMX-40、NikalacMX-31、NikalacMX-270、NikalacMX-280、NikalacMX-290、NikalacMS-11、NikalacMW-30HM、NikalacMW-100LM、NikalacMW-390 (is manufactured by (stock) three and chemistry) above.
The photosensitive resin composition of the present invention uses the cross-linking agent containing alkoxy methyl, the addition of the cross-linking agent containing alkoxy methyl is relative to resinous principle 100 weight portion, it is preferably 0.05 weight portion～50 weight portion, more preferably 0.5 weight portion～10 weight portion.By adding within the scope of this, the excellent solvent resistance of preferred bases dissolubility when can obtain development and the film after hardening.
<there is the compound of at least 1 ethylene unsaturated double-bond>
There is the compound of at least 1 ethylene unsaturated double-bond, it may be preferable to use simple function (methyl) acrylate, 2 officials can (methyl) acrylate, 3 officials can (methyl) acrylate compounds of above (methyl) acrylate etc..
Simple function (methyl) acrylate include, for example: (methyl) acrylic acid 2-hydroxy methacrylate, carbitol (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 3-methoxybutyl, phthalic acid 2-(methyl) acryloyl-oxyethyl-2-hydroxy propyl ester etc..
2 officials can include, for example by (methyl) acrylate: ethylene glycol (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, double; two phenyl phenol fluorenes diacrylate, double; two phenyl phenol fluorenes diacrylates etc..
3 officials can include, for example by (methyl) acrylate above: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tricresyl phosphate ((methyl) acryloxy second) ester, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..
These compounds with at least 1 ethylene unsaturated double-bond can be used alone a kind or by two or more combination use.
The photosensitive resin composition of the present invention has the usage ratio of compound of at least 1 ethylene unsaturated double-bond relative to resinous principle 100 weight portion, it is preferred to below 50 weight portions, more preferably below 30 weight portions.By containing the compound with at least 1 ethylene unsaturated double-bond with this ratio, thermostability and the case hardness etc. of the dielectric film obtained by the photosensitive resin composition of the present invention can be improved.When adding the compound with at least 1 ethylene unsaturated double-bond, it is preferred to add (J) hot radical producing agent.
(E) solvent
The photosensitive resin composition of the present invention usually contains (E) solvent.The photosensitive resin composition of the present invention is preferably to be prepared into and composition, preferred component, any composition will must be dissolved in the solution in (E) solvent.
(E) solvent used in the photosensitive resin composition of the present invention can use known solvent, can illustrate: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, esters, ketone, amide-type, lactone etc..
(E) solvent used in the photosensitive resin composition of the present invention include, for example:
(E-1) the ethylene glycol monoalkyl ether class such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether；
(E-2) the glycol dialkyl ether class such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether；
(E-3) the ethylene glycol monoalkyl ether acetate class such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol ether acetas, ethylene glycol monomethyl ether acetate；
(E-4) the propylene-glycol monoalky lether class such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether；
(E-5) the propylene glycol dialkyl ether such as Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether；
(E-6) the propylene-glycol monoalky lether acetate esters such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetas, propylene glycol monobutyl ether acetas；
(E-7) the diethylene glycol dialkyl ether class such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether；
(E-8) the diethylene glycol monoalkyl ether acetate class such as diethylene glycol monomethyl ether acetas, diethylene glycol monoethyl ether acetas, Diethylene glycol monopropyl ether acetas, butyl carbitol acetate；
(E-9) the dipropylene glycol monoalkylether class such as dipropylene glycol monomethyl ether, DPE, dipropylene glycol monopropyl ether, Dipropylene glycol mono-n-butyl Ether；
(E-9-1) the dipropylene glycol dialkyl ether such as dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether；
(E-10) the dipropylene glycol monoalkylether acetate esters such as dipropylene glycol monomethyl ether acetas, DPE acetas, dipropylene glycol monopropyl ether acetas, Dipropylene glycol mono-n-butyl Ether acetas；
(E-11) lactic acid ester such as methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, n-butyl lactate, isobutyl lactate, N_amyl lactate, isoamyl lactate；
(E-12) the aliphatic carboxylic acid esters such as n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, acetic acid 2-Octyl Nitrite, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl n-butyrate., ethyl n-butyrate., propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butanoic acid, isobutyl isobutyrate (IBIB)；
(E-13) hydroxyl ethyl acetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl ethyl n-butyrate., ethyl methoxyacetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-methoxybutyl acetas, 3-methoxybutyl acetic acid 3-methyl ester, 3-methoxybutyl propanoic acid-3-methyl ester, 3-methoxybutyl butanoic acid-3-methyl ester, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, other esters such as ethyl pyruvate；
(E-14) ketone such as methyl ethyl ketone, methyl acetone, methyl-positive butanone, methylisobutylketone, 2-heptanone, 3-heptanone, dipropyl ketone, Ketohexamethylene；
(E-15) amide-type such as N-METHYLFORMAMIDE, DMF, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrole pyridine ketone；
(E-16) lactone etc. such as gamma-butyrolacton.
Additionally, these solvents can also optionally add further: carbonic acid-1,3-propylene diester, propylene-glycol diacetate, Ethylene glycol acetate, benzyl ether, two hexyl ethers, ethyleneglycol monophenylether acetas, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, sad, 1-capryl alcohol, 1 nonyl alcohol, benzylalcohol, methyl phenyl ethers anisole, benzyl acetate, essence of Niobe, ethyl benzoate, benzyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, carbonic acid-1,3-propylene diester equal solvent.These solvents can be used alone a kind or by two or more mixing use.In the present invention spendable solvent be preferably be used alone a kind or and with 2 kinds, more preferably and with 2 kinds, it is particularly preferred that for by propylene-glycol monoalky lether acetate esters and diethylene glycol dialkyl ether class and use.
The content of (E) solvent in the photosensitive resin composition of the present invention is relative to resinous principle 100 weight portion, it is preferred to 50 weight portion～3,000 weight portion, it is more preferably 100 weight portion～2,000 weight portion, it is particularly preferred that be 150 weight portion～1,500 weight portions.
When (A) resin is without acid labile group, it is more preferably the total solid composition relative to positive-type photosensitive resin composition, comprising (A) alkali soluble resin containing the construction unit represented by formula (1) with mass conversion for the scope of 1%～70%, (B) alkali soluble resin containing acid labile group is comprised in the scope of 30%～99%, and in the scope of 0.1%～10%, comprise (C) radiation acid producing agent (wherein, add up to content not over 100%).Especially the total solid composition relative to positive-type photosensitive resin composition it is particularly preferably, comprising (A) alkali soluble resin containing the construction unit represented by formula (1) with mass conversion for the scope of 1%～50%, (B) alkali soluble resin containing acid labile group is comprised in the scope of 50%～98%, (C) radiation acid producing agent is comprised in the scope of 0.1%～10%, and in the scope of 1%～40%, comprise (D) cross-linking agent (wherein, add up to content not over 100%).
In the positive-type photosensitive resin composition of the present invention, except described composition, adherence modifying agent, alkali compounds, surfactant, plasticiser and hot radical producing agent, antioxidant can be added, with known additives such as thermal acid generator, UV absorbent, tackifier and organic or inorganic antisettling agents.
(F) adherence modifying agent
The photosensitive resin composition of the present invention can also contain (F) adherence modifying agent.In the photosensitive resin composition of the present invention, spendable (F) adherence modifying agent is the inorganic matter becoming base material, for instance the silicon compounds such as silicon, silicon oxide, silicon nitride, improves the compound of the metals such as gold, copper, aluminum and the adherence of dielectric film.Specifically, silane coupler, mercaptan based compound etc. can be enumerated.The silane coupler as (F) adherence modifying agent used in the present invention is the compound for the purpose of the upgrading on surface, is not particularly limited, can use known compound.
Preferred silane coupler include, for example: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyl group trialkoxy silane, γ-glycidoxypropyl group alkyl-dialkoxysilanes, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane.In these compounds, more preferably γ-glycidoxypropyl group trialkoxy silane or γ-methacryloxypropyl trialkoxy silane, it is particularly preferred that for γ-glycidoxypropyl group trialkoxy silane.These compounds can be used alone a kind or by two or more combination use.These compounds are not only effective for the adherence of raising and substrate, and the cone angle of adjustment and substrate is also effective.
The content of (F) the adherence modifying agent in the photosensitive resin composition of the present invention is relative to resinous principle 100 weight portion, it is preferred to 0.1 weight portion～20 weight portion, more preferably 0.5 weight portion～10 weight portion.
(G) alkali compounds
The photosensitive resin composition of the present invention can also contain (G) alkali compounds.(G) alkali compounds can arbitrarily select to use in the compound that chemically amplification resist uses.Include, for example the quarternary ammonium salt etc. of aliphatic amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic acid.
Aliphatic amine include, for example: trimethylamine, diethylamine, triethylamine, two-n-propylamine, three-n-propylamine, two-n-amylamine, three-n-amylamine, diethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine etc..
Aromatic amine include, for example: aniline, benzylamine, DMA, diphenylamines etc..
Hetero ring type amine include, for example: pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, DMAP, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenylimidazolyl, nicotine, niacin, niacin amide, quinoline, 8-phenoxyl quinoline, pyrazine, pyrazoles, pyridazine, purine, Pyrrolizidine, piperidines, piperazine, morpholine, 4-methyl morpholine, 1, 5-diazabicyclo [4.3.0]-5-nonene, 1, 8-diazabicyclo [5.3.0]-7-hendecene etc..
Hydroxide level Four ammonium include, for example: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, four-n-butylammonium hydroxide, four-n-hexyl ammonium hydroxide etc..
The quarternary ammonium salt of carboxylic acid include, for example: tetramethyl-ammonium acetas, tetramethyl-ammonium benzoate, four-normal-butyl ammonium acetas, four-normal-butyl ammonium benzoate etc..
It addition, the present invention can also use the compound represented by formula (g1) as alkali compounds.By using the compound represented by formula (g1), it may be achieved low-k and high substrate adherence.
Formula (g1)
(in formula (g1), R1And R2Separately represent carbon number 1～10 can branch alkyl, can have the aryl of substituent group, the cycloalkyl can with substituent group or morpholinyl；R3Representing oxygen atom or sulphur atom, A represents bivalence linking base.)
R1Preferably can have the aryl of substituent group, the cycloalkyl can with substituent group or morpholinyl, it is particularly preferred that for morpholinyl.
At R1When for aryl, phenyl and naphthyl can be illustrated, more preferably phenyl.Aryl can have substituent group, but is preferably the aryl without substituent group.
At R1When for cycloalkyl, it is preferred to the cycloalkyl of 5 Yuans rings or 6 Yuans rings, it is particularly preferred that be the cycloalkyl of 6 Yuans rings.Cycloalkyl can have substituent group, but is preferably the cycloalkyl without substituent group.
R2Be preferably carbon number 1～10 can branch alkyl, can have the aryl of substituent group or can have the cycloalkyl of substituent group.
At R2When for alkyl, it is preferred to the alkyl of carbon number 1～8.
At R2When for aryl, phenyl and naphthyl can be illustrated, more preferably phenyl.Aryl can have substituent group, but is preferably the aryl without substituent group.
At R2When for cycloalkyl, it is preferred to the cycloalkyl of 5 Yuans rings or 6 Yuans rings, it is particularly preferred that be the cycloalkyl of 6 Yuans rings.Cycloalkyl can have substituent group, but is preferably the cycloalkyl without substituent group.
A represents bivalence linking base, it is preferably alkylidene (such as methylene, ethylidene, propylidene etc.), ring alkylidene (such as cyclohexylene, ring pentylidene etc.), arlydene (such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthylene etc.), ether, carbonyl, ester group, amide groups and comprise the group of combination of these groups, it is particularly preferred that for the group of alkylidene, ether and the combination comprising these groups.
Compound represented by formula (g1) is preferably the compound represented by formula (g2).Formula (g2):
(in formula (g2), R1And R2Separately represent carbon number 1～10 can branch alkyl, can have the aryl of substituent group, the cycloalkyl can with substituent group or morpholinyl；A represents bivalence linking base).
R1、R2, A respectively with the R in described formula (g1)1、R2, A implication identical, it is preferred that scope also implication is identical.
Compound represented by formula (g1) is more preferably the compound represented by formula (g3).
Formula (g3)
(in formula (g3), A represents bivalence linking base.)
A is identical with the A implication in described formula (g1), it is preferred that scope also implication is identical.
In the present invention, spendable alkali compounds can be used alone or two or more kinds may be used.
The content of (G) alkali compounds in the photosensitive resin composition of the present invention is relative to resinous principle 100 weight portion, it is preferably and comprises with the ratio of 0.001 weight portion～2.50 weight portion, more preferably comprise with the ratio of 0.005 weight portion～2.00 weight portion.
(H) surfactant
The photosensitive resin composition of the present invention can contain (H) surfactant.(H) surfactant can use any one in anion system, cation system, nonionic system or both sexes, it is preferred that surfactant is nonionic system surfactant.
The example of nonionic system surfactant can be enumerated: polyoxyethylene higher alkyl ether, polyoxyethylene higher alkylbenzene ethers, the higher aliphatic acid diesters class of polyoxyethylene glycol, poly-silica system, fluorine system surfactant.It addition, following trade name can be enumerated: each series such as KP (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Polyflow (common prosperity company chemistry (stock) manufactures), Eftop (manufacture of JEMCO company), Megafac (DIC (stock) manufacture), Fluorad (Sumitomo 3M (stock) manufacture), AashiGuard, Surflon (Asahi Glass (stock) manufacture), PolyFox (manufacture of OMNOVA company).Additionally, surfactant can be set forth in containing the construction unit A represented by following formula (1) and construction unit B and using oxolane (THF) as solvent when, the weight average molecular weight (Mw) utilizing the polystyrene conversion that gel permeation chromatography measures is 1, more than 000 10, the copolymer of less than 000 is as preferred example.
Construction unit structural unit A B
(in formula (1), R1And R3Separately represent hydrogen atom or methyl, R2Represent the straight-chain alkyl-sub-of carbon number less than more than 14, R4Represent the alkyl of hydrogen atom or carbon number less than more than 14, L represents the alkylidene of carbon number less than more than 36, p and q is the weight percent representing polymerization ratio, p represents the numerical value of below more than 10 weight % 80 weight %, q represents the numerical value of below more than 20 weight % 90 weight %, r represents the integer of less than more than 1 18, and n represents the integer of less than more than 1 10.)
Described L is preferably the branched alkylene groups represented by following formula (2).R in formula (2)5Represent the alkyl of carbon number less than more than 14, with regard to the compatibility and to for the wettability aspect of applied, it is preferred to the alkyl of carbon number less than more than 13, more preferably the alkyl of carbon number 2 or 3.P and q is preferably p+q=100, i.e. 100 weight % with (p+q).
The weight average molecular weight (Mw) of described copolymer is more preferably less than more than 1,500 5,000.
These surfactants can be used alone a kind or by two or more mixing use.
The addition of (H) surfactant in the photosensitive resin composition of the present invention is relative to resinous principle 100 weight portion, it is preferred to below 10 weight portions, more preferably 0.01 weight portion～10 weight portion, it is particularly preferred that be 0.01 weight portion～1 weight portion.
(I) plasticiser
The photosensitive resin composition of the present invention can also contain (I) plasticiser.(I) plasticiser include, for example: dibutyl phthalate, dioctyl phthalate, phthalic acid docosyl ester, Polyethylene Glycol, glycerol, dimethyl glyceryl phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerol etc..
The addition of (I) plasticiser in the photosensitive resin composition of the present invention is relative to resinous principle 100 weight portion, it is preferred to 0.1 weight portion～30 weight portion, more preferably 1 weight portion～10 weight portion.
(J) hot radical producing agent
The photosensitive resin composition of the present invention can also contain (J) hot radical producing agent, the situation of the ethylene unsaturated compound of compound with at least 1 ethylene unsaturated double-bond etc described in contain, it is preferred to containing (J) hot radical producing agent.Hot radical producing agent in the present invention can use known hot radical producing agent.
Hot radical producing agent is to utilize hot energy to produce free radical, the compound of the polyreaction of initiation or promotion polymerizable compound.By adding hot radical producing agent, there is gained cured film and become more tough, the situation that thermostability, solvent resistance improve.
Preferred hot radical producing agent can be enumerated: aromatic series ketone, salt compound, organic peroxide, thio-compounds, six aryl united imidazoles, ketooxime ester compounds, borate compound, piperazine compound, metallocene compound, active ester compound, has the compound of carbon-halogen bond, Azo, bibenzyl derivative etc..(J) hot radical producing agent can be used alone or two or more kinds may be used.
For the viewpoint that film physical property improves, when (A) polymer is set to 100 weight portion, the addition of (J) the hot radical producing agent in the photosensitive resin composition of the present invention is preferably 0.01 weight portion～50 weight portion, it is more preferably 0.1 weight portion～20 weight portion, it is most preferred that be 0.5 weight portion～10 weight portion.
(K) antioxidant
The photosensitive resin composition of the present invention can also contain (K) antioxidant.As (K) antioxidant, known antioxidant can be contained.By adding (K) antioxidant, have the advantage that and can prevent the painted of cured film, or can reduce by decomposing the thickness minimizing caused, it addition, heat resistant transparent is excellent.This antioxidant include, for example: phosphorous antioxidant, hydrazides class, hindered amine system antioxidant, sulfur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, saccharide, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc..In these compounds, for the viewpoint that painted, the thickness of cured film reduces, it is particularly preferred to for phenol system antioxidant.These antioxidants can be used alone a kind, it is also possible to two or more mixing is used.
The commercially available product of phenol system antioxidant include, for example: AdekastabAO-60, AdekastabAO-80 (are manufactured by (stock) ADEKA) above, Irganox1098 (vapour bar Japan (CibaJapan) (stock) manufactures).
Relative to the total solid composition of photosensitive resin composition, the content of (K) antioxidant is preferably 0.1 mass %～6 mass %, more preferably 0.2 mass %～5 mass %, it is particularly preferred to be 0.5 mass %～4 mass %.By being set to this scope, then obtain the substantially transparent property of the film formed, and sensitivity when pattern is formed also becomes good.
Additionally, as the additive beyond antioxidant, it is also possible to the various UV absorbent recorded in " polymeric additive new launches ((stock) daily magazine Jndustrial News company) " or metal inactivator etc. are made an addition in the photosensitive resin composition of the present invention.
<sensitizer>
The photosensitive resin composition of the present invention with in the combination of (C) radiation acid producing agent, in order to promote that it decomposes, it is preferred to containing sensitizer.Sensitizer absorbing activity light or lonizing radiation and become electron excitation state.The sensitizer becoming electron excitation state contacts with light acid producing agent and produces the effect of electron transfer, energy transfer, heating etc..Thus, light acid producing agent produces chemical change and decomposes generation acid.The example of preferred sensitizer can be enumerated and belong to following compounds, and has the compound of absorbing wavelength under any one of 350nm to 450nm wavelength domain.
nullThe polynuclear aromatic same clan is (such as，Pyrene (pyrene)、(perylene)、Triphenylene (triphenylene)、Anthracene (anthracene)、9，10-dibutoxy anthracene (9，10-dibutoxyanthracene)、9，10-diethoxy anthracene (9，10-diethoxyanthracene)、3，7-dimethoxy anthracene (3，7-dimethoxyanthracene)、9，10-dipropoxy anthracene (9，10-dipropyloxyanthracene))、Xanthene (xanthene) class is (such as，Fluorescein (fluorescein)、Eosin (eosin)、Erythrosine (erythrosine)、Rhodamine B (rhodamineB)、Rose-red (rosebengal))、Xanthone (xanthone) class is (such as，Xanthone、Thiaxanthone (thioxanthone)、Diformazan thiaxanthone、Diethyl thiaxanthone)、Cyanine (cyanine) class is (such as，Thia-carbonyl cyanine (thiacarbocyanine)、Oxa-carbocyanine (oxacarbocyanine))、Merocyanine (merocyanine) class is (such as，Merocyanine (merocyanine)、Carbonyl merocyanine (carbomerocyanine))、If red cyanines (rhodacyanine) class、Oxygen (oxonol) class、Thiazine (thiazine) class is (such as，Thionine (thionine)、Methylene blue (methyleneblue)、Toluidine blue (toluidineblue))、Acridine (acridine) class is (such as，Acridine orange (acridineorange)、Chloroflavin (chloroflavin)、Acriflavine (acriflavine))、Acridone (acridone) class is (such as，Acridone、10-butyl-2-chloro-acridine ketone)、Anthraquinone (anthraquinone) class is (such as，Anthraquinone)、In side's acid, salt is (such as，Side's acid inner salt)、Styrene base class、Basis styrene base class is (such as，2-[2-[4-(dimethylamino) phenyl] vinyl] benzothiazole)、Coumarins is (such as，7-lignocaine 4-methylcoumarin、7-hydroxyl 4-methylcoumarin、2，3，6，7-tetrahydrochysene-9-methyl isophthalic acid H，5H，11H [1] .alpha.-5:6-benzopyran also [6，7，8-ij] quinolizine-11-ketone).
In these sensitizers, it is preferred to the polynuclear aromatic same clan, acridine ketone, styrene base class, basis styrene base class, Coumarins, more preferably the polynuclear aromatic same clan.In the polynuclear aromatic same clan, it is most preferred that for anthracene derivant.
(forming method of cured film)
Hereinafter, the forming method of the cured film of the present invention is illustrated.
The forming method of the cured film of the present invention is characterised by including the step of following (1)～(5).
(1) photosensitive resin composition of the present invention is applied to the step on substrate
(2) from the photosensitive resin composition applied, remove the step of solvent
(3) step that active ray is exposed is utilized
(4) aqueous developer solution is utilized to carry out the step developed
(5) step (rear baking procedure) of thermmohardening is carried out
Hereinafter each step is sequentially carried out explanation.
(1) in applying step, the photosensitive resin composition of the present invention is applied (being generally coating) on substrate, form the moistening film containing solvent.
(2) in solvent removal step, utilize the described film applied, by reducing pressure (vacuum) and/or heating, remove solvent and on substrate, form desciccator diaphragm.
(3) active ray in step of exposure, to above below the 450nm of film illumination wavelength 300nm of gained.In this step, (B) light acid producing agent decomposes and produces acid.Utilizing the catalyst action of produced acid, sour decomposability base contained in (A) copolymer is hydrolyzed and generates carboxyl or phenolic hydroxyl group.
In the formation zone of acid catalyst, in order to make described hydrolysis accelerate, can optionally be exposed post-heating and process: PostExposureBake (hereinafter also referred to " PEB ").By PEB, can promote to be generated carboxyl or phenolic hydroxyl group by acid decomposability base.
The activation evergy decomposed due to acid from the sour decomposability base in the construction unit of the monomer represented by formula (a1-1) in the present invention is low, easily utilize and decomposed from the acid of acid producing agent by what expose, produce carboxyl or phenolic hydroxyl group, therefore when PEB need not be carried out, positive image can also be formed by developing.Further, it is also possible to by carrying out PEB at relatively low temperatures, and when not producing cross-linking reaction, promote the hydrolysis of acid decomposability base.The temperature carrying out the situation of PEB is preferably more than 30 DEG C less than 130 DEG C, more preferably more than 40 DEG C less than 110 DEG C, it is particularly preferred to be more than 50 DEG C less than 80 DEG C.
(4), in development step, alkaline-based developer is used to be developed by the copolymer with free carboxyl or phenolic hydroxyl group.The exposure portion region comprising the resin combination with carboxyl or phenolic hydroxyl group being easily dissolved in alkaline-based developer is removed, is consequently formed positive image.
(5) in rear baking procedure, by the positive image of gained is heated, the sour decomposability base in construction unit (a1) is made to carry out thermally decomposing and generating carboxyl or phenolic hydroxyl group, make its crosslinking group with construction unit (a2) cross-link, thus can form cured film.This heating is preferably the high temperature of heating to more than 150 DEG C, more preferably heating is to 180 DEG C～250 DEG C, it is particularly preferred to for heating to 200 DEG C～250 DEG C.Heat time heating time suitably can set according to heating-up temperature etc., it is preferred to is set in the scope of 10 minutes～90 minutes.
If adding before rear baking procedure, active ray, preferably ultraviolet are irradiated in the step of developing pattern comprehensively, then may utilize the acid irradiated by active ray and produce and promote cross-linking reaction.
Then, the forming method of the cured film of the photosensitive resin composition using the present invention is specifically described.
<preparation method of photosensitive resin composition>
With regulation ratio and utilize any means to be mixed by various compositions, be stirred dissolving to prepare photosensitive resin composition.Make each composition be dissolved in (E) solvent the solution obtained in advance for example, it is also possible to make, then they are prepared resin combination with the ratio mixing of regulation.The constituent solution prepared in this way can also after the filter etc. utilizing 0.2 μm of aperture is filtered, in.
<applying step and solvent removal step>
By being applied to by photosensitive resin composition on the substrate of regulation, solvent can be removed by reducing pressure and/or heating (prebake conditions), thus forming required dry coating.As described substrate, for instance in the manufacture of liquid crystal display cells, can illustrate and be provided with Polarizer, and then optionally be provided with black matrix layer, color filter layer, and then be provided with the glass plate etc. of transparent conductive circuit layer.Application process on substrate is not particularly limited, for instance can use the methods such as slot coated method, spurt method, roller rubbing method, method of spin coating.Wherein, the viewpoint of large substrate it is adapted to, it is preferred to slot coated method.If utilizing large substrate to manufacture, then productivity is high, it is preferable that.At this so-called large substrate, refer to the substrate of the size that each limit is more than 1m.
Additionally, (2) heating condition of solvent removal step is that in the construction unit (a1) in the resinous principle in unexposed portion, acid decomposability base decomposes, make resinous principle scope without solubility in alkaline-based developer, can be different according to the kind of each composition or allotment ratio, it is preferred at 80 DEG C～130 DEG C, carry out 30 seconds～about 120 seconds.
<step of exposure and development step (pattern formation method)>
In step of exposure, across the shade with predetermined pattern, the substrate being provided with film is irradiated active ray.After step of exposure, optionally it is heated processing (PEB), then in development step, uses alkaline-based developer to remove exposure portion region and form picture pattern.
Low pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light emitting diode (lightemittingdiode can be used during the exposure of active ray, LED) light source, excimer laser generator etc., it may be preferable to use g line (436nm), i line (365nm), h line (405nm) etc. have the active ray of the wavelength of above below the 450nm of wavelength 300nm.Alternatively, it is also possible to optionally adjust irradiation light by the spectral filter of long wavelength cutoff light filter, short wavelength's cut-off filter, band pass filter etc.
The developer solution used in development step is preferably and comprises alkali compounds.Alkali compounds such as can use: the alkali metal hydroxides such as Lithium hydrate, sodium hydroxide, potassium hydroxide；The alkali carbonate class such as sodium carbonate, potassium carbonate；The alkali metal hydrogencarbonate class such as sodium bicarbonate, potassium bicarbonate；The ammonium hydroxide classes such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, bursine；The aqueous solution of sodium silicate, sodium metasilicate etc..Alternatively, it is also possible to the aqueous solution being used in being added with in the aqueous solution of described bases the water-miscible organic solvents such as appropriate methanol or ethanol or surfactant is used as developer solution.
The pH value of developer solution is preferably 10.0～14.0.
Developing time is preferably 30 seconds～180 seconds, it addition, the method for development can be any one that method (puddlemethod), infusion process etc. are put in leaching.After development, the flowing water that can carry out 30 seconds～90 seconds cleans, and forms required pattern.
<middle baking procedure (shape control)>
For the pattern corresponding with the unexposed area obtained by developing, it is also possible to carry out shape control by adding, before following rear baking procedure, the baking toasting lower temperature more afterwards.Middle baking typically uses the heater such as hot plate or baking oven, after toast lower temperature, such as, at 70 DEG C～130 DEG C, utilize the heat treated that hot plate carries out 1 minute～10 minutes, or utilize the heat treated that baking oven carries out 5 minutes～20 minutes, thus carry out the sclerous reaction under heat flow temperature below, it is suppressed that heat flow during baking after follow-up, make pattern form close to rectangle.
<rear baking procedure (cross-linking step)>
For the pattern corresponding with the unexposed area obtained by developing, by using the heater such as hot plate or baking oven, temperature in regulation, such as, carry out the heat treated of stipulated time at 180 DEG C～250 DEG C, such as carry out on hot plate 5 minutes～60 minutes, or carry out 30 minutes～90 minutes in an oven, the sour decomposability base in resinous principle is made to carry out decomposing and producing carboxyl or phenolic hydroxyl group, it is made to react with the bridging property base in construction unit (a2) and cross-link, thus can form thermostability, the protecting film of the excellence such as hardness or interlayer dielectric.It addition, when being heated processing, it is also possible to improve the transparency by carrying out in a nitrogen environment.In addition, preferably by before heat treated, after utilizing active ray that the figuratum substrate of formation is carried out exposure again, (exposing/baking afterwards again) is toasted after carrying out, and produced acid by (B) composition existed in unexposed portion so that it is play the function as the catalyst promoting cross-linking step.
That is, the forming method of the cured film of the present invention is preferably the step of exposure again including utilizing active ray to expose again between development step and rear baking procedure.As long as the exposure again in step of exposure utilizes the method identical with described step of exposure to carry out, in described step of exposure again, it is preferred to the side the utilizing photosensitive resin composition of the present invention of substrate being formed with to film carries out blanket exposure.
The preferred light exposure of step of exposure is 100mJ/cm again2～1,000mJ/cm2。
The photosensitive resin composition utilizing the present invention also has the interlayer dielectric of high transparent to the situation obtaining insulating properties excellence, at high temperature toast.The interlayer dielectric using the photosensitive resin composition of the present invention and formed has high transparent and cured film physical properties excellent, therefore useful for the purposes of organic EL display or liquid crystal indicator.
The organic EL display of the present invention or liquid crystal indicator are except having the planarization film or interlayer dielectric using the photosensitive resin composition of the described present invention to be formed, there is no particular restriction, can enumerate the known various organic EL displays or liquid crystal indicator of taking various structure.
It addition, the cured film of the photosensitive resin composition of the present invention and the present invention is not limited to described purposes, can be used for various uses.Such as, except planarization film or interlayer dielectric, can be suitable in order to the thickness of the liquid crystal layer in the protecting film of chromatic filter or liquid crystal indicator to be kept the partition fixed, or solid-state imager is arranged at the lenticule etc. on chromatic filter.
Fig. 1 represents the composition concept map of an example of organic EL display.The constructed profile of the substrate in expression bottom emission type organic EL display, has planarization film 4.
Glass substrate 6 is formed bottom gate type TFT1, is formed when covering this TFT1 and comprise Si3N4Dielectric film 3.After forming the contact hole omitting diagram at this on the insulating film 3, the distribution 2 (height 1.0 μm) being connected with TFT1 via this contact hole is formed on dielectric film 3.Distribution 2 is used for being connected the organic EL element formed in step between TFT1 or later with TFT1.
And then, concavo-convex become smooth in order to what make to cause due to the formation of distribution 2, when landfill by distribution 2 cause concavo-convex form planarization layer 4 on the insulating film 3.
Planarization film 4 is formed the organic EL element of bottom emission type.That is, the first electrode 5 comprising ITO is to be connected with distribution 2 be formed on planarization film 4 via contact hole 7.It addition, the first electrode 5 is equivalent to the anode of organic EL element.
It is formed with the dielectric film 8 of the shape of the periphery covering the first electrode 5, by arranging this dielectric film 8, the short circuit between the second electrode formed in the first electrode 5 and step later can be prevented.
And then, Fig. 1 does not illustrate, but via required pattern shade, evaporation arranges electricity hole transport layer, organic luminous layer, electron transfer layer successively, then on whole of surface, form the second electrode comprising Al, by using glass for sealing plate and ultraviolet ray hardening type epoxy resin to carry out fitting sealing, it is thus achieved that connect in each organic EL element and be used for the TFT1 driving this element and the active matric-type organic EL display formed.
Fig. 2 indicates that the profile of the concept of an example of the liquid crystal indicator 10 of active-matrix mode.This color liquid crystal display arrangement 10 is the liquid crystal panel overleaf with backlight unit 12, and liquid crystal panel is configured with the element of TFT16, and the element of this TFT16 is corresponding with all pixels being arranged between the 2 sheet glass substrates 14,15 being pasted with light polarizing film.It is formed on each element on glass substrate, by being formed at contact hole 18 in cured film 17 and the ito transparent electrode 19 of the tangible pixel electrode of distribution.The layer that liquid crystal 20 is set on ito transparent electrode 19 and the RGB color light filter 22 being configured with black matrix.
Example
It is exemplified below example the present invention is specifically described further.Material shown in Examples below, make consumption, ratio, process content, processing sequence etc. without departing from the purport of the present invention, then can suitably change.Therefore, the scope of the present invention is not limited to concrete example shown below.
(synthesis example 1 of binding agent)
In there-necked flask, add the diethylene glycol ethyl methyl ether as solvent (east nation chemical industry manufactures, HisolveEDM, 45g), be warming up to 90 DEG C in a nitrogen environment.In this solution, dissolve the methyl methacrylate (MMA as monomer component, manufacture with the pure pharmaceutical worker's industry of light, 3.27g), methacrylic acid 2-tetrahydrofuran ester (MATHF, composite, 22.17g), hydroxyethyl methacrylate (HEMA, medicine manufacture pure with light, 6.57g), methacrylic acid 3-ethyl-3-oxetanylmethoxy methyl ester (OXE-30, Osaka Organic Chemical Industry manufactures, 20.26g) and n-butoxy methyl acrylamide (NBMA, Tokyo chemical conversion manufactures, 9.43g), and as the 2 of polymerization initiator, double, two (2 Methylpropionic acid) dimethyl ester (V-601 of 2 '-azo, manufacture with the pure pharmaceutical worker's industry of light, 7.36g, for 8mol% for monomer), dripped with 2 hours.Drip and stir 2 hours after terminating.In this solution, add V-601 (1.84g, for 2mol% for monomer) further, and then stir 2 hours, make reaction terminate.It is derived from binding agent S-1.Weight average molecular weight is 12000.
Monomeric species etc. is changed as shown in following table, synthesizes S-2～S-4 in addition in an identical manner.
Table 1
The unit of the monomer component of described table is to represent with a mole %.Initiator is expressed as being set to monomer component mole % during 100 moles of %.Solid component concentration is to represent with monomer weight/(monomer weight+weight of solvent) × 100 (unit: weight %).It addition, reaction temperature when using V-601 as initiator is set to 90 DEG C, reaction temperature when using V-65 as initiator is set to 70 DEG C (also identical for following table).
In described table, PHS represents 4-Vinyl phenol (composite), MAEVE represents methacrylic acid 1-ethoxy ethyl ester (manufacturing with the pure pharmaceutical worker's industry of light), GMA represents glytidyl methacrylate (manufacturing with the pure pharmaceutical worker's industry of light), IBMA represents isobutoxymethyl acrylamide (Tokyo chemical conversion manufactures), St represents styrene (manufacturing with the pure pharmaceutical worker's industry of light), V-65 represents 2,2 '-azo double; two (2,4-methyl pentane nitrile) (manufactures with the pure pharmaceutical worker's industry of light).
(synthesis example 2 of binding agent)
In there-necked flask, add the HisolveEDM (35.7g) as solvent, be warming up to 90 DEG C in a nitrogen environment.This solution dissolves methacrylic acid (MAA, manufacture with the pure pharmaceutical worker's industry of light, 1.72g), MMA (12.65g), HEMA (11.05g), St (5.20g), NBMA (12.5g), V-601 (3.47g, for 8mol% for monomer), dripped with 2 hours.Drip and stir 2 hours after terminating.In this solution, add V-601 (1.84g, for 2mol% for monomer) further, and then stir 2 hours, make reaction terminate.It is derived from adhesive A-1.Weight average molecular weight is 12000.Synthesize A-2～A-21 in an identical manner.The monomeric species used, solvent etc. are shown in following table.
In described table, EHMA represents 2-Ethylhexyl Methacrylate (manufacturing with the pure pharmaceutical worker's industry of light), MMAm represents methoxy acrylamide (manufacture of MRCUnitec company), and PGMEA represents acetic acid methoxyl group propyl ester (Showa electrician manufacture).It addition, α-methylstyrenedimer is by medicine manufacture pure with light, lauryl mercaptan is by medicine manufacture pure with light.
(synthesis example 3 of binding agent)
In there-necked flask, add PGMEA (35.7g), be warming up to 90 DEG C in a nitrogen environment.In this solution, make MAA (1.72g), MAEVE (12.65g), OXE-30 (11.05g), HEMA (5.20g), V-65 (3.47g, for 3mol% for monomer) it is dissolved in PGMEA (35.7g), dripped with 2 hours.Drip and stir 2 hours after terminating, make reaction terminate.It is derived from binding agent B-1.Weight average molecular weight is 15000.
Synthesize B-2～B-18 and B '-1～B '-3 in an identical manner.The monomeric species used, solvent are shown in following table.
In described table, t-BuMA represents Tert-butyl Methacrylate (medicine manufacture pure with light), DCPM represents methacrylic acid bicyclo-pentyl ester (FA-513M, Hitachi's chemical conversion industry manufactures), StOEVE represents 4-(1-ethoxy ethoxy) styrene (also identical for following table).
Table 4
(comparing the synthesis example 1 of binding agent)
In there-necked flask, add PGMEA (35.7g), be warming up to 70 DEG C in a nitrogen environment.This solution dissolves MAA (1.03g), MAEVE (12.65g), OXE-30 (12.52g), HEMA (5.20g), V-65 (3.47g, for 7mol% for monomer), dripped with 2 hours.Stirring after terminating of dripping makes reaction terminate in 4 hours.It is derived from binding agent R-1.Weight average molecular weight is 10000.
Synthesize R-2 in an identical manner.The monomeric species used, solvent are shown in following table.
Table 5
(comparing the synthesis example 2 of binding agent)
According to the method recorded in Japanese Patent Laid-Open 2010-181730 publication, it is thus achieved that PHS/t-BuMA/BnMA polymer (R-3) (A-1 recorded in Japanese Patent Laid-Open 2010-181730 publication).
(comparing the synthesis example 3 of binding agent)
Utilize the method recorded in Japanese Patent Laid-Open 2009-235414 publication, it is thus achieved that the tert-butyl ester/dicyclo (the 2.2.1)-5-in heptan alkene-2-methyl benzoic acid ester (mol ratio: 50/50) of norborene is as R-4.
The synthesis of methacrylic acid 2-tetrahydrofuran ester (MATHF)
Methacrylic acid (86g, 1mol) is cooled to 15 DEG C, adds camphorsulfonic acid (4.6g, 0.02mol).Drip DHF (71g, 1mol, 1.0 equivalent) in this solution.After stirring 1 hour, add saturated sodium bicarbonate aqueous solution (500mL), extract with ethyl acetate (500mL), in addition dried with magnesium sulfate, insoluble matter is filtered, then it is carried out below concentrating under reduced pressure at 40 DEG C, the yellow oil of residue is carried out decompression distillation, it is thus achieved that the fraction MATHF125g of boiling point (bp.) 54 DEG C/3.5mmHg～56 DEG C/3.5mmHg is as colorless oil (productivity 80%).
The synthesis of StOEVE
Synthesize according to the synthesis of described MATHF.
P-1: the synthesis of the oxime sulfonates of following structure
To beta naphthal (10g), chlorobenzene (30mL) aaerosol solution in add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), by mixed liquor heat to 40 DEG C so that it is react 2 hours.Under ice cooling, 4, the HCl/water solution (60mL) of the 4N that drips in reactant liquor, adds ethyl acetate (50mL) and carries out separatory.Potassium carbonate (19.2g) is added in organic layer, after reacting 1 hour at 40 DEG C, the HCl/water solution (60mL) adding 2N carries out separatory, after organic layer is concentrated, utilize diisopropyl ether (10mL) crystallization to be starched again (reslurry), filter, dry and obtain ketonic compound (6.5g).To the ketonic compound (3.0g) of gained, methanol (30mL) aaerosol solution in add acetic acid (7.3g), 50 weight % aqueous hydroxylamine (8.0g), be heated to reflux.After letting cool, add water (50mL), the crystallization precipitated out is filtered, after cleaning with cold methanol, is dried and obtain oxime compound (2.4g).
The oxime compound (1.8g) making gained is dissolved in acetone (20mL), adds triethylamine (1.5g), paratoluensulfonyl chloride (2.4g) under ice cooling, 4, is warming up to room temperature, reacts 1 hour.In reactant liquor, add water (50mL), after the crystallization precipitated out is filtered, starch again with methanol (20mL), filter, dry and obtain B10 (2.3g).
Additionally, B101H-NMR spectrum (300MHz, CDCl3) for δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
P-3: the synthesis of the sulfonium salt of following structure
Methanol (200mL) dissolves triphenyl phosphonium bromide sulfonium (Tokyo chemical conversion company manufactures, 34.3g).In this solution, dripped with 30 minutes and p-methyl benzenesulfonic acid dihydrate (20.8g) is dissolved in the aqueous solution in water (100mL).The crystallization that will precipitate out is filtered, and starches with methanol/water=50/50 (50mL) again, filters, dry and obtain the P-3 of 30.3g.
<preparation of the photosensitive resin composition of example and comparative example>
Composition shown in following is mixed, utilizes Propylene Glycol (MEDG) to adjust in the way of solid component concentration becomes 20 weight %.The politef filter using 0.2 μm is filtered, and prepares positive-type photosensitive resin composition.The allotment ratio of the binding agent in table represents weight ratio.
In described table, the abbreviation of various additives is as follows.
P-1: the oxime sulfonates (composite) of following structure
P-2: the oxime sulfonates (PAI-101, green chemical industrial company manufactures) of following structure
P-3: the sulfonium salt (composite) of following structure
NQD: adjacent naphthoquinone two nitrine (manufacture of compound probability company of Japan)
S-1: the dibutoxy anthracene (Kawasaki is melted into company and manufactures) of following structure
JER: epoxy crosslinking agent (JER150S70, Mitsubishi Chemical manufactures)
JER2: epoxy crosslinking agent (JER1031S, Mitsubishi Chemical manufactures)
EX: epoxy crosslinking agent (DenacolEX-321L, NagaseChemteX manufacture)
MX: methoxy methyl based cross-linker (NikalacMX-270, three manufacture with chemistry)
F-1: γ-glycidoxypropyl group trialkoxy silane
G-1:2,4,5-triphenylimidazolyl
G-2:1,5-diazabicyclo [4.3.0]-5-nonene
G-3:(g4) compound represented by
Formula (g4)
W-1:MegafacF-554 (DIC manufacture)
W-2:FTX-218G (manufacture of Neos company)
In described formula, Ts represents p-toluenesulfonyl, TsO-Represent p-methyl benzenesulfonic acid anion.
<evaluation>
For the constituent obtained, it is evaluated as follows.
<penetrance>
Form the film of thickness 3.0 μm on the glass substrate.Then, using i line stepper (FPA-3000i5+ that Cannon (stock) manufactures), the shade across regulation is exposed.After development is put in the leaching carried out at 23 DEG C 65 seconds in alkaline-based developer (2.38 weight % tetramethylammonium hydroxide aqueous solution), with ultra-pure water drip washing 1 minute.To the film after development, extra-high-pressure mercury vapour lamp is used to irradiate 300mJ/cm under wavelength 365nm2Light after, in an oven with 220 DEG C heat 45 minutes.Spectrophotometer (U-3000:(stock) Hitachi is used to manufacture), the penetrance of this cured film is measured with wavelength 400nm.Minimum penetrance is shown in table (fresh (Fresh) transparency).
And then, heat 2 hours with 230 DEG C in an oven.Measure the penetrance (resistance to thermal penetration) of this cured film in the same manner.
<sensitivity>
The photosensitive resin composition of the slot coated present invention on the Silicon Wafer have silicon oxide layer, then carries out vacuum drying and forms the film of thickness 3 μm.
Then, using i line stepper (FPA-3000i5+ that Cannon (stock) manufactures), the shade across regulation is exposed.In alkaline-based developer (2.38 weight % tetramethylammonium hydroxide aqueous solution), after development is put in the leaching carried out at 23 DEG C 65 seconds, with ultra-pure water drip washing 1 minute.By these operations, will using 1: 1 resolve the line of 5 μm with space time optimum exposure as sensitivity.For productive viewpoint, optimum exposure is preferably 50mJ/cm2Below, more preferably 20mJ/cm2Below.
<residual film ratio during development>
It addition, measure the thickness in the unexposed portion after development, obtain the ratio (thickness × 100 (%) after unexposed portion thickness ÷ coating after development) of the thickness after relative to coating, thus evaluate residual film ratio during development.
<relative dielectric constant>
At the upper slot coated photosensitive resin composition solution of bare silicon wafer (N-type low resistance) (manufacture of SUMCO company), then with 90 DEG C on hot plate prebake conditions 2 minutes and form the photosensitive resin composition layer of thickness 3.0 μm.To the photosensitive resin composition obtained, utilize the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Cannon (stock) manufactures, reach 300mJ/cm with accumulative irradiation dose2(illumination: 20mW/cm2) mode be exposed, then by this substrate in an oven with 220 DEG C heat 1 hour, be derived from cured film.
For this cured film, use CVmap92A (manufacture of FourDimensionsInc. company), to measure frequency 1MHz to measure relative dielectric constant.This value hour, the relative dielectric constant of cured film is good.
<resistance to dry-etching>
At glass substrate (Corning1737,0.7mm thick (manufacture of Corning company)) the upper each photosensitive resin composition of slot coated, then hot plate was heated removing at 90 DEG C/120 seconds solvent, forms the photosensitive resin composition layer of thickness 4.0 μm.
For the photosensitive resin composition layer obtained, utilize the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Cannon (stock) manufactures, reach 300mJ/cm with accumulative irradiation dose2(illumination: 20mW/cm2, i line) mode be exposed, then, by this substrate in an oven with 230 DEG C heat 1 hour, it is thus achieved that cured film.For this cured film, use dry-etching device " CDE-80N ((stock) ShibauraMechatronics manufacture) ", using as the CF4 of etching gas for 50ml/min, O2For 10ml/min, output, to be 400mW, etching period be that the condition of 90 seconds carries out dry-etching.Etching speed is calculated according to its film minimizing amount.Numerical value is more little, and resistance to dry-etching is more high.
<evaluation of resistance to transparency electrode sputtering>
At glass substrate (Corning1737,0.7mm thick (manufacture of Corning company)) the upper each photosensitive resin composition of slot coated, then heated on hot plate with 90 DEG C/120 seconds and remove solvent, form the photosensitive resin composition layer of thickness 4.0 μm.
For the photosensitive resin composition layer obtained, utilize the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Cannon (stock) manufactures, reach 300mJ/cm with accumulative irradiation dose2(illumination: 20mW/cm2, i line) mode be exposed, then, by this substrate in an oven with 230 DEG C heat 1 hour, it is thus achieved that cured film.
On this cured film, form ITO as transparency electrode by sputtering (ULVAC company manufactures, SIH-3030, sputter temperature 250 DEG C).Optical microscope (500 times) is utilized to observe the surface of the cured film after sputtering.By non-wrinkled or slightly gauffer but be shown as OK for the information slip of realistic scale, other are expressed as NG.
<cone angle>
Form the film of thickness 3.0 μm on the glass substrate.Then, using i line stepper (FPA-3000i5+ that Cannon (stock) manufactures), across the shade of regulation, the pattern to have the hollow pattern of the diameter suitable with contact hole 10 μm carries out the exposure of optimum exposure.By the pattern perpendicular cuts of gained, calculate the angle with basal disc according to optical photograph.
<swelling rate>
At glass substrate (Corning1737,0.7mm thick (manufacture of Corning company)) the upper each photosensitive resin composition of slot coated, then heated on hot plate with 90 DEG C/120 seconds and remove solvent, form the photosensitive resin composition layer of thickness 4.0 μm.
For the photosensitive resin composition layer obtained, utilize the PLA-501F exposure machine (extra-high-pressure mercury vapour lamp) that Cannon (stock) manufactures, reach 300mJ/cm with accumulative irradiation dose2(illumination: 20mW/cm2, i line) mode be exposed, then, by this substrate in an oven with 230 DEG C heat 1 hour, it is thus achieved that cured film.
Make this cured film impregnate 6 points of kinds in the mixed solution of monoethanolamine/dimethyl sulfoxide=30/70, mention this film, after the liquid on surface of flipping, measure thickness immediately.Thickness before dipping and the thickness after dipping are compared, the ratio of increase is recorded with percentage ratio.
Thickness (μm) × 100 before thickness (μm)/dipping after swelling rate (%)=dipping
<overall merit>
Comprehensive described evaluation, evaluated with 5 stages.1 is the most excellent.Realistic scale is more than 3.Above result is summed up and is shown in following table.
Expressed according to described table, it is known that, in positive-type photosensitive resin composition, by using the polymer with the construction unit represented by formula (1), and obtain the positive-type photosensitive resin composition that various performance synthesis is excellent.And then, by making Oxymethylene structure be included in the construction unit of resinous principle, not only can improve resistance to dry-etching and K value, and the positive-type photosensitive resin composition that sensitivity is very high can be obtained especially.And then, the photosensitive resin composition of the present invention can improve resistance to stripping fluidity, and the aspect of the cone angle that can improve pattern is also meaningful.
(example 110)
The constituent of use-case 1～example 98, forms the film of thickness 3.0 μm on the glass substrate.Then, using i line stepper (FPA-3000i5+ that Cannon (stock) manufactures), across the shade of regulation, the pattern to have the hollow pattern of the diameter suitable with contact hole 10 μm carries out the exposure of optimum exposure.After development, use baking oven, after carrying out temporarily calcining (be called middle baking) at 90 DEG C～130 DEG C, carry out the rear baking of 1 hour with 230 DEG C in an oven.The pattern perpendicular cuts that will obtain, calculates the angle with basal disc according to optical photograph.Result is following table such as, can realize high coning angle by carrying out middle baking.
Table 12
Table 13
(example 111)
The photosensitive resin composition of use-case 6, uses UV-LED light source exposure machine to replace extra-high-pressure mercury vapour lamp, implements the evaluation identical with described example 6.Result, it is thus achieved that the result identical with example 6.
(example 112)
Except with the photosensitive resin composition of example 6, substrate is changed to beyond glass substrate by Silicon Wafer, in the way of identical with the sensitivity evaluation that the photosensitive resin composition of example 6 is carried out, carries out the evaluation of sensitivity.Result, it is thus achieved that the result identical with example 6.
(example 113)
Photosensitive resin composition except with example 6, the exposure machine that exposure machine is manufactured by Cannon (stock) is changed to beyond (stock) Nikon FX-803M (gh-Line stepper) manufactured, in the way of identical with the sensitivity evaluation that the photosensitive resin composition of example 6 is carried out, carry out the evaluation of sensitivity.Result, it is thus achieved that the result identical with example 6.
(example 114)
Photosensitive resin composition except with example 6, the exposure machine that exposure machine is manufactured by Cannon (stock) is changed to 355nm laser explosure machine, carry out beyond 355nm laser explosure, in the way of identical with the sensitivity evaluation that the photosensitive resin composition of example 6 is carried out, carry out the evaluation of sensitivity.Result, it is thus achieved that the result identical with example 6.
Additionally, 355nm laser explosure machine is to use (stock) V-Technology to manufacture " EGIS " (wavelength 355nm, pulse width 6nsec), light exposure is to use OPHIR company to manufacture " PE10B-V2 " to measure.
As indicated above, it is known that, no matter substrate, exposure machine, the photosensitive resin composition of example all shows the sensitivity of excellence.
(example 115)
Following methods is utilized to make the organic EL display (with reference to Fig. 1) using thin film transistor (TFT) (TFT).
Forming bottom gate type TFT1 on glass substrate 6, the state to cover this TFT1 is formed and comprises Si3N4Dielectric film 3.Then, after this dielectric film 3 is formed the contact hole omitting diagram at this, the distribution 2 (height 1.0 μm) being connected with TFT1 via this contact hole is formed on dielectric film 3.This distribution 2 is used for being connected the organic EL element formed between TFT1 or later step with TFT1.
And then, concavo-convex become smooth in order to what make to cause due to the formation of distribution 2, when landfill by distribution 2 cause concavo-convex form planarization layer 4 on the insulating film 3.Form planarization film 4 on the insulating film 3, be by the photosensitive resin composition rotary coating of example 18 on substrate, after carrying out prebake conditions (90 DEG C × 2 minutes) on hot plate, high-pressure mercury-vapor lamp is used to irradiate i line (365nm) 45mJ/cm from shade2(illumination 20mW/cm2), then utilize alkaline aqueous solution to carry out developing and forming pattern, then at 230 DEG C, carry out the heat treated of 60 minutes.Coating when being coated with this photosensitive resin composition is good, and the cured film obtained after exposure, development, calcining does not find the generation of gauffer or be full of cracks.And then, the average jump of distribution 2 is 500nm, and the thickness of made planarization film 4 is 2,000nm.
Then, the planarization film 4 obtained forms bottom emission type organic EL element.First, on planarization film 4, make the first electrode 5 comprising ITO be connected with distribution 2 formed via contact hole 7.Then, painting erosion resistant agent, carry out prebake conditions, the shade across desirable pattern is exposed, develops.Using this Resist patterns as shade, by using the Wet-type etching of ITO etchant to carry out pattern processing.Then, anticorrosive additive stripping liquid controlling (mixed liquor of monoethanolamine and dimethyl sulfoxide (DMSO)) is used to peel off this Resist patterns.First electrode 5 of such gained is equivalent to the anode of organic EL element.
Then, the dielectric film 8 of the shape of the periphery covering the first electrode 5 is formed.The photosensitive resin composition of use-case 7 in dielectric film, to form dielectric film 8 with described identical method.By arranging this dielectric film, the short circuit between the second electrode formed in the first electrode 5 and step later can be prevented.
And then, in vacuum deposition apparatus, across required pattern shade, it is deposited with successively and electricity hole transport layer, organic luminous layer, electron transfer layer are set.Then, whole of surface is formed the second electrode comprising Al.The described substrate obtained is taken out from evaporator, by using glass for sealing plate and ultraviolet ray hardening type epoxy resin to carry out fitting sealing.
In the manner, it is thus achieved that in each organic EL element, connect the active matric-type organic EL display being used for driving the TFT1 of this element and formed.Good display characteristic is shown, it is known that be the organic EL display that reliability is high when applying voltage via drive circuit.
(example 116)
In example 115, except the photosensitive resin composition of example 6 is replaced by the photosensitive resin composition of example 1, make organic el device in an identical manner.Show good display characteristic, it is known that be the organic EL display that reliability is high.
(example 117)
In example 115, except the photosensitive resin composition of example 6 is replaced by the photosensitive resin composition of example 32, make organic el device in an identical manner.Show good display characteristic, it is known that be the organic EL display that reliability is high.
(example 118)
In the drive matrix type liquid crystal described in Fig. 1 and Fig. 2 of No. 3321003 publications of Japanese Patent No., form cured film 17 as follows as interlayer dielectric, it is thus achieved that the liquid crystal indicator of example 118.
That is, the photosensitive resin composition of use-case 6, with the method identical with the forming method of the planarization film 4 of the organic EL display in described example 115, forms cured film 17 as interlayer dielectric.
When the liquid crystal indicator obtained is applied driving voltage, show good display characteristic, it is known that be the liquid crystal indicator that reliability is high.
(example 119)
In example 118, except the photosensitive resin composition of example 6 is replaced by the photosensitive resin composition of example 1, make liquid crystal indicator in an identical manner.Show good display characteristic, it is known that be the liquid crystal indicator that reliability is high.
(example 120)
In example 118, except the photosensitive resin composition of example 6 is replaced by the photosensitive resin composition of example 32, make liquid crystal indicator in an identical manner.Show good display characteristic, it is known that be the liquid crystal indicator that reliability is high.

Claims (20)

1. a positive-type photosensitive resin composition, it is characterised in that: comprise the A alkali soluble resin containing construction unit represented by formula (1) and C radiation acid producing agent, also meet following (1) and/or (2):
(1) alkali soluble resin that A contains the construction unit represented by formula (1) has acid labile group；
(2) this positive-type photosensitive resin composition comprises B and has the resin of acid labile group,
Alkali soluble resin that wherein said A contains the construction unit represented by formula (1) and/or be the described B resin with acid labile group, construction unit containing the crosslinking group beyond the construction unit comprised represented by formula (1), or more contain the described A alkali soluble resin containing construction unit represented by formula (1) and described B have the resin B beyond the resin of acid labile group ', and described resin B ' construction unit containing the crosslinking group beyond the construction unit comprised represented by formula (1)
Described acid labile group is the residue that carboxyl or phenolic hydroxyl group are protected by acetal, ketal or tert-butyl group system functional group,
Described bridging property base is oxetanyl and/or epoxy radicals:
In formula, R1Represent hydrogen atom or methyl, R2Represent the alkyl of carbon number 1～9.
2. positive-type photosensitive resin composition according to claim 1, wherein said alkali soluble resin containing the construction unit represented by formula (1) and/or be that to have the resin of acid labile group be the resin containing acidic group to described B.
3. positive-type photosensitive resin composition according to claim 1 and 2, wherein C radiation acid producing agent is oxime sulfonate compounds.
4. positive-type photosensitive resin composition according to claim 1 and 2, wherein said alkali soluble resin containing the construction unit represented by formula (1) and/or be the described B at least one having that the resin of acid labile group contains following represented construction unit:
In described formula, R1Represent the alkyl of hydrogen atom or carbon number 1～4, L respectively1Represent carbonyl or phenylene, R2Represent the alkyl of carbon number 1～4 respectively；N1 and n2 respectively 1～5 integer, n3 is the integer of 1～4, and n4 is the integer of 1～3.
5. positive-type photosensitive resin composition according to claim 1 and 2, wherein said alkali soluble resin containing the construction unit represented by formula (1) and/or be that described B has the resin of acid labile group and contains the construction unit represented by following formula (2) or formula (3):
6. positive-type photosensitive resin composition according to claim 5, wherein said alkali soluble resin containing the construction unit represented by formula (1) and/or be that described B has the resin of acid labile group and contains the construction unit represented by formula (2).
7. positive-type photosensitive resin composition according to claim 1 and 2, wherein comprises the A alkali soluble resin containing construction unit represented by formula (1) and alkali soluble resin that B contains acid labile group.
8. positive-type photosensitive resin composition according to claim 7, the free-radical polymerised compound that the alkali soluble resin that wherein said B contains acid labile group is the free-radical polymerised compound that a unsaturated carboxylic acid, b are contained oxetanes or epoxy radicals and c contains acid labile group carries out the resin of combined polymerization.
9. positive-type photosensitive resin composition according to claim 7, the free-radical polymerised compound that the alkali soluble resin that wherein said B contains acid labile group is the free-radical polymerised compound that a unsaturated carboxylic acid, b are contained oxetanyl and c contains acid labile group carries out the resin of combined polymerization.
10. positive-type photosensitive resin composition according to claim 1 and 2, wherein A alkali soluble resin is the polymer also comprising the construction unit containing acidic group.
11. positive-type photosensitive resin composition according to claim 1 and 2, wherein A alkali soluble resin is also to comprise the polymer from cinnamic construction unit.
12. positive-type photosensitive resin composition according to claim 1 and 2, wherein also comprise D cross-linking agent.
13. positive-type photosensitive resin composition according to claim 1 and 2, wherein comprise the B alkali soluble resin containing acid labile group with the ratio of 10 weight %～97 weight % in total resinous principle.
14. positive-type photosensitive resin composition according to claim 1 and 2, wherein also comprise B and contain the B' resin beyond the alkali soluble resin of acid labile group, and comprise this B' resin with the ratio of 3 weight %～70 weight % in total resinous principle.
15. a cured film, positive-type photosensitive resin composition according to claim 1 is applied on substrate, utilizes light and/or heat to make it harden and form.
16. a cured film, positive-type photosensitive resin composition according to claim 1 is applied on substrate, develops by not including heat treated after exposure, and then the step of heating is formed.
17. an interlayer dielectric, use the cured film according to claim 15 or 16.
18. a display device, it is liquid crystal indicator or organic electroluminescence display device, including interlayer dielectric according to claim 17.
19. a forming method for cured film, comprise the following steps: the step that photosensitive resin composition according to claim 1 is applied on substrate by (1)；(2) from the photosensitive resin composition applied, remove the step of solvent；(3) step that activity lonizing radiation are exposed is utilized；(4) aqueous developer solution is utilized to carry out the step developed；And (5) carry out the step of thermmohardening.
20. the forming method of cured film according to claim 19, wherein after the described step carrying out and developing, carry out the step of thermmohardening before include the step of blanket exposure.
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