CN106104381A - Photosensitive polymer combination, the manufacture method of cured relief pattern and semiconductor device - Google Patents

Photosensitive polymer combination, the manufacture method of cured relief pattern and semiconductor device Download PDF

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Publication number
CN106104381A
CN106104381A CN201580013242.7A CN201580013242A CN106104381A CN 106104381 A CN106104381 A CN 106104381A CN 201580013242 A CN201580013242 A CN 201580013242A CN 106104381 A CN106104381 A CN 106104381A
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composition
resin
formula
mass parts
organic group
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CN106104381B (en
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安西信裕
笹野大辅
古贺寻子
井上泰平
赖末友裕
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Photosensitive polymer combination comprises: (A) is selected from by least a kind of resin in the group forming as the polyamic acid of polyimide precursor, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, the polyhydroxyamide that can become polyazole precursor, polyaminoamide, polyamide, polyamidoimide, polyimides, polybenzoxazole, polybenzimidazoles, polybenzothiozole and phenolic resin；(B) emulsion；And (C) is selected from least a kind in the group that the low-molecular-weight imide compound less than 1000 forms by multifunctional (methyl) acrylate and molecular weight.

Description

Photosensitive polymer combination, the manufacture method of cured relief pattern and semiconductor Device
Technical field
The present invention relates to the insulating materials of such as electronic unit, the passivating film in semiconductor device, buffering film and layer Between the embossing pattern such as dielectric film formation used in photosensitive polymer combination, the manufacture using its cured relief pattern Method, possess the semiconductor device of cured relief pattern and the resin film of the excellent adhesion with polybenzoxazole resin.
Background technology
In the past, the passivating film of the insulating materials of electronic unit and semiconductor device, surface protection film, interlayer dielectric etc. Middle use has the resins such as the polyimides of excellent heat resistance, electrical characteristics and mechanical property.The resins such as this polyimides it In, the resin providing with the form of sensitive polyimide precursor can by utilize the coating of this precursor, exposure, development, with And the hot-imide of solidification processes the embossing pattern overlay film being readily formed heat resistance.Sensitive polyimide precursor with Past non-photo-sensing type polyimides is compared, and has the feature that can significantly shorten operation.
On the other hand, improve and from the viewpoint of short and smallization of chip size from integrated level and function in recent years, will Semiconductor device is installed to the method for printed circuit board also in change.Utilize metal needle and lead-tin eutectic solder from conventional Installation method be changed into and use as can BGA (Ball Grid Array, BGA), the CSP (Chip of more high-density installation Size Package, chip size packages body) etc. the resin coatings such as such, polyimides directly contact the knot of solder projection Structure.When forming such projection cube structure, this overlay film needs high-fire resistance and chemical reagent resistance.Disclose by comprising polyamides The composition of imines precursor or polybenzoxazole precursor adds thermal cross-linking agent, thus improves polyimides overlay film or polyphenyl And the method (with reference to patent document 1) of the heat resistance of azoles overlay film.
Prior art literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-287889 publication
Content of the invention
Problems to be solved by the invention
In the cabling processes again of semiconductor device, the manufacturer of front operation and the manufacturer of rear operation are implemented interlayer respectively exhausted Velum formation process, therefore forms the resins such as polyimides on the polybenzoxazole overlay film being formed by front operation in rear operation The situation of overlay film increases.But, for conventional photosensitive polymer combination, polybenzoxazole overlay film forms additional covering During film, adaptation is insufficient, therefore there is problem peeling-off after development/solidification.Additionally, in the past known be improved resin Relative to the closely sealed auxiliary agent of the adaptation of Si substrate and Cu substrate, but when using closely sealed auxiliary agent, there is the resolution of embossing pattern The problem that rate or heat resistance deteriorate.
And then, when forming the crystal seed layer of metal wiring layer again, need at the surface of resin seamlessly splash-proofing sputtering metal.For This, it is desirable to the opening portion of photosensitive resin pattern, when patterning terminates, is formed with side vertical bottom face than mild positive cone Shape, preferred cone angle are less than 80 °, but use conventional photosensitive polymer combination when patterning terminates, it is also difficult to make out The side of oral area becomes positive taper.
Therefore, it is within the contemplation of the invention that solve the problem in that, provide for make with polybenzoxazole resin, Si substrate and The excellent adhesion of Cu substrate, resolution ratio and heat resistance are high, and then the side of opening portion becomes the sense of the cured film of positive taper Photosensitive resin composition, uses the manufacture method of the cured relief pattern of this photosensitive polymer combination, possesses this cured relief The semiconductor device of pattern, and the resin film layer of the excellent adhesion with polybenzoxazole resin is stacked in glass transition temperature Duplexer on the resin substrate of less than 250 DEG C.
For solution to problem
The present inventor etc. find: arbitrary by the species of specific resin structure, the species of initiator and couplant Photosensitive polymer combination obtained from person give with polybenzoxazole resin, Si substrate and Cu substrate excellent adhesion, Resolution ratio and high and then opening portion the side of heat resistance become the cured relief pattern of positive taper, and comprise specifically to set Fat and there is the resin film of specific crosslink density and specific 5% weightless temperature and the adaptation of polybenzoxazole resin Excellent and can be layered on the resin substrate of below glass transition temperature 250 DEG C, complete the present invention.That is, the present invention is such as The following stated.
[1] a kind of photosensitive polymer combination, it comprises following component:
(A) selected from by as the polyamic acid of polyimide precursor, poly amic acid ester, polyamic acid salt, polyamic acid acyl Amine, the polyhydroxyamide that polyazole precursor can be become, polyaminoamide, polyamide, polyamidoimide, polyimides, polyphenyl And at least a kind of resin in the group of azoles, polybenzimidazoles, polybenzothiozole and phenolic resin composition；
(B) emulsion；And
(C) selected from the low-molecular-weight imide compound less than 1000 by multifunctional (methyl) acrylate and molecular weight In the group of composition at least a kind.
[2] photosensitive polymer combination recorded according to [1], wherein, aforementioned (A) composition is for selected from by as polyimides The polyamic acid of precursor, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, polyamide, polyamidoimide, polyamides are sub- At least a kind of resin in the group of amine, polybenzoxazole, polybenzimidazoles and polybenzothiozole composition.
[3] photosensitive polymer combination recorded according to [1] or [2], wherein, aforementioned (C) composition is aforementioned molecular weight Low-molecular-weight imide compound less than 1000.
[4] according to the photosensitive polymer combination recorded any one of [1]～[3], wherein, aforementioned (A) composition for by under State the polyimide precursor that formula (A1) represents:
In formula (A1), X1It is the organic group of 4 valencys, Y1For the organic group of divalent, l is integer, the R of 2～1501And R2 The separately organic group for hydrogen atom or 1 valency of free redical polymerization.Wherein, R1And R2Both are hydrogen when different Atom., and
Aforementioned (C) composition comprises the maleimide being represented by following formula (C1):
In formula (C1), R3For the organic group of singly-bound, hydrogen atom or 1～trivalent, R4And R5Separately former for hydrogen Son, the alkyl of carbon number 1～10, the cycloalkyl of carbon number 3～10, aryl, alkoxyl or halogen atom, and m be more than 1 whole Number.}.
[5] according to the photosensitive polymer combination recorded any one of [1]～[4], wherein, aforementioned (A) composition for by under State the polyimide precursor that formula (A2) represents:
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7 The organic group of 1 valency separately for hydrogen atom, being represented by following formula (A3) or the representative examples of saturated aliphatic of carbon number 1～4 Group；Wherein, R6And R7Both are hydrogen atom when different.
(in formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is The integer of 2～10.)}.
[6] according to the photosensitive polymer combination recorded any one of [1]～[5], wherein, aforementioned (C) composition comprise by The maleimide that following formula (C2) represents:
In formula (C2), R11For the organic group of singly-bound, hydrogen atom or 1～trivalent, R12And R13It is separately hydrogen Atom, the alkyl of carbon number 1～10, the cycloalkyl of carbon number 3～10, aryl, alkoxyl or halogen atom, and q be 2～4 whole Number.}.
[7] photosensitive polymer combination recorded according to any one of [1]～[6], wherein, aforementioned (B) composition is oxime system Photoepolymerizationinitiater initiater.
[8] photosensitive polymer combination recorded according to any one of [1]～[7], wherein, aforementioned (B) composition comprises choosing At least one in the group that freely following (B1) and (B2) one-tenth is grouped into:
(B1) the i ray absorbance of 0.001wt% solution is 0.15～0.5 and the g ray of 0.001wt% solution is inhaled Luminosity and the oxime ester compound that h ray absorbance is less than 0.2；And
(B2) the i ray absorbance of 0.001wt% solution is less than 0.1, and the g ray extinction of 0.001wt% solution Degree or the oxime ester compound that h ray absorbance is more than 0.05.
[9] photosensitive polymer combination recorded according to [8], wherein, the i of the 0.001wt% solution of aforementioned (B1) composition Ray absorbance is 0.15～0.35.
[10] photosensitive polymer combination recorded according to [8] or [9], wherein, aforementioned (B1) composition comprise selected from by In the group of the oxime ester compound composition that following formula (B11) and (B12) represent at least a kind:
In formula (B11), R14For the fluorine-containing alkyl of C1～C10, R15、R16, and R17It is separately C1～C20Alkane Base, C3～C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that r is 0～5.}
In formula (B12), R18For C1～C30The organic group of divalent, R19～R26It is separately C1～C20Alkyl, C3～C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that s is 0～3.}.
[11] photosensitive polymer combination recorded according to any one of [1]～[10], wherein, becomes at above-mentioned (A)～(C) On the basis of dividing,
Comprise the silicon-containing compound that (D) is represented by following formula (D1):
In formula (D1), R27And R28For C1～C4Alkyl, R29For C1～C6The organic group of divalent, R30For via choosing Atom in the group of free nitrogen, oxygen and sulphur composition and the C of carbonyl linkage1～C20Organic group, t is for selected from the 1st, 2 and 3 Whole, u for selected from the 0th, 1 and 2 integer, and t and u meet the relation of t+u=3.}.
[12] photosensitive polymer combination recorded according to [11], wherein, as aforementioned (D) composition, by previously described formula (D1), on the basis of the silicon-containing compound representing, the silicon-containing compound being represented by following formula (D2) is also comprised:
In formula (D2), R31And R32For C1～C4Alkyl, R33For C1～C6The organic group of divalent, v is for selected from the 1st, 2 And 3 integer, w for selected from the 0th, 1 and 2 integer, and v and w meet the relation of v+w=3.}.
[13] photosensitive polymer combination recorded according to any one of [1]～[10], wherein, becomes at above-mentioned (A)～(C) On the basis of dividing,
Comprise the sulfur-containing compound that (E) is represented by following formula (E1):
In formula (E1), R34For C1～C20Organic group or siliceous organic group, R35For via selected from by nitrogen, oxygen, And the C that the atom in the group of sulphur composition is bonded with thiocarbonyl1～C20Organic group.}.
[14] photosensitive polymer combination recorded according to any one of [1]～[10], wherein, becomes relative to aforementioned (A) Divide 100 mass parts, comprise aforementioned (B) composition 0.1～20 mass parts, and aforementioned (C) composition 1～40 mass parts.
[15] photosensitive polymer combination recorded according to any one of [1]～[10], wherein, becomes relative to aforementioned (A) Divide 100 mass parts, comprise aforementioned (B) composition 0.1～20 mass parts, and aforementioned (C) composition 10～35 mass parts.
[16] photosensitive polymer combination recorded according to [11] or [12], wherein, relative to aforementioned (A) composition 100 Mass parts, comprises aforementioned (B) composition 0.1～20 mass parts, aforementioned (C) composition 1～40 mass parts, and aforementioned (D) composition 0.1 ～20 mass parts.
[17] photosensitive polymer combination recorded according to [11] or [12], wherein, relative to aforementioned (A) composition 100 Mass parts, comprises aforementioned (B) composition 0.1～20 mass parts, aforementioned (C) composition 10～35 mass parts, and aforementioned (D) composition 0.1～20 mass parts.
[18] photosensitive polymer combination recorded according to [13], wherein, relative to aforementioned (A) composition 100 mass parts, bag Containing aforementioned (B) composition 0.1～20 mass parts, aforementioned (C) composition 1～40 mass parts, and aforementioned (E) composition 0.1～20 mass Part.
[19] photosensitive polymer combination recorded according to [13], wherein, relative to aforementioned (A) composition 100 mass parts, bag Containing aforementioned (B) composition 0.1～20 mass parts, aforementioned (C) composition 10～35 mass parts, and aforementioned (E) composition 0.1～20 mass Part.
[20] a kind of photosensitive polymer combination, it comprises following component:
(AX) sensitive polyimide precursor；With
At least one selected from being become by following (B1) and (B2) in the group being grouped into: the i of (B1) 0.001wt% solution penetrates Line absorbance is 0.15～0.5 and the g ray absorbance of 0.001wt% solution and h ray absorbance are less than 0.2 Oxime ester compound, and
(B2) the i ray absorbance of 0.001wt% solution is less than 0.1 and the g ray extinction of 0.001wt% solution Degree or the oxime ester compound that h ray absorbance is more than 0.05.
[21] photosensitive polymer combination recorded according to [20], wherein, aforementioned (AX) composition is for by following formula (A2) The polyimide precursor representing:
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7 The organic group of 1 valency separately for hydrogen atom, being represented by following formula (A3) or the representative examples of saturated aliphatic of carbon number 1～4 Group；Wherein, R6And R7Both are hydrogen atom when different.
(in formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is The integer of 2～10.)}.
[22] photosensitive polymer combination recorded according to [20] or [21], wherein, aforementioned (B1) composition The i ray absorbance of 0.001wt% solution is 0.15～0.35.
[23] photosensitive polymer combination recorded according to any one of [20]～[22], wherein, aforementioned (B1) becomes subpackage Containing in the group that the oxime ester compound being represented by following formula (B11) and (B12) forms at least a kind:
In formula (B11), R14For C1～C10Fluorine-containing alkyl, R15、R16, and R17It is separately C1～C20Alkane Base, C3～C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that r is 0～5.}
In formula (B12), R18For C1～C30The organic group of divalent, R19～R26It is separately C1～C20Alkyl, C3～C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that s is 0～3.}.
[24] photosensitive polymer combination recorded according to any one of [20]～[23], wherein, relative to 100 mass parts The total content of aforementioned (B1) composition of aforementioned (AX) composition and (B2) composition is 0.1～10 mass parts.
[25] photosensitive polymer combination recorded according to any one of [20]～[24], wherein, relative to 100 mass parts The total content of aforementioned (B1) composition of aforementioned (AX) composition and (B2) composition is 0.5～5 mass parts.
[26] a kind of resin combination, it comprises following composition:
(AY) polyimide precursor；And
(D) silicon-containing compound being represented by following formula (D1):
In formula (D1), R27And R28For C1～C4Alkyl, R29For C1～C6The organic group of divalent, R30For via choosing Atom in the group of free nitrogen, oxygen and sulphur composition and the C of carbonyl linkage1～C20Organic group, t is for selected from the 1st, 2 and 3 Integer, u for selected from the 0th, 1 and 2 integer, and t and u meet the relation of t+u=3.}.
[27] resin combination recorded according to [26], wherein, as aforementioned (D) composition, is being represented by previously described formula (D1) Silicon-containing compound on the basis of, also comprise the silicon-containing compound being represented by following formula (D2):
In formula (D2), R31And R32For C1～C4Alkyl, R33For C1～C6The organic group of divalent, v is for selected from the 1st, 2 And 3 integer, w for selected from the 0th, 1 and 2 integer, and v and w meet the relation of v+w=3.}.
[28] a kind of resin combination, it comprises following composition:
(AY) polyimide precursor；And
(E) sulfur-containing compound being represented by following formula (E1):
In formula (E1), R34For C1～C20Organic group or siliceous organic group, R35For via selected from by nitrogen, oxygen, And the C that the atom in the group of sulphur composition is bonded with thiocarbonyl1～C20Organic group.}.
[29] according to the resin combination recorded any one of [26]～[28], wherein, aforementioned (AY) composition is for by following The polyimide precursor that formula (A2) represents:
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7 The organic group of 1 valency separately for hydrogen atom, being represented by following formula (A3) or the representative examples of saturated aliphatic of carbon number 1～4 Group；Wherein, R6And R7Both are hydrogen atom when different.
(in formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is The integer of 2～10.)}.
[30] resin combination recorded according to [27], wherein, aforementioned relative to 100 mass parts (AY) composition, before comprising State (D1) composition 0.1～20 mass parts, and aforementioned (D2) composition 0.1～20 mass parts.
[31] resin combination recorded according to [28] or [29], wherein, aforementioned relative to 100 mass parts (AY) becomes Point, comprise aforementioned (E) composition 0.1～20 mass parts.
[32] resin combination recorded according to any one of [26]～[31], wherein, possibly together with (B) emulsion.
[33] manufacture method of a kind of cured relief pattern, it comprises following operation:
(1) photosensitive polymer combination recorded any one of coating [1]～[25] on substrate or [32] are recorded Resin combination, forms the operation of photo-sensitive resin on the substrate；
(2) operation that this photo-sensitive resin is exposed；
(3) make the photo-sensitive resin after this exposure develop, form the operation of embossing pattern；With
(4) by this embossing pattern for heating, the operation of cured relief pattern is formed.
[34] a kind of semiconductor device, it possesses the cured relief pattern that the manufacture method recorded by [33] obtains.
[35] a kind of resin film, comprises following composition: (A) is selected from by the polyamic acid, poly-as polyimide precursor Amic acid esters, polyamic acid salt, polyamic acid acid amides, the polyhydroxyamide that polyazole precursor can be become, polyaminoamide, polyamides Amine, polyamidoimide, polyimides, polybenzoxazole, polybenzimidazoles, polybenzothiozole and phenolic resin composition At least a kind of resin in group,
Crosslink density is 1.0 × 10-4mol/cm3Above and 3.0 × 10-3mol/cm3Hereinafter, and
5% weightless temperature is more than 250 DEG C and less than 400 DEG C.
[36] resin film recorded according to [35], wherein, aforementioned crosslink density is 3.0 × 10-4mol/cm3Above and 2.0 ×10-3mol/cm3Below.
[37] resin film recorded according to [35] or [36], wherein, aforementioned (A) composition is for selected from by as polyimides The polyamic acid of precursor, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, polyamide, polyamidoimide, polyamides are sub- At least a kind of resin in the group of amine, polybenzoxazole, polybenzimidazoles and polybenzothiozole composition.
[38] a kind of duplexer, wherein, the resin film layer recorded any one of [35]～[37] is laminated on glass transition temperature Degree is on the resin substrate of less than 200 DEG C.
[39] a kind of duplexer, wherein, the resin film layer recorded any one of [35]～[37] is laminated on glass transition temperature Degree is on the resin substrate of less than 250 DEG C.
The effect of invention
According to the present invention, provide for make excellent adhesion with polybenzoxazole resin, Si substrate and Cu substrate, Resolution ratio and high and then opening portion the side of heat resistance become the photosensitive polymer combination of the cured film of positive taper, use The manufacture method of the cured relief pattern of this photosensitive polymer combination, possesses the semiconductor device of this cured relief pattern, with And the resin film of the excellent adhesion with polybenzoxazole resin, and this resin film layer is laminated on glass transition temperature 250 DEG C The following duplexer on resin substrate.
Brief description
Figure 1A is for representing the schematic diagram of an operation of the evaluation method of cone angle.
Figure 1B is for representing the schematic diagram of an operation of the evaluation method of cone angle.
Fig. 1 C is for representing the schematic diagram of an operation of the evaluation method of cone angle.
Fig. 1 D is for representing the schematic diagram of an operation of the evaluation method of cone angle.
Fig. 1 E is for representing the schematic diagram of an operation of the evaluation method of cone angle.
Detailed description of the invention
For the present invention, illustrating in detail below.It should be noted that pass through this specification, with same symbol in formula Number structure representing when existing multiple in the molecule, is optionally same to each other or different to each other.
<resin combination>
Illustrating for resin combination, it comprises:
(A) selected from by as the polyamic acid of polyimide precursor, poly amic acid ester, polyamic acid salt, polyamic acid acyl Amine, the polyhydroxyamide that polyazole precursor can be become, polyaminoamide, polyamide, polyamidoimide, polyimides, polyphenyl And at least a kind of resin in the group of azoles, polybenzimidazoles, polybenzothiozole and phenolic resin composition；
(B) emulsion；And
(C) selected from the low-molecular-weight imide compound less than 1000 by multifunctional (methyl) acrylate and molecular weight In the group of composition at least a kind.
(A) composition
(A) composition used in this composition is for selected from by as the polyamic acid of polyimide precursor, polyamic acid Ester, polyamic acid salt, polyamic acid acid amides, the polyhydroxyamide that polyazole precursor can be become, polyaminoamide, polyamide, In the group of polyamidoimide, polyimides, polybenzoxazole, polybenzimidazoles, polybenzothiozole and phenolic resin composition At least a kind of resin.Wherein, from the adaptation of polybenzoxazole resin from the viewpoint of, be preferably selected from by polyamic acid, poly- Amic acid esters, polyamic acid salt, polyamic acid acid amides, polyamide, polyamidoimide, polyimides, polybenzoxazole, polyphenyl And at least a kind of resin in the group of imidazoles, polybenzothiozole composition.
From the viewpoint of heat resistance after heat treatment for the weight average molecular weight of these resins and mechanical property, with based on solidifying Glue penetration chromatographic polystyrene conversion meter is preferably more than 1,000, more preferably more than 5,000.The upper limit of weight average molecular weight It is preferably less than 100,000.
For the resin of (A) composition, in order to resin combination is formed embossing pattern, preferably photoresist.Photosensitive Property resin be following resin, when used along with (B) described later emulsion, form photosensitive polymer combination, afterwards In developing procedure, cause based on dissolving or undissolved development.
As photoresist, as the polyamic acid of polyimide precursor, poly amic acid ester, polyamic acid salt, poly- Amic acid acid amides, polyamide, polyamidoimide, polyimides, polybenzoxazole, polybenzimidazoles and polybenzothiozole Among, the heat resistance of resin after heat treatment and mechanical property excellent from the viewpoint of, be preferably used polyimide precursor, Polyamide and/or polyimides.Additionally, prepare minus and eurymeric from these photoresists together with (B) described later emulsion One of the viewpoint etc. of photosensitive polymer combination set out, can select according to desired purposes.
[polyimide precursor]
In the resin combination of the present invention, from the viewpoint of heat resistance and photonasty, for (A) resin, (AX) One of sensitive polyimide precursor and (AY) polyimide precursor, it is however preferred to have the structure being represented by following formula (A1) Polyamide:
In formula (A1), X1It is the organic group of 4 valencys, Y1For the organic group of divalent, l is the integer of 2～150, R1And R2 The separately organic group for hydrogen atom or 1 valency of free redical polymerization.Wherein, R1And R2Both are hydrogen when different Atom.,
More preferably there is the polyamide of the structure being represented by following formula (A2):
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7 The organic group of 1 valency separately for hydrogen atom, being represented by following formula (A3) or the representative examples of saturated aliphatic of carbon number 1～4 Group.Wherein, R6And R7Both are hydrogen atom when different.
(in formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is The integer of 2～10.)}.
(A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor are by heating (such as 180 DEG C Cyclisation above) processes thus is changed into polyimides.
In formula (A2), by X2The organic group of 4 valencys representing is from the viewpoint of heat resistance and photobehavior, preferably For the organic group of carbon number 6～40, more preferably-COOR6Base and-COOR7Base and the fragrance at-CONH-base ortho position each other Race's group or ester ring type aliphatic group.As by X2The organic group of 4 valencys representing, it is further preferred that, Ke Yilie Enumerate the structure being represented by following formula:
It is not limited to them.X2Structure can be a kind or combination of more than two kinds.
In formula (A2), by Y2The organic group of the divalent representing, from the viewpoint of heat resistance and photobehavior, excellent Elect the aromatic group of carbon number 6～40 as, for example, it is possible to list the structure being represented by following formula:
{ in formula, A represents methyl (-CH3), ethyl (-C2H5), propyl group (-C3H7) or butyl (-C4H9)., do not limit In them.Additionally, Y2Structure can be a kind or combination of more than two kinds.
For R6And R7, R in formula (A3)8It is preferably hydrogen atom or methyl, R9And R10From the sight of photobehavior Point sets out, preferably hydrogen atom.Additionally, p is from the viewpoint of photobehavior, the integer of preferably more than 2 and less than 10, more excellent Elect the integer of more than 2 and less than 4 as.
In the case of using polyimide precursor as the resin of (A) composition, and use (AX) photosensitive polyimide In the case of precursor or (AY) polyimide precursor, give photosensitive mode as to photosensitive polymer combination, permissible List ester bond type and ion of bonding.The former is to be introduced by ester bond to have optical polymerism base on the side chain of polyimide precursor The method of the group i.e. compound of olefinic double bond, the latter is to make the carboxyl of polyimide precursor via ionic bond and have amino The amino bonded of (methyl) acrylic compounds thus the method that gives optical polymerism group.
[preparation method of polyimide precursor]
The polyimide precursor of ester bond type can obtain in the following way: first, comprises aforesaid 4 valency organic groups X2Tetracarboxylic dianhydride react with the alcohols of the unsaturated double-bond with optical polymerism and arbitrary representative examples of saturated aliphatic alcohols, system The tetrabasic carboxylic acid (hereinafter also referred to acid/ester body) of standby partial esterification, then so that it is with comprise aforesaid divalent organic group Y2Two Amine carries out amide polycondensation.
(preparation of acid/ester body)
As the organic group X comprising 4 valencys using aptly to prepare the polyimide precursor of ester bond type2Four Carboxylic acid dianhydride, for example, it is possible to list pyromellitic dianhydride, diphenyl ether-3,3 ', 4,4 '-tetracarboxylic dianhydride, BP-3,3 ', 4,4 '-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride, diphenyl sulfone-3,3 ', 4,4 '-tetracarboxylic dianhydride, hexichol Methylmethane-3,3 ', 4,4 '-tetracarboxylic dianhydride, double (3,4-phthalic anhydride) propane of 2,2-, double (the 3,4-O-phthalic of 2,2- Acid anhydrides)-1,1,1,3,3,3-HFC-236fa etc., it is not limited to them.They can be with independent or two or more mixture side Formula uses.
Double as unsaturation that use aptly to prepare the polyimide precursor of ester bond type, that there is optical polymerism The alcohols of key, for example, it is possible to list 2-acryloxy ethanol, 1-acryloxy-3-propyl alcohol, 2-acrylamide ethanol, Methylol vinyl ketone, 2-hydroxyethylvinyl ketone, 2-hydroxy-3-methoxy propyl acrylate, 2-hydroxyl-3-butoxy Propyl acrylate, 2-hydroxyl-3-phenoxypropylacrylate, 2-hydroxyl-3-butoxypropyl acrylate, 2-hydroxyl- 3-tert-butoxy propyl acrylate, 2-hydroxyl-3-cyclohexyloxypropyl acrylate, 2-methacryloxy ethanol, 1- Methacryloxy-3-propyl alcohol, 2-MAAm ethanol, 2-hydroxy-3-methoxy propyl methacrylate, 2-hydroxyl Base-3-butoxypropyl methacrylate, 2-hydroxyl-3-phenoxy propyl methacrylate, 2-hydroxyl-3-butoxy third Methyl acrylate, 2-hydroxyl-3-tert-butoxy propyl methacrylate, 2-hydroxyl-3-cyclohexyloxypropyl methyl-prop Olefin(e) acid ester etc..
Can also come the representative examples of saturated aliphatic alcohol of mixed carbon number 1～4 in there is the alcohols of unsaturated double-bond of optical polymerism Use, as the representative examples of saturated aliphatic alcohol of described carbon number 1～4, such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol Deng.
Can be by the preferred alcohols of the preferred tetracarboxylic dianhydride of described above and described above at base catalysts such as pyridines In the presence of, through stirring in 4～10 hours, dissolving, mixing in suitable reaction dissolvent, at temperature 20～50 DEG C, thus enter The esterification of row acid anhydrides, obtains desired acid/ester body.
As reaction dissolvent, preferably completely dissolving acid/ester body and as its amide polycondensation product with diamine component The solvent of polyimide precursor, for example, it is possible to list METHYLPYRROLIDONE, DMA, N, N-diformazan Base formamide, dimethyl sulfoxide (DMSO), tetramethylurea, gamma-butyrolacton etc..
As other reaction dissolvent, ketone, esters, lactone, ethers, halogenated hydrocarbons, hydro carbons etc., example can be listed As, can list acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, Diethy-aceto oxalate, glycol dimethyl ether, diethylene glycol dimethyl ether, oxolane, dichloromethane, 1,2-dichloroethanes, 1,4-bis- Chlorobutane, chlorobenzene, o-dichlorohenzene, hexane, heptane, benzene,toluene,xylene etc..They can be used alone as required also may be used To be mixed with two or more.
(preparation of polyimide precursor)
In acid/ester body (for Dian Xing, solution) in reaction dissolvent, lower put into suitable dehydrating condensation agent ice-cold, For example, dicyclohexyl carbodiimide, 1-ethoxy carbonyl-2-ethyoxyl-1,2-EEDQ, 1,1-carbonylic dioxo base-two- 1,2,3-BTA, N, N '-two succinimdyl carbonate etc. simultaneously mixes, acid/ester body is changed into condensing model.Then, make Preferably comprise the organic group Y of divalent1Diamines dissolve or be distributed to solution or the dispersion of other solvent Body, is added drop-wise to this solution or dispersion in condensing model so that it is amide polycondensation, such that it is able to obtain target photoresist.
As the organic group Y comprising divalent1Preferred Diamines, for example, it is possible to list p-phenylenediamine, m-phenylene diamine (MPD), 4,4-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 4,4 '-diamino diphenyl sulfide, 3, 4 '-diamino diphenyl sulfide, 3,3 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,4 '-diaminourea hexichol Base sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 4, 4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 4,4 '-diamino-diphenyl first Double (4-amino-benzene oxygen) benzene of alkane, 3,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 1,4-, 1,3-are double (4-amino-benzene oxygen) benzene, 1,3-double (3-amino-benzene oxygen) benzene, double (4-(4-amino-benzene oxygen) phenyl) sulfone, double (4-(3-ammonia Phenoxyl) phenyl) sulfone, double (4-amino-benzene oxygen) biphenyl of 4,4-, 4,4-double (3-amino-benzene oxygen) biphenyl, double (4-(4-ammonia Phenoxyl) phenyl) ether, double (4-(3-amino-benzene oxygen) phenyl) ether, double (4-aminophenyl) benzene of 1,4-, double (the 4-ammonia of 1,3- Base phenyl) benzene, double (4-aminophenyl) anthracene of 9,10-, double (4-aminophenyl) propane of 2,2-, double (4-aminophenyl) hexafluoro of 2,2- Double (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of double (4-(4-amino-benzene oxygen) phenyl) propane of propane, 2,2-, 2,2-, 1, Double (the 3-dimethyl silicyl) benzene of 4-, o-tolidine sulfone, double (4-aminophenyl) fluorenes of 9,9-；These Diamines Phenyl ring on the compound that replaced by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen etc. of the part of hydrogen atom, example As, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '- Diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-diaminodiphenyl-methane, 3,3 '-dimethoxy-4 ', 4 '-diaminourea Biphenyl, 3,3 '-two chloro-4,4 '-benzidines；And their mixture etc., it is not limited to them.
And then, in order to improve by be applied to the photosensitive polymer combination of the present invention on substrate thus on substrate shape The adaptation of the photo-sensitive resin and the various substrates that become, when using polyimide precursor as the resin of (A) composition and make When standby (AX) sensitive polyimide precursor or (AY) polyimide precursor, it is also possible to by 1, double (3-aminopropyl) tetramethyl of 3- The diaminourea type siloxane copolymerization such as double (3-aminopropyl) the tetraphenyl disiloxane of base disiloxane, 1,3-.
The water suction accessory substance of the dehydrating condensation agent coexisting in reactant liquor after filtering amide polycondensation reaction terminating as required, Then, the component of polymer obtained by putting into the poor solvents such as water, aliphatic lower alcohol or their mixed liquor, makes Component of polymer separates out, and then, repeat re-dissolved, reprecipitation precipitation operation etc., so that polymer purification, carry out vacuum and do Dry, separate target polyimide precursor.In order to improve purification degrees, anion and/or sun can be made with suitable organic solvent Ion exchange resin is swelling and the solution of this polymer that circulates in the post filled, removes ionic impurity.
The weight average molecular weight of the polyimide precursor of ester bond type is in terms of the polystyrene conversion based on gel permeation chromatography It is preferably 8,000～150,000, more preferably 9,000～50,000.Weight average molecular weight is 8, and when more than 000, mechanical properties is good Good, it is 150, when less than 000, to the favorable dispersibility of developer solution, and the resolution performance of embossing pattern is good.Ooze as gel Saturating chromatographic developing solvent, it is recommended that oxolane and/or METHYLPYRROLIDONE.Additionally, molecular weight is by using standard Monodisperse polystyrene and the calibration curve that is made and obtain.As standard monodisperse polystyrene, preferably select Showa electrician The organic solvent system standard specimen STANDARD SM-105 of company.
(B) emulsion
As (B) emulsion, can at random select to be used as the compound of the Photoepolymerizationinitiater initiater of UV solidification in the past.Make For the compound of (B) emulsion can be used as aptly, for example, it is possible to list benzophenone, o-benzoyl yl benzoic acid first The benzophenone derivates such as ester, 4-benzoyl-4 '-methyldiphenyl base ketone, dibenzyl ketone, Fluorenone；2,2 '-diethoxybenzene second The acetophenone derivs such as ketone, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexylphenylketone；Thioxanthones, 2-methyl thioxanthones, The thioxanthone derivates such as ITX, diethyl thioxanthone；Benzil (benzil), benzil dimethyl ketal, benzene The benzil derivatives such as even acyl-'beta '-methoxy ethyl acetal；The benzoin derivatives such as benzoin, benzoin methylether；1-phenyl- 1,2-diacetyl-2-(O-methoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-methoxy carbonyl) oxime, 1-phenyl-1, 2-propanedione-2-(adjacent ethoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl base) oxime, 1,3-diphenylprop three Ketone-2-(adjacent ethoxy carbonyl) oximes such as oxime, 1-phenyl-3-ethoxy-c triketone-2-(o-benzoyl base) oxime；The sweet ammonia of N-phenyl The N-aryl glycine classes such as acid；The peroxides such as peroxidating chlorobenzoyl；Aromatic series bisglyoxaline classes etc., are not limited to it ?.Additionally, they can use a kind also can use mixture of more than two kinds.Among them, particularly from the sight of speed Point sets out, more preferably oximes.
The oximes using as (B) emulsion is preferably selected from being become in the group being grouped into extremely by following (B1) and (B2) Few a kind:
(B1) for 0.001wt% solution, g ray absorbance and h ray absorbance are less than 0.2, and i ray is inhaled Luminosity is the oxime ester compound of 0.15～0.5；And
(B2) for 0.001wt% solution, g ray absorbance or h ray absorbance are more than 0.05, and i ray Absorbance is the oxime ester compound of less than 0.1.
The absorbance of oxime ester compound can make this compound be dissolved in 1-METHYLPYRROLIDONE with the concentration of 0.001wt% In, use the quartz colorimetric utensil of 1cm and common spectrophotometer to be measured.
As the preferred compound of (B1) composition, for example, it is possible to list Irgacure OXE03 (BASF AG's system, Trade name), Adekaoptomer NCI831 (ADEKA society system, trade name), (Changzhou electronic strong new material has TR-PBG326 Limit company system, trade name), HTPI426 (Heraeus Company system, trade name), HTPI428 (Heraeus Company system, Trade name) etc. or their mixture etc..
As (B1) composition, when using the compound that the i ray absorbance of 0.001wt% solution is less than 0.15, absorbance Insufficient, therefore to solidification needs to add substantial amounts of initiator.Now, film coated surface is not easily susceptible to the impact that oxygen hinders, because of This surface cure degree improves, and the opening portion after exposure and development does not becomes positive cone-shaped.For i ray absorbance more than 0.5 When or at least one of g ray absorbance and h ray absorbance more than 0.2 when, absorbance is too high, and surface cure easily enters OK, expose and the opening portion after development does not becomes positive cone-shaped.
More preferably (B1) composition is the oxime ester compound that the i ray absorbance of 0.001wt% solution is 0.15～0.35, enters Preferred (B1) composition of one step in the group that the oxime ester compound being represented by following formula (B11) and (B12) forms extremely Few a kind:
In formula (B11), R14For C1～C10Fluorine-containing alkyl, R15、R16, and R17It is separately C1～C20Alkane Base, C3～C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that r is 0～5.}
In formula (B12), R18For C1～C30The organic group of divalent, R19～R26It is separately C1～C20Alkyl, C3～C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that s is 0～3.}.
In the photosensitive polymer combination of the present invention, the oxime ester compound of (B2) composition is also as Photoepolymerizationinitiater initiater Function.
(B2) absorbance of the oxime ester compound of composition can the situation of oxime ester compound with (B1) composition be entered in the same manner Row measures.
As the preferred compound of (B2) composition, for example, it is possible to list TR-PBG340 (Changzhou electronic strong new material Co., Ltd's system, trade name).
As (B2) composition, the g ray absorbance of 0.001wt% solution and h ray absorbance is used to be less than 0.05 During compound, absorbance is insufficient, therefore to solidification needs to add substantial amounts of initiator.Now, film coated surface is not easily susceptible to The impact that oxygen hinders, therefore surface cure degree improves, and the opening portion after exposure and development does not becomes positive cone-shaped.I is penetrated The situation more than 0.1 for the line absorbance, absorbance is too high, and surface cure is easily carried out, and the opening portion after exposing and developing is not yet Become positive cone-shaped.
Relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor (B1) total usage amount of composition and (B2) composition is preferably in the scope of 0.1～20 mass parts, more preferably 0.5～5 mass The scope of part.(B1) total usage amount of composition and (B2) composition is relative to 100 mass parts (A) resin, (AX) photonasty polyamides When imines precursor or (AY) polyimide precursor are more than 0.1 mass parts, speed is excellent, and is below 20 mass parts When, positive cone is excellent.
(C) selected from the low-molecular-weight imide compound less than 1000 by multifunctional (methyl) acrylate and molecular weight In the group of composition at least a kind
(C) composition is for selected from the low-molecular-weight acid imide less than 1000 by multifunctional (methyl) acrylate and molecular weight In the group of compound composition at least a kind." (methyl) acrylate " means acrylate or methacrylate.(C) Composition can be polymerisable monomer.It is preferably by the glass transition temperature of homopolymers obtained from only polymerization (C) composition More than 200 DEG C.
As multifunctional (methyl) acrylate, three (methyl) acrylic acid isocyanuric acid ester, three (methyl) can be listed Acrylate, pentaerythritol, four (methyl) acrylate, pentaerythritol, two trimethylolpropane four (methyl) acrylate, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester etc..
The maleimide that the low-molecular-weight imide compound less than 1000 for the molecular weight is preferably represented by following formula (C1) Amine:
In formula (C1), R3For the organic group of singly-bound, hydrogen atom or 1～trivalent, R4And R5Separately former for hydrogen Son, the alkyl of carbon number 1～10, the cycloalkyl of carbon number 3～10, aryl, alkoxyl or halogen atom, and m be more than 1 whole Number }.
In formula (C1), m can be more than 2 integer or more than 3 integer.
The Malaysia that the low-molecular-weight imide compound less than 1000 for the molecular weight is more preferably represented by following formula (C2) Acid imide:
In formula (C2), R11For the organic group of singly-bound, hydrogen atom or 1～trivalent, R12And R13It is separately hydrogen Atom, the alkyl of carbon number 1～10, the cycloalkyl of carbon number 3～10, aryl, alkoxyl or halogen atom, and q be 2～4 whole Number.}.
By using low-molecular-weight imide compound as (C) composition, can obtain on polybenzoxazole resin The cured film of excellent adhesion after development.The mechanism of excellent adhesion after the development of the embossing pattern on polybenzoxazole resin It is still not clear, thus it is speculated that in the heating process (about 100 DEG C) of the solvent seasoning when the film for embossing pattern is formed, as (C) the low-molecular-weight imide compound of composition and polybenzoxazole buildup of resin, interact at resin boundary surface, thus suppress The dissolving that the infiltration to the interface between film and polybenzoxazole resin for developer solution during development or solvation cause, result The stripping of embossing pattern can be suppressed.
As the specific example of (C) low-molecular-weight imide compound, 1-Phenylpyrrolidine-2,5-bis-can be listed Ketone, succinimide, N-amyl group succinimide, 4-amino-2,6-pyridinedione, 2,6 (1H, 3H)-pyridinediones, N-ethyl Maleimide, fluorine acid imide, N-phenylmaleimide, N-(4-chlorphenyl) maleimide, N-(2-chlorphenyl) Malaysia Acid imide, N-(4-aminomethyl phenyl) maleimide, N-(4-ethoxyl phenenyl) maleimide, N-isopropyl maleimide Amine, N-methylmaleimido, N-(2-nitrobenzophenone) maleimide, N-(2-aminomethyl phenyl) maleimide, 1-(2,4- 3,5-dimethylphenyl)-3-pyrrolin-2,5-diketone, 1-(1,1 '-biphenyl-4-base)-1H-pyrrole-2,5-diones, N-cyclohexyl horse Come acid imide, N-butyl maleimide, 1-(hydroxymethyl)-1H-pyrrole-2,5-diones, 3-methyl-4-vinyl-1H-pyrrole Cough up-2,5-diketone, N-(4-aminophenyl) maleimide, 3,4-bis-bromo-3-pyrrolin-2,5-diketone, N-benzyl Malaysia acyl Imines, 6,7-methene base dioxy-4-methyl-3-maleimide cumarin, maleimide, 2,3-dichloro maleimide, N-(4-hydroxy phenyl) maleimide, N-(4-acetylphenyl) maleimide, N-propylmaleimide, N-(1-pyrene Base) maleimide, N-(4-methoxyphenyl) maleimide, N-(firefly anthracene-3-base) maleimide, N-(4-vinyl Phenyl) maleimide, N-(ethenylphenyl) maleimide, 4-[(2,5-dioxo-1-pyrrole radicals) methyl] hexamethylene Alkane carboxylic acid succinimide, eosin-5-maleimide (Eosin-5-maleimide), MF59 maleimide, N-(2,4, 6-tribromo phenyl) maleimide, UVINUL MS 40-maleimide, maleimide NO free radical (マ レ イ ミ De ニ ト ロ キ シ De maleimide nitroxide), N-(3-nitrobenzophenone) maleimide, N-(4-nitrobenzophenone) maleimide Amine, the acid of 2,5-dioxo-3-pyrrolin-1-hexane, 3-(N-dimaleoyl imino propiono) biocytin, N-(2,4-dinitro Base aniline) maleimide, cumarin maleimide (Coumarin maleimide), N-(4-bromophenyl) maleimide Amine, N-isobutyl group maleimide, N-tert-butylmaleimide, N-octyl group maleimide, N-decyl maleimide, N- Bromomethyl maleimide, N-cyano methyl maleimide, N-ethoxyl methyl maleimide, N-3-nitro-4-methyl Benzyl maleimide, N-aryloxy group methylmaleimido (N-(Allyloxymethyl) maleimide), N-amino methyl Maleimide, N-diethylamino methyl maleimide, N-dibutylaminomethyl maleimide, N-(1-piperidyl Methyl) maleimide, N-(1-morpholinyl methyl) maleimide, N-anilinomethyl maleimide, N-(2-ethyoxyl second Base) maleimide, propionic acid-2-(2,5-dioxo-3-pyrrolin-1-base) ethyl ester, N-(2,2,2-trifluoroethyl) Malaysia acyl Imines, N-(methyl Malaysia acyl ethyl) maleimide, N-(3-acetyloxypropyl) maleimide, 1-(2-hydroxyl third Base)-1H-pyrrole-2,5-diones, N-methoxyl group maleimide, N-acetoxyl group maleimide, N-benzyloxy maleimide Amine, N-phenylsulfonyloxy maleimide, N-(dimethylamino) maleimide, N-acetyl-amino maleimide, N- (1-morpholinyl) maleimide, N-(phenyl sulfonyl) maleimide, N-aniline maleimide, N, N '-(sub-benzene of 1,2- Base) double (maleimides), N, N '-(1,3-phenylene) double (maleimide), N, N '-ethylenebis (maleimide), 1,6-bisinaleimidohexane, N-dodecyl maleimide, N-(2-methoxyphenyl) maleimide, N-(chloromethane Base) maleimide, N, N '-(4-methyl isophthalic acid, 3-phenylene) double (maleimides), 4,4 '-BMI diphenyl Methane, N, N '-(1,4-phenylene) double (maleimide), polyphenylene methane maleimide, N, N '-[sulfonyl pair (4, 1-phenylene)] double (maleimides), N-[4-(phenylazo) phenyl] maleimide, 1,1 '-(2,2,4-trimethyl oneself Alkane-1,6-diyl) double (1H-pyrrole-2,5-diones), 1,1 '-[di-2-ethylhexylphosphine oxide (2-ethyl-6-methyl-4,1-phenylene)] be double (1H-pyrrole-2,5-diones), N, N '-[(1,3-phenylene) dioxygen base is double (3,1-phenylene)] double (maleimides), N- (4-maleimidobutyryloxy) succinimide, N-(8-maleimide octanoyloxy) succinimide, 4-[(2,5- Dioxo-1-pyrrole radicals) methyl] hexamethylene-1-carboxylic acid 3-thiosuccimide, 2,2 ', 3,3 '-tetraphenyl-N, N '-Asia second Base dimaleimide, fluorescein maleimide, N, N ', N "-[nitrilo-three (ethylidene)] three (maleimides) etc..
From with the intermolecular interaction of polybenzoxazole resin from the viewpoint of, low-molecular-weight imide compound is preferred There is circulus, more preferably there is in circulus unsaturated bond.Even if having the low of unsaturated bond in circulus Among molecular weight imide compound, as represented by formula (C1) or (C2), there is flatness and easily With the compound of the maleimide structure of benzothiazole stereo stocking after the development on polybenzoxazole resin adaptation From the viewpoint of more preferably.
And then, have among the compound of maleimide structure, from being difficult to by cross-linking reaction be dissolved in development From the viewpoint of in liquid, the maleimide of preferred divalent compared with the maleimide of 1 valency.Additionally, the maleimide of divalent Compared with the maleimide of trivalent sterically hindered little and easily with polybenzoxazole accumulation.Therefore, from polybenzoxazole From the viewpoint of the adaptation of resin, further preferred BMI.Wherein, double (3-ethyl-5-methyl-4-Malaysia acyls Imines phenyl) methane, 4,4 '-BMI diphenyl methane or polyphenylene methane maleimide be from suppression sense The contraction during solidification of photosensitive resin composition, and improve the sight with polyimides or the adaptation of polybenzoxazole resin Point sets out further preferably.
Comprise resin and 0.1～20 mass parts (B) composition of 100 mass parts (A) composition at photosensitive polymer combination When, the use level of (C) composition is 1～40 mass parts, preferably 10～35 mass parts.(C) use level of composition is less than 1 mass parts When, adaptation is insufficient, and during more than 40 mass parts, the cured relief pattern being obtained by said composition becomes fragile, be unsuitable for passivating film, The buffering purposes such as film, interlayer dielectric.
(D) silicon-containing compound
(D) composition is the silicon-containing compound being represented by following formula (D1):
In formula (D1), R27And R28For C1～C4Alkyl, R29For C1～C6The organic group of divalent, R30For via choosing C from the atom of nitrogen, oxygen and sulphur and carbonyl linkage1～C20Organic group, t for selected from the 1st, 2 and 3 integer, u for choosing From the integer of the 0th, 1 and 2, and t and u meets the relation of t+u=3.}.
As R30, specifically, can list:
Methylamino, ethylamino, n-propyl amino, n-butylamino, n-hexyl amino, n-octyl amino, isopropyl Amino, isobutylamino, tert-butylamino, c, cyclopenta, Cyclohexylamino, dimethylamino, diethyl amino Alkyl monosubstituted amino and the dialkyl amidos such as base, dibutylamino, dicyclohexyl amino；
The amino containing aromatic rings such as phenyl amino, benzylamino, diphenyl amino；
The amino containing heterocycle such as picolyl, amino three acyl group, Furfurylamino, morpholinyl；
The alkoxyls such as methoxyl group, ethyoxyl, n-butoxy, tert-butoxy, hexyloxy, cyclohexyloxy；
Alkyl-aryloxy or the aryl alkyl epoxides such as phenoxy group, benzyloxy, tolyl epoxide；
The alkoxyl containing heterocycle such as furfuryl group alkoxyl, 2-pyridine radicals ethyoxyl；
Alkylthio group or the thiophenyls such as methyl mercapto, ethylmercapto group, positive butylthio, tertiary butylthio, own sulfenyl, cyclohexylthio；
Their mixture etc..
The silicon-containing compound being represented by formula (D1) obtains by the following method: makes isocyanate compound and has amino The method of silicon compound reaction, the method etc. making amine, alcohol or mercaptan and reacting with the silicon compound with NCO.
Relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, by The use level of the silicon-containing compound that formula (D1) represents is preferably 0.1～20 mass parts, from the sight improving heat resistance and adaptation Point sets out, more preferably 0.5～10 mass parts.Relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or Person (AY) polyimide precursor coordinates the silicon-containing compound being represented by formula (D1) of more than 0.1 mass parts, so that it is guaranteed that excellent Adaptation, by coordinate below 20 mass parts, thus keeping excellent heat resistance.
As (D) composition, on the basis of the silicon-containing compound being represented by formula (D1), preferably at photosensitive polymer combination In add the silicon-containing compound being represented by following formula (D2) further:
In formula (D2), R31And R32For C1～C4Alkyl, R33For C1～C6The organic group of divalent, v is for selected from the 1st, 2 And 3 integer, w for selected from the 0th, 1 and 2 integer, and v and w meet the relation of v+w=3.}.
As the silicon-containing compound being represented by formula (D2), for example, it is possible to list 3-ureidopropyltriethoxysilane, 3- Ureido-propyl trimethoxy silane, 3-ureido-propyl ethyoxyl dimethoxysilane, 3-ureido-propyl diethoxy methoxyl group silicon Alkane, 3-ureido-propyl methyldiethoxysilane, 3-ureido-propyl methyl dimethoxysilane, 3-ureido-propyl ethyl diethoxy Base silane, 3-ureido-propyl ethyldimethoxysilane, 3-ureido-propyl dimethylethoxysilane, 3-ureido-propyl dimethyl Methoxy silane etc., and their mixture.
Relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, by The use level of the silicon-containing compound that formula (D2) represents is preferably 0.1～20 mass parts, from the sight improving heat resistance and adaptation Put more preferably 0.5～10 mass parts of setting out.Prepare the situation of the resin combination of the present invention as photosensitive polymer combination Under, on the basis of the silicon-containing compound being represented by formula (D1), and then add the silicon-containing compound being represented by formula (D2) to tree In oil/fat composition, such that it is able to the adaptation of embossing pattern obtained by improving and heat resistance and improve resolution ratio.
(E) sulfur-containing compound
(E) composition is the sulfur-containing compound being represented by following formula (E1):
In formula (E1), R34For C1～C20Organic group or siliceous organic group, R35For via selected from nitrogen, oxygen, with And the C that the atom of sulphur is bonded with thiocarbonyl1～C20Organic group.}.
For R34, as C1～C20Organic group, methyl, ethyl, propyl group, butyl, phenyl, toluene can be listed Base, benzyl etc., and as siliceous organic group, trimethoxy-silylpropyl, triethoxy-silicane can be listed Base propyl group, methyl dimethoxy epoxide silylpropyl, methyl diethoxy silylpropyl, triethoxysilylethyl Deng.
As R35, for example, it is possible to list:
Methylamino, ethylamino, n-propyl amino, n-butylamino, n-hexyl amino, n-octyl amino, isopropyl Amino, isobutylamino, tert-butylamino, c, cyclopenta, Cyclohexylamino, dimethylamino, diethyl amino Alkyl monosubstituted amino and the dialkyl amidos such as base, dibutylamino, dicyclohexyl amino；
The amino containing aromatic rings such as phenyl amino, benzylamino, diphenyl amino；
The amino containing heterocycle such as picolyl, amino three acyl group, Furfurylamino, morpholinyl；
The alkoxyls such as methoxyl group, ethyoxyl, n-butoxy, tert-butoxy, hexyloxy, cyclohexyloxy；
Alkyl-aryloxy or the aryl alkyl epoxides such as phenoxy group, benzyloxy, tolyl epoxide；
The alkoxyl containing heterocycle such as furfuryl group alkoxyl, 2-pyridine radicals ethyoxyl；
Alkylthio group or the thiophenyls etc. such as methyl mercapto, ethylmercapto group, positive butylthio, tertiary butylthio, own sulfenyl, cyclohexylthio.
(E) use level of sulfur-containing compound relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or Person (AY) polyimide precursor is preferably 0.1～20 mass parts, from the viewpoint of improving heat resistance and adaptation more preferably It is 0.5～10 mass parts.Relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimides Precursor coordinates (E) sulfur-containing compound in the way of more than 0.1 mass parts, so that it is guaranteed that excellent adaptation, by with 20 mass Coordinate below part, thus keep excellent heat resistance.
Other compositions
The oil/fat composition of the present invention can contain the composition in addition to (A)～(E) composition further.
As other compositions, it is possible to use solvent.At this point it is possible to dissolve (A)～(E) composition in a solvent, obtain varnish The negative light-sensitive resin combination of shape.
As solvent, molten from for (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor From the viewpoint of solution property, polar organic solvent is preferably used.Specifically, it is possible to use DMF, N-methyl- 2-Pyrrolidone, N-ethyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, ring penta Ketone, gamma-butyrolacton, α-acetyl group-gamma-butyrolacton, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrole Pyrrolidone etc..They can be used alone or be applied in combination two or more.
Solvent according to the desired coating film thickness of resin combination and viscosity, relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, for example, it is possible in the scope, excellent of 30～1500 mass parts The scope being selected in 100～1000 mass parts uses.
And then, from the viewpoint of the storage stability improving resin combination, preferably comprise the solvent of alcohols.As alcohol Class, the alcohol that for example, there is alcohol hydroxyl group in intramolecular and not there is olefinic double bond, as its specific example, can enumerate Go out the alkanols such as methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol；The lactic acid esters such as ethyl lactate；Third Glycol-1-methyl ether, propane diols-2-methyl ether, propane diols-1-ether, propane diols-2-ether, propane diols-1-(n-propyl) ether, third The propylene-glycol monoalky lether classes such as glycol-2-(n-propyl) ether；The unitary such as EGME, ethylene glycol ethyl ether, ethylene glycol positive propyl ether Alcohols；2-hydroxy-isobutyric esters of gallic acid；The glycols such as ethylene glycol and propane diols.Among them, preferably alkanols, lactic acid ester, Propylene-glycol monoalky lether class and 2-hydroxy-isobutyric esters of gallic acid.As alkanols, preferred alcohol.More preferably ethyl lactate, the third two Alcohol-1-methyl ether, propane diols-1-ether and propane diols-1-(n-propyl) ether.
In the case that solvent contains the alcohol without olefinic double bond, the alcohol without olefinic double bond occupies in whole solvents Content be preferably 5～50 mass %, more preferably 10～30 mass %.The content of the alcohol without olefinic double bond is 5 matter During amount more than %, the storage stability of resin combination is good, when being below 50 mass %, and (A) resin, (AX) photonasty polyamides Imines precursor or the favorable solubility of (AY) polyimide precursor.
The resin combination of the present invention can also containing except above-mentioned (A) resin, (AX) sensitive polyimide precursor with And the resinous principle beyond (AY) polyimide precursor.As the resinous principle that can contain, epoxy resin, silicon can be listed Oxygen alkane resin, acrylic resin etc..The use level of these resinous principles is gathered relative to 100 mass parts (A) resin, (AX) photonasty Imide precursor or (AY) polyimide precursor are preferably in the scope of 0.01～20 mass parts.
When the resin combination of the present invention is photonasty, resin combination can become containing except above-mentioned (B1) and (B2) Emulsion beyond Fen, and, as the emulsion in addition to (B1) and (B2) composition, UV can be arbitrarily chosen as solid Change and commonly used Photoepolymerizationinitiater initiater.
Do not limit as commonly used Photoepolymerizationinitiater initiater, for example, it is preferable to:
Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-benzoyl-4 '-methyldiphenyl base ketone, dibenzyl ketone, fluorenes The benzophenone derivates such as ketone；
The acetophenones such as 2,2 '-diethoxy acetophenone, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexylphenylketone spread out Biological；
The thioxanthone derivates such as thioxanthones, 2-methyl thioxanthones, ITX, diethyl thioxanthone；
The benzil derivatives such as benzil, benzil dimethyl ketal, benzil-'beta '-methoxy ethyl acetal；
The benzoin derivatives such as benzoin, benzoin methylether；
1-phenyl-1,2-diacetyl-2-(O-methoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(O-methoxy carbonyl Base) oxime, 1-phenyl-1,2-propanedione-2-(adjacent ethoxy carbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl base) Oxime, 1,3-diphenylprop triketone-2-(adjacent ethoxy carbonyl) oxime, 1-phenyl-3-ethoxy-c triketone-2-(o-benzoyl base) Oxime, Irgacure OXE01 (BASF AG's system, trade name), Irgacure OXE02 (BASF AG's system, trade name), Adekaoptomer N-1919 (ADEKA society system, trade name), TR-PBG304 (Changzhou Tronly New Electronic Materials Co., Ltd.'s system, Trade name), the oximes such as TR-PBG305 (Changzhou Tronly New Electronic Materials Co., Ltd.'s system, trade name)；
The N-aryl glycine classes such as N-phenylglycine；
The peroxides such as peroxidating chlorobenzoyl；
Aromatic series bisglyoxaline class etc..
They can use one kind or two or more mixture.Among above-mentioned emulsion, go out from the viewpoint of speed Send out, more preferably oximes.
The use level of above-mentioned emulsion relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor is preferably 0.1～20 mass parts, from the viewpoint of speed, and preferably 2～15 mass parts.Relatively In 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor with 0.1 mass parts more than Coordinate above-mentioned emulsion, such that it is able to obtain the excellent photosensitive polymer combination of speed, by joining below 20 mass parts Close, such that it is able to obtain the excellent photosensitive polymer combination of thick film curability.
During additionally, the resin combination of the present invention is photonasty, in order to improve speed, can appoint in resin combination Meaning ground coordinates sensitizer.
As sensitizer, for example, it is possible to list Michler's keton, 4,4 '-bis-(diethylamino) benzophenone, 2,5-is double Double (the 4 '-diethylamino benzal) cyclohexanone of (4 '-diethylamino benzal) pentamethylene, 2,6-, double (the 4 '-diethyl of 2,6- Base amino benzal)-4-methyl cyclohexanone, 4,4 '-bis-(dimethylamino) chalcone, 4,4 '-bis-(diethylaminos) look into ear Ketone, to dimethylamino cinnamylidene indone, (sub-to dimethylaminophenyl to dimethylamino benzal indone, 2- Xenyl)-benzothiazole, 2-(to dimethylaminophenyl ethenylidene) benzothiazole, 2-(to dimethylaminophenyl sub-second Thiazolinyl) different aphthothiazoles, double (the 4 '-dimethylamino benzal) acetone of 1,3-, double (the 4 '-diethylamino benzal) third of 1,3- Ketone, 3,3 '-carbonyl-bis-(7-diethyl amino coumarins), 3-acetyl group-7-dimethylamino butylcoumariii, 3-ethoxy carbonyl- 7-dimethylamino butylcoumariii, 3-benzyloxycarbonyl-7-dimethylamino butylcoumariii, 3-methoxycarbonyl-7-diethylamino Cumarin, 3-ethoxy carbonyl-7-diethyl amino coumarin, N-phenyl-N '-ehtylethanolamine, N-phenyldiethanol-amine, N- P-methylphenyl diethanol amine, N-phenylethanol amine, 4-morpholino benzophenone, dimethylaminobenzoic acid isopentyl ester, diethyl Aminobenzoic isoamyl valerate, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-tetrazole, 2-mercaptobenzothiazole, 2-are (to dimethyl Aminostyryl) benzothiazole, 2-(to dimethylaminostyryl) benzothiazole, 2-is (to dimethylaminostyrene Base) naphtho-(1,2-d) thiazole, 2-(to dimethvlaminobenzovl) styrene etc..They can be used alone or for example with 2 ～5 kinds be applied in combination.
In the case that negative light-sensitive resin combination contains the sensitizer in order to improve speed, relative to 100 matter Amount part (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, the use level of sensitizer is preferably 0.1～25 mass parts.
In order to improve the resolution ratio of embossing pattern, can be by the unsaturated bond with optical polymerism different from (C) composition Monomer be coupled in resin combination.As such monomer, carry out radical polymerization preferably by Photoepolymerizationinitiater initiater anti- (methyl) acrylic compounds answered, but it is not limited to this, can list with dimethacrylate, tetrem Mono acrylic ester that diol dimethacrylate etc. are the ethylene glycol of representative or polyethylene glycol or diacrylate and Methacrylate；The mono acrylic ester of propane diols or polypropylene glycol or diacrylate and methacrylate；Sweet The mono-, di-of oil or triacrylate and methacrylate；Cyclohexane diacrylate and dimethylacrylate；1, The diacrylate of 4-butanediol and dimethylacrylate；The diacrylate of 1,6-HD and dimethacrylate Ester；The diacrylate of neopentyl glycol and dimethylacrylate；The mono acrylic ester of bisphenol-A or diacrylate and Methacrylate；Benzene trimethyl acrylic ester；Isobornyl acrylate and methacrylate；Acrylamide and derivative Thing；MAAm and its derivative etc..
In order to improve the resolution ratio of embossing pattern, in negative light-sensitive resin combination, containing above-mentioned, there is photopolymerization In the case of the monomer of the unsaturated bond of property, relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, the use level of monomer is preferably 1～50 mass parts.
The film being formed to improve the resin combination using the present invention and the cohesive of base material, can be in resin combination Thing coordinates bonding agent.As bonding agent, gamma-amino propyldimethoxy-silane, N-(beta-amino second can be listed Base)-gamma-amino hydroxypropyl methyl dimethoxysilane, γ-glycidoxypropyl dimethoxysilane, γ-mercaptopropyi Methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyl three Methoxy silane, dimethoxy-methyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropyl silane, N- (3-diethoxymethyl silylpropyl) succinimide, N-(3-(triethoxysilyl) propyl group) phthalamide Acid, BP-3, the double (N-of 3 '-bis-(N-(3-triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids, benzene-1,4- (3-triethoxysilyl) propyl amides)-2,5-dicarboxylic acids, 3-(triethoxysilyl) propylsuccinic anhydride, N- The silane couplers such as phenyl amino propyl trimethoxy silane；And three (ethyl acetoacetate) aluminium, aluminium tris(acetylacetonate), second The aluminium system bonding agents such as ethyl acetoacetic acid ethyl ester diisopropyl aluminum oxide.
Among these bonding agents, from the viewpoint of bonding force, preferably silane coupler.Negative light-sensitive resin combination In the case of containing bonding agent, the use level of bonding agent is sub-relative to 100 mass parts (A) resin, (AX) photonasty polyamides Amine precursor or (AY) polyimide precursor are preferably in the scope of 0.5～25 mass parts.
When the state with the solvent-laden solution of bag preserves, in order to improve the viscosity of photosensitive polymer combination and photosensitive The stability of degree, can coordinate thermal polymerization inhibitor in photosensitive polymer combination.As thermal polymerization inhibitor, it is possible to use Quinhydrones, N-nitrosodiphenylamine int he, p-tert-butyl catechol, phenthazine, N-phenyl naphthyl amines, ethylene diamine four acetic acid, 1, 2-cyclohexane diamine four acetic acid, GEDTA, 2,6-di-tert-butyl methyl phenol, 5-nitroso-8-hydroxyl Quinoline, 1-Nitroso-2-naphthol, 2-nitroso-1-naphthols, 2-nitroso-5-(N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt etc..
Relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, sense The use level of the thermal polymerization inhibitor in photosensitive resin composition is preferably the scope of 0.005～12 mass parts.
According to expectation, crosslinking agent can be coordinated in resin combination.In the shape to the resin combination using the present invention The embossing pattern becoming is when being heating and curing, and crosslinking agent can be by (A) resin, (AX) sensitive polyimide precursor or (AY) Polyimide precursor is crosslinked or can be formed cross-linked network by crosslinking agent self.Crosslinking agent can be strengthened by minus further The heat resistance of the cured film that photosensitive polymer combination is formed and chemical reagent resistance.As crosslinking agent, use ammonia aptly Base resin and its derivative, wherein, more appropriately use urea resin, glycoluril resin, hydroxyl ethylene urea resin, melamine Resin, benzoguanamine resin and their derivative.Particularly preferred crosslinking agent be aikoxymethytated urea compounds with And alkoxymethylated melamine compound, as their example, MX-290 (Nippon Carbide can be listed Co., Ltd. system), UFR-65 (Japan サ イ テ ッ Network society system) and MW-390 (Nippon Carbide Co., Ltd. system).
In order to keep the balance of heat resistance and chemical reagent resistance and performance in addition, the friendship in resin combination The use level of connection agent is relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor It is preferably 0.5～20 mass parts, more preferably 2～10 mass parts.When this use level is more than 0.5 mass parts, show good Heat resistance and chemical reagent resistance, when being below 20 mass parts, excellent storage stability.
When using the substrate being formed by copper or copper alloy, in order to suppress the variable color of substrate surface, can be in resin group Compound coordinates azole compounds.As azole compounds, can list 1H-triazole, 5-methyl isophthalic acid H-triazole, 5-ethyl- 1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, the 4-tert-butyl group-5-phenyl-1H-triazole, 5-hydroxy phenyl- 1H-triazole, Phenyltriazole, to ethoxyl phenenyl triazole, 5-phenyl-1-(2-dimethyl aminoethyl) triazole, 5-benzyl-1H- Triazole, hydroxy phenyl triazole, 1,5-triazol-dimethyl, 4,5-diethyl-1H-triazole, 1H-BTA, 2-(5-methyl-2- Hydroxy phenyl) BTA, 2-[2-hydroxyl-3,5-double (bis (alpha, alpha-dimethylbenzyl) base) phenyl]-BTA, 2-(3,5-bis-uncle Butyl-2-hydroxy phenyl) BTA, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-BTA, 2-(3,5-bis-uncle Amyl group-2-hydroxy phenyl) BTA, 2-(2 '-hydroxyl-5 '-t-octyl phenyl) BTA, hydroxy phenyl BTA, Tolyl-triazole, 5-methyl isophthalic acid H-BTA, 4-methyl isophthalic acid H-BTA, 4-carboxyl-1H-BTA, 5-carboxyl- 1H-BTA, 1H-TETRAZOLE, 5-methyl isophthalic acid H-tetrazolium, 5-phenyl-1H-TETRAZOLE, 5-amino-1H-TETRAZOLE, 1-methyl isophthalic acid H-tetra- Azoles etc..As preferred azole compounds, can list tolyl-triazole, 5-methyl isophthalic acid H-BTA and 4-methyl- 1H-BTA.These azole compounds can use a kind also can use mixture of more than two kinds.
The use level of the azole compounds in resin combination is relative to 100 mass parts (A) resin, (AX) photonasty polyamides Imines precursor or (AY) polyimide precursor are preferably 0.1～20 mass parts, are more preferably 0.5 from the viewpoint of speed ～5 mass parts.Azole compounds is relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyamides When the use level of imines precursor is more than 0.1 mass parts, when copper or copper alloy form the resin combination of the present invention, press down Copper processed or the variable color of copper alloy surface, when being below 10 mass parts, speed is excellent.
Additionally, the variable color on the surface in order to suppress the substrate being formed by copper or copper alloy, can be in resin combination Coordinate hindered phenol compound.As hindered phenol compound, 2 can be listed, 6-di-tert-butyl-4-methy phenol, 2,5-bis-uncle Butylhydroquinone, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, iso-octyl-3-(3,5-di-t-butyl-4- Hydroxy phenyl) propionic ester, 4,4 '-methylene-bis(2,6-di-t-butyl phenol), 4,4 '-thiobis (3-methyl-6-tert butyl benzene Phenol), 4,4 '-butane double (3 methy 6 tert butyl phenol), the double (3-(the 3-tert-butyl group-5-methyl-4-hydroxy benzenes of triethylene glycol Base) propionic ester), 1,6-HD-bis-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester), 2,2-thiodiethylene Double (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic esters), N, the double (3,5-di-t-butyl-4-hydroxyl-hydrogenation of N ' hexa-methylene Cinnamamide), 2,2 '-methylene-bis-(4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis-(4-ethyl-6-tert-butyl group Phenol), pentaerythrite four (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester), three (3,5-di-t-butyl-4-hydroxyl benzyls Base)-isocyanuric acid ester, 1,3,5-trimethyl-2,4,6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-tri-(3-hydroxyl Base-2,6-dimethyl-4-isopropyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(the tertiary fourth of 4- Base-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(4-sec-butyl- 3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-[4-(1-ethyl third Base)-3-hydroxyl-2,6-dimethyl benzyl]-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-[4-triethyl group Methyl-3-hydroxyl-2,6-dimethyl benzyl]-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(3-hydroxyl- 2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(the 4-tert-butyl group-3- Hydroxyl-2,5,6-trimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(the 4-tert-butyl group-5- Ethyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(the tertiary fourth of 4- Base-6-ethyl-3-hydroxy-2-methyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(the tertiary fourth of 4- Base-6-ethyl-3-hydroxyl-2,5-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(4- The tert-butyl group-5,6-diethyl-3-hydroxy-2-methyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5- Three (the 4-tert-butyl group-3-hydroxy-2-methyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(uncle 4- Butyl-3-hydroxyl-2,5-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(the tertiary fourth of 4- Base-5-ethyl-3-hydroxy-2-methyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketones etc., it is not limited to it ?.Among them, preferably 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6- (1H, 3H, 5H)-triketone etc..
It relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor, is subject to The use level of resistance phenolic compounds is preferably 0.1～20 mass parts, more preferably 0.5～10 mass from the viewpoint of speed Part.Hindered phenol compound is relative to 100 mass parts (A) resin, (AX) sensitive polyimide precursor or (AY) polyimides When the use level of precursor is more than 0.1 mass parts, for example, on copper or copper alloy, form the resin combination of the present invention When, the variable color corrosion of copper or copper alloy can be prevented, when being below 20 mass parts, speed is excellent.
<manufacture method of cured relief pattern and semiconductor device>
When the resin combination of the present invention is photonasty, it is provided that comprise the manufacture of the cured relief pattern of following operation Method:
(1) it on substrate, is coated with above-mentioned photosensitive polymer combination, form the work of photo-sensitive resin on the substrate Sequence；
(2) operation that this photo-sensitive resin is exposed；
(3) photo-sensitive resin after this exposure is developed, form the operation of embossing pattern；With
(4) by this embossing pattern for heating, the operation of cured relief pattern is formed.
Hereinafter, the typical way for each operation illustrates.
(1) photosensitive resin coating composition on substrate, forms the operation of photo-sensitive resin on the substrate
In this operation, base material is coated with the photosensitive polymer combination of the present invention, as required, makes it do behind Dry, form photo-sensitive resin.As coating process, it is possible to use so far used in the coating of photosensitive polymer combination Method, be for example coated with spin coater, rod coating device, Scraper applicator, curtain coaters, screen process press etc. Method, carries out the method etc. of spraying coating by spray applicators.
As required, the dried coating film being formed by photosensitive polymer combination can be made, as drying means, use wind The methods such as heat drying, the vacuum drying of doing, utilize baking oven or hot plate.Additionally, the drying of film is preferably photosensitive not cause The sensitive polyimide precursor of the denaturation of (A) resin in property resin combination or (AX), the polyimide precursor of (AY) The condition of the imidizate of (poly amic acid ester) is carried out.Specifically, carry out air-drying or during heat drying, can 20 DEG C～ It is dried under conditions of 140 DEG C and 1 minute～1 hour.As above photo-sensitive resin can be formed on substrate.
(2) operation that photo-sensitive resin is exposed
In this operation, use the exposure devices such as contact exposure machine, mirror surface projection formula exposure machine, step-by-step exposure machine, profit With ultraviolet light source etc., across the figuratum photomask of tool or reticle mask (reticle) or directly to above-mentioned middle formation Photo-sensitive resin be exposed.
Afterwards, to improve the purposes such as speed, as required, it is possible to implement based on the combination of arbitrary temperature and time Postexposure bake (PEB) and/or development before baking.The scope preferable temperature of baking condition is 40～120 DEG C, the time is 10 seconds It～240 seconds, as long as not damaging each characteristic of the photosensitive polymer combination of the present invention, is then not limited to this scope.
(3) photo-sensitive resin after exposure is developed, form the operation of embossing pattern
In this operation, among the photo-sensitive resin after exposure, the development of unexposed portion is removed.As to exposure (irradiation) After the developing method that develops of photo-sensitive resin, for example can revolve from the developing method of in the past known photoresist Turn spray-on process, agitation method, the infusion process etc. that processes with ultrasonic wave selects arbitrary method to use.Additionally, after Xian Ying, with For the purpose of the shape of adjustment embossing pattern etc., after the development based on arbitrary temperature and ageing can be implemented as required Baking.
As the developer solution used in development, good solvent or this preferably with respect to photosensitive polymer combination are good Solvent and the combination of poor solvent.As good solvent, preferably METHYLPYRROLIDONE, CHP, N, N-dimethylacetylamide, cyclopentanone, cyclohexanone, gamma-butyrolacton, α-acetyl group-gamma-butyrolacton etc., as poor solvent, preferably Toluene, dimethylbenzene, methyl alcohol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate and water etc..It is used in mixed way good solvent During with poor solvent, the dissolubility adjustment poor solvent preferably according to the polymer in photosensitive polymer combination is molten relative to good The ratio of agent.Furthermore, it is possible to use each solvent in the way of two or more such as multiple combination.
(4) by embossing pattern for heating, the operation of cured relief pattern is formed
In this operation, heat for by embossing pattern obtained from above-mentioned development, disperseed by making photographic composition, and (A) resin, (AX) sensitive polyimide precursor or (AY) polyimide precursor are heating and curing, thus it is floating to be changed into solidification Engraving patterns.As the method being heating and curing, the method using hot plate, the method using baking oven, use can be selected to set The various methods such as the method for the temperature lifting type baking oven of temperature program(me).Heating for example can be little at 200 DEG C～400 DEG C and 30 minutes～5 When under conditions of carry out.As atmosphere gas when being heating and curing, it is possible to use air, it is possible to use nitrogen, argon gas etc. are non- Active gases.
<semiconductor device>
May also provide having and float according in solidification obtained from the manufacture method of the cured relief pattern of above-mentioned middle explanation The semiconductor device of engraving patterns.More specifically, it is provided that have as the base material of semiconductor element and utilize above-mentioned consolidating The semiconductor device of the cured relief pattern of the polyimides changed embossing pattern manufacture method and formed on the substrate.Additionally, The present invention is readily adaptable for use in the manufacture method of following semiconductor device: use semiconductor element as base material, as one Operation break-down comprises the manufacture method of above-mentioned cured relief pattern.The semiconductor device of the present invention can manufacture as follows, as table Surface protective film, interlayer dielectric, again wiring dielectric film, flip-chip device diaphragm or there is projection cube structure half The diaphragm etc. of conductor device, it is possible to use the manufacture method of the cured relief pattern of above-mentioned middle explanation forms cured relief figure Case, and the manufacture method of cured relief pattern and the manufacture method of known semiconductor device are combined.
<resin film>
Comprise selected from by as the polyamic acid of polyimide precursor, poly amic acid ester, polyamic acid as (A) composition Salt, polyamic acid acid amides, the polyhydroxyamide that polyazole precursor can be become, polyaminoamide, polyamide, polyamidoimide, At least a kind of tree in the group of polyimides, polybenzoxazole, polybenzimidazoles, polybenzothiozole and phenolic resin composition Fat, crosslink density is 1.0 × 10-4mol/cm3Above and 3.0 × 10-3mol/cm3Hereinafter, and 5% weightless temperature is 250 DEG C Above and the resin film of less than 400 DEG C is also one of embodiments of the present invention.
(A) composition contained in resin film can with as institute in above-mentioned photosensitive polymer combination or resin combination (A) composition that contains and the resin-phase that illustrates with.From with the adaptation of polybenzoxazole resin from the viewpoint of, as (A) composition, It is preferably selected from by polyamic acid, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, polyamide, polyamidoimide, gather At least a kind of resin in the group of acid imide, polybenzoxazole, polybenzimidazoles and polybenzothiozole composition.In resin film, (A) composition preferably comprises more than 50 mass %, further preferably 70 matter relative to the gross mass of the whole compositions constituting resin film Amount more than %.As required, the resin in addition to A composition can also be comprised in resin film.
Heat resistance after heat treatment for the weight average molecular weight of the resin comprising in resin film and the viewpoint of mechanical property go out Send out, in terms of the polystyrene conversion based on gel permeation chromatography, be preferably 1, more than 000, more preferably 5, more than 000.Weight average The upper limit of molecular weight is preferably less than 100,000.
Crosslink density is 1cm3The molal quantity of the functional group of chemical crosslinking contained in resin film.Crosslinking reaches in the following manner Become: first make to have monomer and (A) composition copolymerization of cross-linking functional group, make the side that their cross-linking functional group reacts with each other Method；First add for the crosslinking agent with (A) composition generation chemical crosslink reaction in (A) composition, make (A) to become via this crosslinking agent The method that the strand dividing is cross-linked to each other；In (A) composition, first add polyfunctional monomer, make these polyfunctional monomers be cross-linked to each other Method etc..Resin causes crosslinking situation, storage modulus more than glass transition temperature according to crosslink density on Rise.Now, in the case that elasticity is only caused by preferable caoutchouc elasticity, known following pass between crosslink density and storage modulus It is that formula is set up:
N=E '/3RT
{ n: crosslink density, E ': storage modulus, R: gas constant, T: absolute temperature }.
Therefore, in the case of preferable rubber elastomer, can by measure resin film glass transition temperature with Storage modulus when upper thus obtain crosslink density.Storage modulus when more than glass transition temperature for example can use dynamic State determination of viscoelasticity device measures.But, reality elastomer and nonideal rubber elastomer, therefore crosslink density with Between storage modulus, this relational expression might not strictly be set up.Now, if for example using Measurement of Dynamic Viscoelasticity device to confirm glass The situation that storage modulus more than glass transition temperature rises, and obtain crosslinking contained in resin film by the method for spectroscopy Property the number of functional group and its reactivity, then they can be calculated crosslink density.
The crosslink density of the resin film using in the present invention is 1.0 × 10-4mol/cm3Above and 3.0 × 10-3mol/cm3 Hereinafter, preferably 3.0 × 10-4mol/cm3Above and 2.0 × 10-3mol/cm3Below.Crosslink density is less than 1.0 × 10-4mol/ cm3When, resin film is insufficient with the adaptation of polybenzoxazole resin.Crosslink density is more than 3.0 × 10-3mol/cm3When, resin Film becomes fragile, be not suitable for it is contemplated by the invention that passivating film, buffering film and interlayer dielectric etc. purposes.
5% weightless temperature is obtained by using thermogravimetric determinator to heat up with the speed of 10 DEG C/min under a nitrogen. When 5% weightless temperature is less than 250 DEG C, heat resistance is too low, be unsuitable for it is contemplated by the invention that passivating film, buffering film and interlayer exhausted The purposes such as velum.When 5% weightless temperature is more than 400 DEG C, insufficient with the adaptation of polybenzoxazole resin.
For resin film, base material is coated with the solution of the composition being for example dissolved with the precursor as resin film, at 250 DEG C Heat at a temperature of below thus obtain.Can have exposure process before heating.Additionally, now, by heating-up temperature It is set to less than 250 DEG C, thus form this resin on the base material comprising the resin substrate that glass transition temperature is less than 250 DEG C Film, or heating-up temperature is set to less than 200 DEG C, thus comprising the resin substrate that glass transition temperature is less than 200 DEG C Base material on form this resin film, duplexer can be obtained.
The resin combination of the present invention is in addition to being applied to semiconductor device as described above, at the layer of multilayer circuit Between the purposes such as insulation, the cap rock of flexible copper-clad plate, solder resist film and liquid crystal orientation film be also useful.
Embodiment
Hereinafter, specifically describe the present invention by embodiment, but the present invention is not limited to them.In embodiment, compare In example and Production Example, according to the physical property of following method mensuration and evaluating resin, resin film and resin combination.
(1) weight average molecular weight
Measure the weight average molecular weight (Mw) of resin by gel permeation chromatography method (polystyrene standard conversion).Mensuration makes Pillar be Showa Denko K. K Shodex (trade (brand) name) 805M/806M series connection, as standard monodisperse polystyrene Alkene, selects Showa Denko K. K Shodex STANDARD SM-105, and developing solvent is METHYLPYRROLIDONE, And use Showa electrician Shodex (trade (brand) name) RI-930 as detector.
(2) the adaptation evaluation with polybenzoxazole resin
Be coated with on polybenzoxazole resin 6 inches of Silicon Wafers solidifying, the precursor of rotary coating resin film or Photosensitive polymer combination is simultaneously dried, and forms the film of about 10 μ m-thick as resin film precursor or photo-sensitive resin.At this Use the reticle mask of tape test pattern on film, utilize i ray step-by-step exposure machine NSR2005i8A (NIKON CORPORATION system), irradiate 1500mJ/cm2Energy is exposed.Then, use cyclopentanone, utilize developing machine (D- SPIN636 type, Japan, DAINIPPON SCREEN MFG.CO., LTD. system) carry out spraying to the film being formed on wafer aobvious Shadow, rinses the unexposed portion of removal of developing, obtains resin film precursor or photosensitive resin composition with propylene glycol methyl ether acetate The embossing pattern of thing.
Heating schedule formula curing oven (VF-2000 type, Japan, Koyo are used for the wafer being formed with embossing pattern Thermo Systems CO., Ltd. system), carry out under nitrogen atmosphere 2 hours heating at 200～300 DEG C, thus applying Cloth polybenzoxazole resin simultaneously makes to obtain on its substrate solidifying the cured relief of resin film or photosensitive polymer combination Pattern.Determining film thickness uses Tencor P-15 type difference in height meter (KLA-Tencor Japan Ltd. system) to carry out.For institute The each pattern obtaining, observes the width of pattern form and drafting department under an optical microscope, evaluates based on following benchmark:
Good: the area of the opening portion of 20 μm of obtained patterns is more than the 1/2 of corresponding pattern mask aperture area And do not peel off.
Bad: 1/2 or existence of the corresponding pattern mask aperture area of area deficiency of opening portion are peeled off.
(3) the cone angle evaluation of patterns of openings
It photosensitive polymer combination is spun onto on 6 inches of Silicon Wafers and is dried, forming the painting of 8.5 μ m-thick Film.Prisma GHI (U.S., Ultratech, Inc. system) is utilized to irradiate for this film across the mask of tape test pattern 500mJ/cm2Energy.Then, use cyclopentanone, utilize developing machine (D-SPIN636 type, Japan, DAINIPPON SCREEN MFG.CO., LTD. system) spray development is carried out to the film after irradiating, it is rinsed with propylene glycol methyl ether acetate and develop Except unexposed portion, thus obtain embossing pattern.
Be immersed in the Silicon Wafer with this embossing pattern in liquid nitrogen, by 50 μm of lines/intervals (1:1) of width part along The direction being perpendicular to lines is cut off.Utilize SEM (Hitachi High-Technologies Corporation S-4800 type) Cross section obtained by observing.With reference to Figure 1A～Fig. 1 E, the method comprising following operation 1～5 is utilized to evaluate cone angle:
1. draw the bottom and upper segment (Figure 1A) of opening portion；
2. determine the height (Figure 1B) of opening portion；
3. be drawn through height middle body and with top and straight line (Central Line) (Fig. 1 C) parallel below；
4. obtain the intersection point (central point) (Fig. 1 D) of Central Line and opening portion pattern；And
5. the slope of the pattern at cooperation central point, draws tangent line, and with the following angle being formed, this tangent line is considered as cone angle (figure 1E)。
For above-mentioned wafer, use heating schedule formula curing oven (VF-2000 type, Japan, Koyo Thermo Systems CO., Ltd. system), under nitrogen atmosphere, carry out at 200～390 DEG C 2 hours heating, thus on Silicon Wafer, obtain about 4～5 The cured relief pattern of μ m-thick.
For this embossing pattern, Tencor P-15 type difference in height meter (KLA-Tencor Japan Ltd. system) is used to carry out Determining film thickness, operates as described above, obtains the cone angle of lines/interval (Line and Space) (1:1) part.
(4) minimum patterns of openings Size Evaluation
Resin combination is spun onto on 6 inches of Silicon Wafers, is dried, form the film of 8.5 μ m-thick.To this painting Film uses the mask of tape test pattern to utilize Prisma GHI (U.S., Ultratech, Inc. system) to irradiate 500mJ/cm2Energy Amount.Then, use cyclopentanone, utilize developing machine (D-SPIN636 type, Japan, DAINIPPON SCREEN MFG.CO., LTD. System) spray development is carried out to the film after irradiating, it is rinsed with propylene glycol methyl ether acetate and the unexposed portion of removal of developing, from And obtain embossing pattern.
The wafer being formed with this embossing pattern is used heating schedule formula curing oven (VF-2000 type, Japan, Koyo Thermo Systems CO., Ltd. system) under nitrogen atmosphere, carry out 2 hours heating at 200～390 DEG C, thus at silicon wafer The cured relief pattern of the polyimides of about 4～5 μ m-thick is respectively obtained on circle and on copper base.
Determining film thickness uses Tencor P-15 type difference in height meter (KLA-Tencor Japan Ltd. system) to carry out.For The pattern obtaining on Si, observes the width of pattern form and drafting department under an optical microscope, obtains minimum patterns of openings Size.
(5) mensuration of the glass transition temperature (Tg) of cured film
Become substrate 6 inches of Silicon Wafers (Japan, Fujimi Electronic Industrial Co., Ltd. system, Thickness 625 ± 25 μm) upper and carrying out sputtering with the order of the thick Cu of thick Ti and 400nm of 200nm to this Silicon Wafer On the sputtering body becoming, rotary coating resin combination is so that the thickness after Gu Hua becomes to be about 4～5 μm respectively.Then, resin group Compound be photosensitive in the case of, utilize directional light mask exposure machine PLA-501FA (Japan, Canon Inc. system) to irradiate 500mJ/cm2Energy.Resin combination in the case of photosensitive, does not carry out this irradiation.
Then, under nitrogen atmosphere, carry out heating in 2 hours at 200～390 DEG C and heat cure, thus obtain cured film.By institute The cured film obtaining is peeled off from wafer, obtains solidification band.
At load 200g/mm2, programming rate 10 DEG C/min, utilize thermomechanical experimental rig under the scope of 20～500 DEG C (Shimadzu Seisakusho Ltd. TMA-50) measures obtained solidification band, the survey that will obtain for the longitudinal axis with temperature as transverse axis, with displacement Determine the point of intersection of tangents of the hot yield point that the solidification in figure carries as glass transition temperature (Tg).
(6) mensuration of the Si adaptation of cured film and Cu adaptation
Become substrate 6 inches of Silicon Wafers (Japan, Fujimi Electronic Industrial Co., Ltd. system, Thickness 625 ± 25 μm) upper and carrying out sputtering with the order of the thick Cu of thick Ti and 400nm of 200nm to this Silicon Wafer On the sputtering body becoming, rotary coating resin combination is so that the thickness after Gu Hua becomes to be about 4～5 μm respectively.Then, resin group Compound be photosensitive in the case of, utilize directional light mask exposure machine PLA-501FA (Japan, Canon Inc. system) to irradiate 500mJ/cm2Energy.Resin combination in the case of photosensitive, does not carry out this irradiation.
Afterwards, under nitrogen atmosphere carry out at, 200 DEG C～390 DEG C 2 hours heating and heat cure, thus obtain cured film.
Closely sealed relative to Si or Cu of cured film obtained by utilizing grid test (JIS K5400) to evaluate Property.That is, on film, mark 100, the square square of 1mm with cutter, attach cellophane (registration mark) from top Band so that it is closely sealed till not having bubble, when then peeling off, count stay on substrate not invest The foursquare number that cellophane (registration mark) carries, thus evaluate.
(7) crosslink density
After resin film peeled off by base material, use Measurement of Dynamic Viscoelasticity device RHEOVIBRON model DDV-01FP (Orientec Inc. system), from 30 DEG C to 400 DEG C with 5 DEG C/min heat up and with the 3.5th, the 11st, the 35th, 110Hz each frequency compose Give small vibration, thus obtain storage modulus at each temperature.Additionally, 380 types FTIR of use (Nicolet, Inc. system), Obtain the reactivity of crosslinked group in resin film, thus calculate crosslink density.
(8) 5% weightless temperatures
After resin film peeled off by base material, use thermogravimetric determinator (Shimadzu Seisakusho Ltd. TGA-50), from 30 DEG C to 500 DEG C under a nitrogen with 10 DEG C/min of intensifications, obtain weight and reduce by the temperature of 5% from initial value.
<Production Example 1>(as the synthesis of polyimide precursor A (polymer A) of (A) composition)
By 155.1g 4, the double phthalic anhydride (ODPA) of 4 '-oxygen is encased in the removable flask of 2 liters of capacity, puts into 131.2g 2-HEMA (HEMA) and 400ml gamma-butyrolacton, be at room temperature stirred, while stirring Add 81.5g pyridine, obtain reactant mixture.After the heat release that reaction produces terminates, place and be cooled to room temperature, carry out 16 hours Place.
Then, it under ice-cold, is dissolved into 206.3g dicyclohexyl carbodiimide (DCC) in 180ml gamma-butyrolacton To solution spend within 40 minutes, add in reactant mixture while stirring, then, 93.0g 4,4 '-diaminodiphenyl ether will be made (DADPE) it is suspended in material obtained from 350ml gamma-butyrolacton and spend interpolation in 60 minutes while stirring.And then, at room temperature After stirring 2 hours, add 30ml ethanol and carry out stirring in 1 hour, then, add 400ml gamma-butyrolacton.Utilize to filter and remove The sediment generating in reactant mixture, obtains reactant liquor.
Obtained reactant liquor is added in the ethanol of 3 liters, generate the sediment being formed by crude polymer.Filter and generate Crude polymer, be dissolved in 1.5 liters of oxolanes, obtain crude polymer solution.By obtained crude polymer solution dropping In the water of 28 liters, make polymer precipitate, after the sediment obtained by leaching, be vacuum dried, obtain the poly-of powder Compound (polyimide precursor A (hereinafter also referred to as " polymer A ")).With gel permeation chromatography (polystyrene standard conversion) Measuring the molecular weight of polyimide precursor A, result weight average molecular weight (Mw) is 20,000.
<Production Example 2>(as the synthesis of polyimide precursor B (polymer B) of (A) composition)
3,3 ' 4,4 '-biphenyl tetracarboxylic dianhydride 147.1g is used to replace the double phthalic anhydride of 4,4 '-oxygen of Production Example 1 155.1g, operates as the method that aforesaid Production Example 1 is recorded in addition, reacts, obtain polyimide precursor B (following, also referred to as " polymer B ").Measure polyimide precursor B's with gel permeation chromatography (polystyrene standard conversion) Molecular weight, result weight average molecular weight (Mw) is 22,000.
<Production Example 3>(synthesis of polyamic acid (polymer C))
4,4 '-diaminodiphenyl ether (DADPE) 93.0g is put in the removable flask of 2 liters of capacity, add N-methyl Pyrrolidones 400ml, is at room temperature stirred dissolving.Afterwards, 4 are added, the double phthalic anhydride (ODPA) of 4 '-oxygen 155.1g, makes it react at 80 DEG C 5 hours, thus obtains the molten of polymer C (as the polyamic acid of polyimide precursor) Liquid.Measure the molecular weight of polymer A-1, result weight average molecular weight (Mw) with gel permeation chromatography (polystyrene standard conversion) It is 20,000.
<Production Example 4>(synthesis of silicon-containing compound D-1)
In 3 mouthfuls of flasks of 500ml, put into 10.2g hexyl amine, add 1-METHYLPYRROLIDONE 146.4g so that it is dissolve Afterwards, drip 3-ureidopropyltriethoxysilane 26.4g from dropping funel, be directly stirred at room temperature and make it react 5 hours, Thus obtain the solution of silicon-containing compound D-1.
<embodiment 1>
Use polyimide precursor A (polymer A) and polyimide precursor B (polymer B), prepared by following method Photosensitive polymer combination, the evaluation of the composition being prepared.Will be as polymer A 50g of (A) composition and polymer B 50g, with as (B) composition Adekaoptomer NCI831 (ADEKA society system, trade name, the g ray of 0.001wt% solution, H ray and i ray absorbance are respectively the 0th, 0.13 and 0.22) 2g, as the 4 of (C) composition, 4 '-BMI Diphenyl methane 10g, and HMMM 4g and TEG dimethylacrylate 8g, as (D) The silicon-containing compound D-1 3g of composition, and 2-nitroso-1-naphthols 0.05g be together dissolved in by 1-METHYLPYRROLIDONE (with Under, referred to as NMP) in the mixed solvent that formed of 80g and ethyl lactate 20g.By add further this small amount of mixed solvent from And the viscosity by obtained solution is adjusted to about 35 pools, make photosensitive polymer combination.
Said composition is applied to Silicon Wafer according to the method for aforesaid (2) and the adaptation evaluation of polybenzoxazole resin On, and make it be dried, exposure, development, close on polybenzoxazole (PBO) resin base material when carrying out heat cure at 200 DEG C Conjunction property is " well ".
<embodiment 2>
Use level using the 4,4 '-BMI diphenyl methane as (C) composition in the present invention of embodiment 1 It is changed to 20g, prepares negative light-sensitive resin combination, carry out evaluation similarly to Example 1.Evaluate at PBO resin base material On adaptation result be " well ".Wherein, now the heat curing temperature of said composition is set to 200 DEG C.
<embodiment 3>
(C) composition in the present invention of embodiment 1 is changed to double (3-ethyl-5-methyl-4-maleimide phenyl) Methane, prepares photosensitive polymer combination, carries out evaluation similarly to Example 1.Evaluate the adaptation on PBO resin base material Result be " well ".Wherein, now the heat curing temperature of said composition is set to 200 DEG C.
<embodiment 4>
Using double (3-ethyl-5-methyl-4-maleimide phenyl) as (C) composition in the present invention of embodiment 3 The use level of methane is changed to 20g, prepares photosensitive polymer combination, carries out evaluation similarly to Example 3.Evaluate at PBO The result of the adaptation on resin base material is " well ".Wherein, now the heat curing temperature of said composition is set to 200 DEG C.
<embodiment 5>
(C) composition in the present invention of embodiment 1 is changed to N-phenylmaleimide, prepares photosensitive resin composition Thing, carries out evaluation similarly to Example 1.The result evaluating the adaptation on PBO resin base material is " well ".Wherein, this When said composition heat curing temperature be set to 200 DEG C.
<embodiment 6>
(C) composition in the present invention of embodiment 1 is changed to N, N ', N "-[nitrilo-three (ethylidene)] three (Malaysia acyls Imines), prepare photosensitive polymer combination, carry out evaluation similarly to Example 1.Evaluate closely sealed on PBO resin base material Property result be " well ".Wherein, now the heat curing temperature of said composition is set to 200 DEG C.
<embodiment 7>
(C) composition in the present invention in embodiment 2 is changed to belong to the glass transition temperature of homopolymers be 200 DEG C with On the isocyanuric acid triacrylate of multifunctional methacrylate, prepare photosensitive polymer combination, carry out and embodiment 2 Same evaluation.The result evaluating the adaptation on PBO resin base material is " well ".Wherein, the thermosetting of now said composition Change temperature and be set to 200 DEG C.
<comparative example 1>
Remove in the present invention of embodiment 1 as the 4 of (C) composition, 4 '-BMI diphenyl methane, preparation Negative light-sensitive resin combination, carries out evaluation similarly to Example 1.The knot of adaptation on PBO resin base material for the evaluation Fruit is " bad ".Wherein, now the heat curing temperature of said composition is set to 200 DEG C.
The evaluation result of embodiment 1～7 and comparative example 1 shown in table 1 below.
[table 1]
The explanation of the abbreviation in table 1
B1:Adekaoptomer NCI831 (ADEKA society system, trade name)
C1:4,4 '-BMI diphenyl methane
C2: double (3-ethyl-5-methyl-4-maleimide phenyl) methane
C3:N-phenyl maleimide
C4:N, N ', N "-[nitrilo-three (ethylidene)] three (maleimides)
C5: isocyanuric acid triacrylate
D1: silicon-containing compound D-1
<embodiment 8>
Will be as polymer A 50g of (AX) composition and polymer B 50g, as the Irgacure of (B) composition (the 0th, the 0th, the g ray of 0.001wt% solution, h ray and i ray absorbance are respectively OXE03 for BASF AG's system, trade name And 0.27) 2g, TEG dimethylacrylate 8g and 2-nitroso-1-naphthols 0.05g and diphenylacetamide 5g, N-(3-(triethoxysilyl) propyl group) phthalyl amino acid 0.5g and BP-3,3 '-bis-(N-(3-tri- Triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids 0.5g is dissolved in by 1-METHYLPYRROLIDONE and ethyl lactate shape In the mixed solvent (weight is than 8:2) becoming, adjust the amount of solvent so that viscosity becomes is about 35 pools, thus obtain photoresist group Polymer solution.
For said composition, the cone angle evaluation of aforesaid (3) patterns of openings and (4) minimum patterns of openings size is utilized to comment Valency method is evaluated.
<embodiment 9>
Will be as polymer A 50g of (AX) composition and polymer B 50g, as the Irgacure of (B) composition OXE03 2g, as the 4 of (C) composition, 4 '-BMI diphenyl methane 16g, TEG dimethylacrylate 8g And the adjacent benzene of 2-nitroso-1-naphthols 0.05g and diphenylacetamide 5g, N-(3-(triethoxysilyl) propyl group) Diamides acid 0.5g and BP-3,3 '-bis-(N-(3-triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids 0.5g is dissolved in the mixed solvent (mass ratio 8:2) being formed by 1-METHYLPYRROLIDONE and ethyl lactate, adjusts solvent Amount is about 35 pools so that viscosity becomes, thus obtains photosensitive polymer combination solution.
For said composition, method similarly to Example 8 is utilized to evaluate.
<embodiment 10>
Use Adekaoptomer NCI831 (ADEKA society system, trade name, the g ray of 0.001wt% solution, h ray, And i ray absorbance is respectively the 0th, 0.13 and 0.22) 2g replaces the Irgacure as (B) composition in embodiment 9 OXE03 2g, operates in addition similarly to Example 9, prepares photosensitive polymer combination solution.
For said composition, method similarly to Example 8 is utilized to evaluate.
<embodiment 11>
In embodiment 9, use TR-PBG340 (Changzhou Tronly New Electronic Materials Co., Ltd.'s system, commodity as (B) composition Name, the g ray of 0.001wt% solution, h ray and i ray absorbance are respectively the 0.04th, 0.06 and 0.04) 2g, remove this Operate similarly to Example 9 in addition, prepare photosensitive polymer combination solution.
For said composition, method similarly to Example 8 is utilized to evaluate.
<comparative example 2>
In embodiment 8, as the replacement composition of (B) composition, (Changzhou electronic strong new material is limited to use TR-PBG304 Company's system, trade name, the g ray of 0.001wt% solution, h ray and i ray absorbance are respectively the 0th, 0 and 0.12) 4g, prepares photosensitive polymer combination in addition similarly to Example 8.
For said composition, method similarly to Example 8 is utilized to evaluate.
The evaluation result of embodiment 8～11 and comparative example 2 shown in table 2 below.
[table 2]
The explanation of the abbreviation in table 2
-(B) composition-
B1:Irgacure OXE03 (BASF AG's system, trade name)
B2:Adekaoptomer NCI831 (ADEKA society system, trade name)
B3:TR-PBG340 (Changzhou Tronly New Electronic Materials Co., Ltd.'s system, trade name)
-(C) composition-
C1:4,4 '-BMI diphenyl methane
-replacement composition-
B4:TR-PBG304 (Changzhou Tronly New Electronic Materials Co., Ltd.'s system, trade name)
<embodiment 12>
Will as the polymer C 100g of (AY) composition, as (B) composition Irgacure OXE03 (BASF AG's system, Trade name) and the silicon-containing compound D-1 3g as (D) composition be dissolved in by 1-METHYLPYRROLIDONE and ethyl lactate shape In the mixed solvent (mass ratio 8:2) becoming, adjust the amount of solvent so that viscosity becomes is about 35 pools, thus obtain resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<embodiment 13>
Will be as polymer A 50g of (AY) composition and polymer B 50g, as the Irgacure of (B) composition OXE03 (BASF AG's system, trade name) 4g, as the silicon-containing compound D-1 3g of (D) composition, TEG dimethacrylate Ester 8g, 2-nitroso-1-naphthols 0.05g and diphenylacetamide 5g is dissolved in by 1-METHYLPYRROLIDONE and lactic acid second In the mixed solvent (mass ratio 8:2) that ester is formed, adjust the amount of solvent so that viscosity becomes is about 35 pools, thus obtain resin combination Thing.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<embodiment 14>
Will be as polymer A 50g of (AY) composition and polymer B 50g, as the Irgacure OXE3 of (B) composition (BASF AG's system, trade name) 4g, as the silicon-containing compound D-1 3g of (D) composition and by A-1160 (3-ureido-propyl three 50 mass % solution of Ethoxysilane, Momentive Inc. system) the methanol solution 3g that makes, TEG dimethyl allene Acid esters 8g, 2-nitroso-1-naphthols 0.05g and diphenylacetamide 5g is dissolved in by 1-METHYLPYRROLIDONE and lactic acid In the mixed solvent (mass ratio 8:2) that ethyl ester is formed, adjust the amount of solvent so that viscosity becomes is about 35 pools, thus obtain resin group Compound.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<embodiment 15>
The heating-up temperature being used for solidification in embodiment 14 is changed to 390 DEG C from 200 DEG C, in addition, with embodiment 14 Same operation, forms cured film, evaluates.
<embodiment 16>
Will be as polymer A 50g of (AY) composition and polymer B 50g, and as (B) composition Adekaoptomer NCI831 (ADEKA society system, trade name) 4g, as the 4 of (C) composition, 4 '-BMI diphenyl Methane 16g, as the silicon-containing compound D-1 3g of (D) composition and by A-1160 (the 50 of 3-ureidopropyltriethoxysilane Quality % solution, Momentive Inc. system) the methanol solution 3g that makes, TEG dimethylacrylate 8g, 2-nitrous Base-1-naphthols 0.05g and diphenylacetamide 5g is together dissolved in and is formed by 1-METHYLPYRROLIDONE and ethyl lactate In mixed solvent (mass ratio 8:2), adjust the amount of solvent so that viscosity becomes is about 35 pools, thus obtain resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<embodiment 17>
(C) composition is changed to double (3-ethyl-5-first from 4,4 '-BMI diphenyl methane by embodiment 16 Base-4-maleimide phenyl) methane, operate similarly to Example 16 in addition, obtain resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<embodiment 18>
Embodiment 16 use dicyclohexyl thiourea 3g to replace (D) composition as (E) composition, in addition, with embodiment 16 operate equally, obtain resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<comparative example 3>
In embodiment 12, as the replacement composition of (D) composition, use the adjacent benzene of N-(3-(triethoxysilyl) propyl group) Diamides acid 0.5g and BP-3,3 '-bis-(N-(3-triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids 0.5g, operates in addition similarly to Example 12, obtains resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<comparative example 4>
In embodiment 14, as the replacement composition of (D) composition, use the adjacent benzene of N-(3-(triethoxysilyl) propyl group) Diamides acid 0.5g and BP-3,3 '-bis-(N-(3-triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids 0.5g, operates in addition similarly to Example 14, obtains resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
<comparative example 5>
In embodiment 15, as the replacement composition of (D) composition, use the adjacent benzene of N-(3-(triethoxysilyl) propyl group) Diamides acid 0.5g and BP-3,3 '-bis-(N-(3-triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids 0.5g, operates in addition similarly to Example 15, obtains resin combination.
For this resin combination, utilize the mensuration of the glass transition temperature (Tg) of aforesaid (5) cured film, (6) solid Change the mensuration of Si, Cu adaptation of film, (4) minimum patterns of openings Size Evaluation method is evaluated.
The evaluation result of embodiment 12～18 and comparative example 3～5 shown in Table 3 below.
[table 3]
The explanation of the abbreviation in table 3
B1:Irgacure OXE03 (BASF AG's system, trade name)
B2:Adekaoptomer NCI831 (ADEKA society system, trade name)
C1:4,4 '-BMI diphenyl methane
C2: double (3-ethyl-5-methyl-4-maleimide phenyl) methane
D1: silicon-containing compound D-1
D2: silicon-containing compound D-1/A-1160 (50% solution of 3-ureidopropyltriethoxysilane, Momentive Inc. system)
D3:N-(3-(triethoxysilyl) propyl group) phthalyl amino acid/BP-3,3 '-bis-(N-(3-tri- Triethoxysilyl) propyl amides)-4,4 '-dicarboxylic acids
<embodiment 19>
Will be as polymer A 50g of (A) composition and polymer B 50g and Adekaoptomer NCI831 (ADEKA Society's system, trade name, the g ray of 0.001wt% solution, h ray and i ray absorbance are respectively the 0th, 0.13 and 0.22) 2g, 4,4 '-BMI diphenyl methane 10g, silicon-containing compound D-1 3g and 2-nitroso-1-naphthols 0.05g mono- With being dissolved in the mixed solvent being formed by 1-METHYLPYRROLIDONE (hereinafter referred to as NMP) 80g and ethyl lactate 20g, obtain molten Liquid.By add this small amount of mixed solvent further thus the viscosity by obtained solution be adjusted to about 35 pool, felt Photosensitive resin composition.
According to the method for aforesaid (2) and the adaptation evaluation of polybenzoxazole resin, said composition is applied to Silicon Wafer On so that it is it is dried, be exposed, develop, heat cure at 200 DEG C, obtain resin film.Now, in polybenzoxazole (PBO) tree Adaptation on aliphatic radical material is " well ".
Additionally, for aforesaid (7) crosslink density, by the reactivity of the maleimide based on IR and form, density Obtain is 7.0 × 10-4mol/cm3.Additionally, 110Hz, 300 DEG C when storage modulus be 0.08GPa, aforesaid (8) 5% weightless Temperature is 340 DEG C.
<embodiment 20>
In embodiment 19, the addition of 4,4 '-BMI diphenyl methane is changed to 20g, in addition with Embodiment 19 similarly modulates photosensitive polymer combination.
According to the method for aforesaid (2) and the adaptation evaluation of polybenzoxazole resin, said composition is applied to Silicon Wafer On so that it is it is dried, be exposed, develop, heat cure at 200 DEG C, obtain resin film.Now, in polybenzoxazole (PBO) tree Adaptation on aliphatic radical material is " well ".
Additionally, for aforesaid (7) crosslink density, by the reactivity of the maleimide based on IR and form, density Obtain is 1.4 × 10-3mol/cm.Additionally, 110Hz, 300 DEG C when storage modulus be 0.16GPa, aforesaid (8) 5% weightless temperature Degree is 370 DEG C.
<comparative example 6>
In embodiment 19, without 4,4 '-BMI diphenyl methane, in addition similarly to Example 19 Resin composition modulation, obtains the heat reactive resin film of said composition.Now, according to aforesaid (2) and polybenzoxazole resin The adaptation on polybenzoxazole (PBO) resin base material evaluated of the method for adaptation evaluation be " bad ".
Additionally, for aforesaid (7) crosslink density, by the reactivity of the maleimide based on IR and form, density Obtain as 0mol/cm3.Additionally, 110Hz, 300 DEG C when storage modulus be 0.02GPa, aforesaid (8) 5% weightless temperatures are 320℃。
Embodiment 19 and 20 and the evaluation result of comparative example 6 shown in table 4 below.
[table 4]
Industrial applicability
The resin combination of the present invention and resin film can be aptly for example for semiconductor device, multilayer wiring bases The field of photosensitive material useful in the manufacture of the electric and electronic material of plate etc. utilizes.

Claims (39)

1. a photosensitive polymer combination, it comprises following component:
(A) selected from by as the polyamic acid of polyimide precursor, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, can Become the polyhydroxyamide of polyazole precursor, polyaminoamide, polyamide, polyamidoimide, polyimides, polyphenyl simultaneously At least a kind of resin in the group of azoles, polybenzimidazoles, polybenzothiozole and phenolic resin composition；
(B) emulsion；And
(C) selected from by multifunctional (methyl) acrylate and molecular weight, the low-molecular-weight imide compound less than 1000 forms Group at least a kind.
2. photosensitive polymer combination according to claim 1, wherein, described (A) composition is for selected from by as polyamides Asia The polyamic acid of amine precursor, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, polyamide, polyamidoimide, polyamides At least a kind of resin in the group of imines, polybenzoxazole, polybenzimidazoles and polybenzothiozole composition.
3. the photosensitive polymer combination according to claims 1 or 2, wherein, described (C) composition be described molecular weight not The low-molecular-weight imide compound of foot 1000.
4. the photosensitive polymer combination according to according to any one of claims 1 to 3, wherein, described (A) composition is for by following The polyimide precursor that formula (A1) represents:
In formula (A1), X1It is the organic group of 4 valencys, Y1For the organic group of divalent, l is the integer of 2～150, R1And R2Respectively solely The on the spot organic group for hydrogen atom or 1 valency of free redical polymerization；Wherein, R1And R2Both are hydrogen atom when different；
Further, described (C) composition comprises the maleimide being represented by following formula (C1):
In formula (C1), R3For the organic group of singly-bound, hydrogen atom or 1～trivalent, R4And R5It is separately hydrogen atom, carbon The alkyl of several 1～10, the cycloalkyl of carbon number 3～10, aryl, alkoxyl or halogen atom, and the integer that m is more than 1.
5. the photosensitive polymer combination according to according to any one of Claims 1 to 4, wherein, described (A) composition is for by following The polyimide precursor that formula (A2) represents:
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7Respectively solely The organic group of 1 valency on the spot for hydrogen atom, being represented by following formula (A3) or the saturated aliphatic groups of carbon number 1～4； Wherein, R6And R7Both are hydrogen atom when different,
In formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is 2～10 Integer.
6. the photosensitive polymer combination according to according to any one of Claims 1 to 5, wherein, described (C) composition comprise by under State the maleimide that formula (C2) represents:
In formula (C2), R11For the organic group of singly-bound, hydrogen atom or 1～trivalent, R12And R13Separately for hydrogen atom, The alkyl of carbon number 1～10, the cycloalkyl of carbon number 3～10, aryl, alkoxyl or halogen atom, and the integer that q is 2～4.
7. the photosensitive polymer combination according to according to any one of claim 1～6, wherein, described (B) composition is oxime system light Polymerization initiator.
8. the photosensitive polymer combination according to according to any one of claim 1～7, wherein, described (B) composition comprises to be selected from In the group being grouped into by following (B1) and (B2) one-tenth at least a kind:
(B1) the i ray absorbance of 0.001wt% solution is 0.15～0.5 and the g ray absorbance of 0.001wt% solution And the oxime ester compound that h ray absorbance is less than 0.2；And
(B2) the i ray absorbance of 0.001wt% solution be less than 0.1 and the g ray absorbance of 0.001wt% solution or Person's h ray absorbance is the oxime ester compound of more than 0.05.
9. photosensitive polymer combination according to claim 8, wherein, the i of the 0.001wt% solution of described (B1) composition Ray absorbance is 0.15～0.35.
10. the photosensitive polymer combination according to Claim 8 or described in 9, wherein, described (B1) composition comprise selected from by under State formula (B11) and in the group of oxime ester compound composition that (B12) represents at least a kind:
In formula (B11), R14For C1～C10Fluorine-containing alkyl, R15、R16, and R17It is separately C1～C20Alkyl, C3~ C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that r is 0～5；
In formula (B12), R18For C1～C30The organic group of divalent, R19～R26It is separately C1～C20Alkyl, C3~ C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that s is 0～3.
11. photosensitive polymer combinations according to according to any one of claim 1～10, wherein, become at above-mentioned (A)～(C) On the basis of dividing,
Comprise the silicon-containing compound that (D) is represented by following formula (D1):
In formula (D1), R27And R28For C1～C4Alkyl, R29For C1～C6The organic group of divalent, R30For via selected from by Atom in the group of nitrogen, oxygen and sulphur composition and the C of carbonyl linkage1～C20Organic group, t for selected from the 1st, 2 and 3 whole Number, u is the integer selected from the 0th, 1 and 2, and t and u meets the relation of t+u=3.
12. photosensitive polymer combinations according to claim 11, wherein, as described (D) composition, by described formula (D1), on the basis of the silicon-containing compound representing, the silicon-containing compound being represented by following formula (D2) is also comprised:
In formula (D2), R31And R32For C1～C4Alkyl, R33For C1～C6The organic group of divalent, v is for selected from the 1st, 2 and 3 Integer, w for selected from the 0th, 1 and 2 integer, and v and w meet the relation of v+w=3.
13. photosensitive polymer combinations according to according to any one of claim 1～10, wherein, become at above-mentioned (A)～(C) On the basis of dividing,
Comprise the sulfur-containing compound that (E) is represented by following formula (E1):
In formula (E1), R34For C1～C20Organic group or siliceous organic group, R35For via selected from by nitrogen, oxygen and sulphur The C that atom in the group of composition is bonded with thiocarbonyl1～C20Organic group.
14. photosensitive polymer combinations according to according to any one of claim 1～10, wherein, relative to described (A) composition 100 mass parts, comprise described (B) composition 0.1～20 mass parts, and described (C) composition 1～40 mass parts.
15. photosensitive polymer combinations according to according to any one of claim 1～10, wherein, relative to described (A) composition 100 mass parts, comprise described (B) composition 0.1～20 mass parts, and described (C) composition 10～35 mass parts.
16. photosensitive polymer combinations according to claim 11 or 12, wherein, relative to described (A) composition 100 matter Amount part, comprises described (B) composition 0.1～20 mass parts, described (C) composition 1～40 mass parts, and described (D) composition 0.1～ 20 mass parts.
17. photosensitive polymer combinations according to claim 11 or 12, wherein, relative to described (A) composition 100 matter Amount part, comprises described (B) composition 0.1～20 mass parts, described (C) composition 10～35 mass parts, and described (D) composition 0.1 ～20 mass parts.
18. photosensitive polymer combinations according to claim 13, wherein, relative to described (A) composition 100 mass parts, Comprise described (B) composition 0.1～20 mass parts, described (C) composition 1～40 mass parts, and described (E) composition 0.1～20 matter Amount part.
19. photosensitive polymer combinations according to claim 13, wherein, relative to described (A) composition 100 mass parts, Comprise described (B) composition 0.1～20 mass parts, described (C) composition 10～35 mass parts, and described (E) composition 0.1～20 matter Amount part.
20. 1 kinds of photosensitive polymer combinations, it comprises following component:
(AX) sensitive polyimide precursor；With
Become at least a kind in the group being grouped into selected from by following (B1) and (B2): the i ray of (B1) 0.001wt% solution is inhaled Luminosity is 0.15～0.5 and the g ray absorbance of 0.001wt% solution and the oxime ester that h ray absorbance is less than 0.2 Compound, and
(B2) the i ray absorbance of 0.001wt% solution is less than 0.1, and 0.001wt% solution g ray absorbance or Person's h ray absorbance is the oxime ester compound of more than 0.05.
21. photosensitive polymer combinations according to claim 20, wherein, described (AX) composition is for by following formula (A2) The polyimide precursor representing:
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7Respectively solely The organic group of 1 valency on the spot for hydrogen atom, being represented by following formula (A3) or the saturated aliphatic groups of carbon number 1～4； Wherein, R6And R7Both are hydrogen atom when different,
In formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is 2～10 Integer.
22. photosensitive polymer combinations according to claim 20 or 21, wherein, described (B1) composition The i ray absorbance of 0.001wt% solution is 0.15～0.35.
23. photosensitive polymer combinations according to according to any one of claim 20～22, wherein, described (B1) composition comprises In the group that the oxime ester compound being represented by following formula (B11) and (B12) forms at least a kind:
In formula (B11), R14For C1～C10Fluorine-containing alkyl, R15、R16, and R17It is separately C1～C20Alkyl, C3~ C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that r is 0～5；
In formula (B12), R18For C1～C30The organic group of divalent, R19～R26It is separately C1～C20Alkyl, C3~ C20Cycloalkyl, C6～C20Aryl or C1～C20Alkoxyl, and the integer that s is 0～3.
24. photosensitive polymer combinations according to according to any one of claim 20～23, wherein, relative to 100 mass parts The total content of described (B1) composition of described (AX) composition and (B2) composition is 0.1～10 mass parts.
25. photosensitive polymer combinations according to according to any one of claim 20～24, wherein, relative to 100 mass parts The total content of described (B1) composition of described (AX) composition and (B2) composition is 0.5～5 mass parts.
26. 1 kinds of resin combinations, it comprises following component:
(AY) polyimide precursor；And
(D) silicon-containing compound being represented by following formula (D1):
In formula (D1), R27And R28For C1～C4Alkyl, R29For C1～C6The organic group of divalent, R30For via selected from by Atom in the group of nitrogen, oxygen and sulphur composition and the C of carbonyl linkage1～C20Organic group, t for selected from the 1st, 2 and 3 whole Number, u is the integer selected from the 0th, 1 and 2, and t and u meets the relation of t+u=3.
27. resin combinations according to claim 26, wherein, as described (D) composition, are being represented by described formula (D1) Silicon-containing compound on the basis of, also comprise the silicon-containing compound being represented by following formula (D2):
In formula (D2), R31And R32For C1～C4Alkyl, R33For C1～C6The organic group of divalent, v is for selected from the 1st, 2 and 3 Integer, w for selected from the 0th, 1 and 2 integer, and v and w meet the relation of v+w=3.
28. 1 kinds of resin combinations, it comprises following composition:
(AY) polyimide precursor；And
(E) sulfur-containing compound being represented by following formula (E1):
In formula (E1), R34For C1～C20Organic group or siliceous organic group, R35For via selected from by nitrogen, oxygen and sulphur The C that atom in the group of composition is bonded with thiocarbonyl1～C20Organic group.
29. resin combinations according to according to any one of claim 26～28, wherein, described (AY) composition is for being led to by following The polyimide precursor that formula (A2) represents:
In formula (A2), X2It is the organic group of 4 valencys, Y2For the organic group of divalent, n is the integer of 2～150, R6And R7Respectively solely The organic group of 1 valency on the spot for hydrogen atom, being represented by following formula (A3) or the saturated aliphatic groups of carbon number 1～4； Wherein, R6And R7Both are hydrogen atom when different,
In formula (A3), R8、R9And R10It is separately the organic group of hydrogen atom or carbon number 1～3, and p is 2～10 Integer.
30. resin combinations according to claim 27, wherein, relative to (AY) composition described in 100 mass parts, comprise institute State (D1) composition 0.1～20 mass parts, and described (D2) composition 0.1～20 mass parts.
31. resin combinations according to claim 28 or 29, wherein, relative to (AY) composition described in 100 mass parts, Comprise described (E) composition 0.1～20 mass parts.
32. resin combinations according to according to any one of claim 26～31, wherein, possibly together with (B) emulsion.
The manufacture method of 33. 1 kinds of cured relief patterns, it includes following operation:
(1) on substrate, it is coated with the photosensitive polymer combination according to any one of claim 1～25 or claim 32 Described resin combination, forms the operation of photo-sensitive resin on the substrate；
(2) operation that this photo-sensitive resin is exposed；
(3) make the photo-sensitive resin after this exposure develop, form the operation of embossing pattern；With
(4) by this embossing pattern for heating, the operation of cured relief pattern is formed.
34. 1 kinds of semiconductor devices, it possesses the cured relief pattern being obtained by the manufacture method described in claim 33.
35. 1 kinds of resin films, it comprises following composition: (A) is selected from by as the polyamic acid of polyimide precursor, polyamide Acid esters, polyamic acid salt, polyamic acid acid amides, the polyhydroxyamide that polyazole precursor can be become, polyaminoamide, polyamide, In the group of polyamidoimide, polyimides, polybenzoxazole, polybenzimidazoles, polybenzothiozole and phenolic resin composition At least a kind of resin,
Crosslink density is 1.0 × 10-4mol/cm3Above and 3.0 × 10-3mol/cm3Hereinafter, and
5% weightless temperature is more than 250 DEG C and less than 400 DEG C.
36. resin films according to claim 35, wherein, described crosslink density is 3.0 × 10-4mol/cm3Above and 2.0 ×10-3mol/cm3Below.
37. resin films according to claim 35 or 36, wherein, described (A) composition is for selected from by as polyimides The polyamic acid of precursor, poly amic acid ester, polyamic acid salt, polyamic acid acid amides, polyamide, polyamidoimide, polyamides are sub- At least a kind of resin in the group of amine, polybenzoxazole, polybenzimidazoles and polybenzothiozole composition.
38. 1 kinds of duplexers, wherein, the resin film layer according to any one of claim 35～37 is laminated on glass transition temperature It is on the resin substrate of less than 200 DEG C.
39. 1 kinds of duplexers, wherein, the resin film layer according to any one of claim 35～37 is laminated on glass transition temperature It is on the resin substrate of less than 250 DEG C.
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