CN110088680A - The double-deck photosensitive layer volume - Google Patents

The double-deck photosensitive layer volume Download PDF

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Publication number
CN110088680A
CN110088680A CN201780078288.6A CN201780078288A CN110088680A CN 110088680 A CN110088680 A CN 110088680A CN 201780078288 A CN201780078288 A CN 201780078288A CN 110088680 A CN110088680 A CN 110088680A
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photosensitive layer
group
formula
integer
divalent
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CN110088680B (en
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藤田充
谷崎洋子
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Abstract

Photosensitive layer volume includes support body thin film；With, photosensitive layer, it is set on support body thin film and includes photosensitive polymer combination, photosensitive polymer combination includes at least one kind of resin in the group being made of phenolic resin, polyimide precursor, polybenzoxazoles precursor and soluble polyimide, and photosensitive layer is the layer for becoming 500Pas temperature spot below with melt viscosity.

Description

The double-deck photosensitive layer volume
Technical field
The present invention relates to photosensitive layer volumes.
Background technique
In the past, the pattern as semiconductor device, liquid crystal display element, printed circuit board etc. formed the middle image shape utilized At method, it is however generally that, it is known to photoetching process.In photoetching process, usually using any one during there are as below methods: by photonasty The solution coating of resin combination is on the substrates such as copper-clad laminated board and dry method；Or, supporter, packet will be sequentially laminated with Layer containing photosensitive polymer combination is (hereinafter also referred to as the photo-sensitive resin of " photosensitive layer " and covering film as needed Stack (hereinafter also referred to as " dry film photoresist ") is layered in the method on substrate.In the manufacture of printed circuit board, after most use Person.
Dry film photoresist is taken care of in the form of volume (referring to patent document 1) sometimes.In patent document 1, in order to from dry film The volume of resist omits covering film to cut down manufacturing cost, proposes a kind of photosensitive sex camplex, successively includes: photosensitive Layer；With, non-adhesive outer layer, the thickness below of 1/5th of the thickness with photosensitive layer.
From the viewpoint of the operation of dry film photoresist, it is desirable that dry film photoresist resists without adhesiveness, by dry film at room temperature Mobility is embodied whens erosion agent hot pressing is connected to substrate etc. (that is, when lamination) (referring to patent document 2).One is proposed in patent document 2 Kind photonasty covers film, without adhesiveness at 20 DEG C of substrate temperature, and is easy to carry out position being placed on substrate Amendment.
In addition, in patent document 3, it is thus identified that by photosensitive polymer combination by the phenolic aldehyde tree with specific structure Rouge is applied in combination with nonionic surfactant, can take into account the chemical resistance of curability at low temperatures and cured film.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2001-175000 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2003-149803 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2013-190697 bulletin
Summary of the invention
Problems to be solved by the invention
In general, manufacturing photoresist laminated body in the form of volume, cuts into required width and use.However, photosensitive Layer by the group being made of phenolic resin, polyimide precursor, polybenzoxazoles precursor and soluble polyimide extremely In the case where the previous photoresist laminated body that few a kind of resin is formed, exists and generate fold or crackle, difficulty when being cut The problem of to be cut in the mode for keeping section smoothened.
The solution to the problem
The inventors of the present invention's discovery: by adjusting the melt viscosity or removal covering film of photosensitive layer, it can solve above-mentioned ask Topic, completes the present invention.That is, the present invention is as described below.
[1]
A kind of photosensitive layer volume, includes
Support body thin film；With,
Photosensitive layer is set on aforementioned support body thin film and includes photosensitive polymer combination,
Photosensitive resin combination include selected from by phenolic resin, polyimide precursor, polybenzoxazoles precursor and At least one kind of resin in the group of soluble polyimide composition, and aforementioned photosensitive layer is to become 500Pas with melt viscosity The layer of temperature spot below.
[2]
The volume of the photosensitive layer according to [1], wherein aforementioned photosensitive layer is below as 350Pas with melt viscosity The layer of temperature spot.
[3]
It is rolled up according to photosensitive layer described in [1] or [2], wherein the melt viscosity at 100 DEG C of aforementioned photosensitive layer is 500Pas or less.
[4]
The volume of the photosensitive layer according to [3], wherein melt viscosity at 100 DEG C of aforementioned photosensitive layer be 350Pas with Under.
[5]
The volume of the photosensitive layer according to any one of [1]~[4], wherein be equipped with aforementioned supporter in aforementioned photosensitive layer The opposite side of the side of film has covering film, and the softening temperature of aforementioned covering film is 90 DEG C or more.
[6]
The volume of the photosensitive layer according to [5], wherein the softening temperature of aforementioned covering film is 110 DEG C or more.
[7]
The volume of the photosensitive layer according to any one of [1]~[6], wherein organic solvent contained in aforementioned photosensitive layer Measuring relative to the total amount of aforementioned photosensitive layer is 0.1 mass % or more and 15 mass % or less.
[8]
The volume of the photosensitive layer according to [7], wherein the amount of organic solvent contained in aforementioned photosensitive layer is relative to aforementioned sense The total amount of photosphere is 1 mass % or more and 15 mass % or less.
[9]
According to photosensitive layer described in [7] or [8] roll up, wherein aforementioned organic solvents include selected from by gamma-butyrolacton, acetone, In the group that methyl ethyl ketone, n-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, the tert-butyl alcohol and tetrahydrofurfuryl alcohol form It is at least one.
[10]
The volume of the photosensitive layer according to [9], wherein aforementioned organic solvents include selected from by gamma-butyrolacton, acetone, first and second At least one of ketone, n-methyl-2-pyrrolidone and group of dimethyl sulfoxide composition.
[11]
The volume of the photosensitive layer according to any one of [1]~[10], wherein photosensitive resin combination includes aforementioned Polyimide precursor.
[12]
The volume of the photosensitive layer according to any one of [1]~[10], wherein photosensitive resin combination includes aforementioned Polybenzoxazoles precursor.
[13]
The volume of the photosensitive layer according to any one of [1]~[10], wherein photosensitive resin combination includes aforementioned Soluble polyimide.
[14]
The volume of the photosensitive layer according to any one of [1]~[10], wherein photosensitive resin combination includes aforementioned Phenolic resin.
[15]
The volume of the photosensitive layer according to [14], wherein aforementioned phenolic resin has structure conduct shown in the following general formula (1) Repetitive unit:
{ in formula (1), the integer that a is 1~3, the integer that b is 0~3 is 1≤(a+b)≤4, R1It indicates selected from by carbon number 1 The substituent group for 1 valence in group that organic group, halogen atom, nitro and the cyano of~20 1 valence form, when b is 2 or 3 Multiple R1It is optionally same or different to each other, and X indicates the chain selected from the divalent by the carbon number 2~10 optionally with unsaturated bond Aliphatic group, the ester ring type group of the divalent of carbon number 3~20, divalent shown in the following general formula (2) alkylidene oxide and have The organic group of divalent in the group of the organic group composition of the divalent of aromatic ring,
——CpH2pO --- (formula 2)
(in formula (2), p be 1~10 integer.)}.
[16]
The volume of the photosensitive layer according to [15], wherein the X in aforementioned formula (1) is selected from as shown in the following general formula (3) The organic group of divalent in the group of the group composition of divalent shown in the group and the following general formula (4) of divalent,
In formula (3), R2、R3、R4And R5Be each independently hydrogen atom, carbon number 1~10 1 valence aliphatic group or The aliphatic group of 1 valence of carbon number 1~10 made of part or all of hydrogen atom is replaced with fluorine atom, n1 be 0~4 it is whole Number, the R when n1 is 1~4 integer6For the organic group of halogen atom, hydroxyl or 1 valence, at least one R6For hydroxyl, work as n1 For 2~4 integer when multiple R6Optionally it is same or different to each other.}
In formula (4), R7、R8、R9And R10Each independently represent hydrogen atom, carbon number 1~10 1 valence aliphatic group, Or part or all of hydrogen atom replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, and W be singly-bound, Selected from the carbon number 3~20 by optionally being replaced with the chain fatty race group of the carbon number 1~10 of fluorine atom substitution, optionally with fluorine atom Ester ring type group, divalent shown in the following general formula (2) alkylidene oxide and following formula (5) shown in divalent group composition Group in divalent organic group,
——CpH2pO --- (formula 2)
(in formula (2), p be 1~10 integer.)
[17]
It is rolled up according to photosensitive layer described in [15] or [16], wherein the X in aforementioned formula (1) is 2 shown in following formula (6) The organic group of valence,
[18]
The volume of the photosensitive layer according to [17], wherein the X in aforementioned formula (1) is having for divalent shown in following formula (7) Machine group,
[19]
The volume of the photosensitive layer according to any one of [15]~[18], wherein aforementioned phenolic resin is in same resin matrix It is interior that there is both repetitive units shown in repetitive unit shown in the following general formula (8) and the following general formula (9),
In formula (8), R11For the group of 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy, n2 1 ~3 integer, the integer that n3 is 0~2, the integer that m1 is 1~500 is 2≤(n2+n3)≤4, the R when n3 is 211Optionally that This is identical or different.}
In formula (9), R12And R13It is each independently the carbon number 1~10 in the group being made of alkyl and alkoxy The group of 1 valence, n4 be 1~3 integer, n5 be 0~2 integer, n6 be 0~3 integer, m2 be 1~500 integer, be 2≤ (n4+n5)≤4, the R when n5 is 212Optionally it is same or different to each other, the R when n6 is 2 or 313It is optionally mutually the same or not Together.}.
[20]
A kind of photosensitive layer volume, includes
Support body thin film；With,
Photosensitive layer is set on aforementioned support body thin film and includes photosensitive polymer combination,
Photosensitive resin combination include selected from by phenolic resin, polyimide precursor, polybenzoxazoles precursor and At least one kind of resin in the group of soluble polyimide composition, and the two sides of aforementioned support body thin film is contacted with aforementioned photosensitive layer.
[21]
The volume of the photosensitive layer according to [20], wherein the amount of organic solvent contained in aforementioned photosensitive layer is relative to aforementioned The total amount of photosensitive layer is 0.1 mass % or more and 15 mass % or less.
[22]
The volume of the photosensitive layer according to [21], wherein the amount of organic solvent contained in aforementioned photosensitive layer is relative to aforementioned The total amount of photosensitive layer is 1 mass % or more and 15 mass % or less.
[23]
It is rolled up according to photosensitive layer described in [21] or [22], wherein photosensitive resin combination includes aforementioned phenolic aldehyde tree Rouge.
[24]
The volume of the photosensitive layer according to any one of [21]~[23], wherein aforementioned organic solvents include selected from by γ-fourth Lactone, acetone, methyl ethyl ketone, n-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, the tert-butyl alcohol and tetrahydrofurfuryl alcohol group At at least one of group.
[25]
The volume of the photosensitive layer according to [24], wherein aforementioned organic solvents include selected from by gamma-butyrolacton, acetone, first and second At least one of ketone, n-methyl-2-pyrrolidone and group of dimethyl sulfoxide composition.
[26]
The volume of the photosensitive layer according to any one of [20]~[25], wherein before photosensitive resin combination includes State polyimide precursor.
[27]
The volume of the photosensitive layer according to any one of [20]~[25], wherein before photosensitive resin combination includes State polybenzoxazoles precursor.
[28]
The volume of the photosensitive layer according to any one of [20]~[25], wherein before photosensitive resin combination includes State soluble polyimide.
[29]
The volume of the photosensitive layer according to any one of [20]~[25], wherein photosensitive resin combination includes phenol Urea formaldehyde.
[30]
The volume of the photosensitive layer according to [29], wherein aforementioned phenolic resin has structure conduct shown in the following general formula (1) Repetitive unit,
{ in formula (1), the integer that a is 1~3, the integer that b is 0~3 is 1≤(a+b)≤4, R1It indicates selected from by carbon number 1 The substituent group for 1 valence in group that organic group, halogen atom, nitro and the cyano of~20 1 valence form, when b is 2 or 3 Multiple R1It is optionally same or different to each other, and X indicates the chain selected from the divalent by the carbon number 2~10 optionally with unsaturated bond Aliphatic group, the ester ring type group of the divalent of carbon number 3~20, divalent shown in the following general formula (2) alkylidene oxide and have The organic group of divalent in the group of the organic group composition of the divalent of aromatic ring,
——CpH2pO --- (formula 2)
(in formula (2), p be 1~10 integer.)}.
[31]
The volume of the photosensitive layer according to [30], wherein the X in aforementioned formula (1) is selected from as shown in the following general formula (3) The organic group of divalent in the group of the group composition of divalent shown in the group and following formula (4) of divalent,
In formula (3), R2、R3、R4And R5Be each independently hydrogen atom, carbon number 1~10 1 valence aliphatic group or The aliphatic group of 1 valence of carbon number 1~10 made of part or all of hydrogen atom is replaced with fluorine atom, n1 be 0~4 it is whole Number, the R when n1 is 1~4 integer6For the organic group of halogen atom, hydroxyl or 1 valence, at least one R6For hydroxyl, work as n1 For 2~4 integer when multiple R6Optionally it is same or different to each other.}
In formula (4), R7、R8、R9And R10Each independently represent hydrogen atom, carbon number 1~10 1 valence aliphatic group, Or part or all of hydrogen atom replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, and W be singly-bound, Selected from the carbon number 3~20 by optionally being replaced with the chain fatty race group of the carbon number 1~10 of fluorine atom substitution, optionally with fluorine atom Ester ring type group, divalent shown in the following general formula (2) alkylidene oxide and following formula (5) shown in divalent group composition Group in divalent organic group,
——CpH2pO --- (formula 2)
(in formula (2), p be 1~10 integer.)
[32]
It is rolled up according to photosensitive layer described in [30] or [31], wherein the X in aforementioned formula (1) is 2 shown in following formula (6) The organic group of valence,
[33]
The volume of the photosensitive layer according to [32], wherein the X in aforementioned formula (1) is having for divalent shown in following formula (7) Machine group,
[34]
The volume of the photosensitive layer according to any one of [30]~[33], wherein aforementioned phenolic resin is in same resin matrix It is interior that there is both repetitive units shown in repetitive unit shown in the following general formula (8) and the following general formula (9),
In formula (8), R11For the group of 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy, n2 1 ~3 integer, the integer that n3 is 0~2, the integer that m1 is 1~500 is 2≤(n2+n3)≤4, the R when n3 is 211Optionally that This is identical or different.}
In formula (9), R12And R13It is each independently the carbon number 1~10 in the group being made of alkyl and alkoxy The group of 1 valence, n4 be 1~3 integer, n5 be 0~2 integer, n6 be 0~3 integer, m2 be 1~500 integer, be 2≤ (n4+n5)≤4, the R when n5 is 212Optionally it is same or different to each other, the R when n6 is 2 or 313It is optionally mutually the same or not Together.}.
[35]
A kind of manufacturing method of cutting photosensitive layer volume, the manufacturing method is with cutting machine by any one of [1]~[34] institute The photosensitive layer volume stated cuts and manufactures cutting photosensitive layer volume.
[36]
The manufacturing method of cutting photosensitive layer volume according to [35], wherein heat the tooth of aforementioned cutting machine.
[37]
The manufacturing method of cutting photosensitive layer volume according to [36], wherein the tooth of aforementioned cutting machine is heated to 100 DEG C More than.
[38]
A kind of manufacturing method of cutting photosensitive layer volume comprising process below:
[1] photosensitive layer described in any one of~[34] is rolled up in the side for being equipped with aforementioned support body thin film of aforementioned photosensitive layer Opposite side have covering film in the case where, by it is aforementioned covering film removing process；
The process for being cut the aforementioned photosensitive layer volume for not having aforementioned covering film with cutting machine；With,
On the aforementioned photosensitive layer volume of cutting, attach the covering film of aforementioned removing or with the covering film of aforementioned removing not Processes of other same covering films.
[39]
The manufacturing method of cutting photosensitive layer volume according to [38], wherein heat the tooth of aforementioned cutting machine.
[40]
The manufacturing method of cutting photosensitive layer volume according to [39], wherein the tooth of aforementioned cutting machine is heated to 100 DEG C More than.
The effect of invention
According to the present invention it is possible to provide: being not likely to produce fold or crackle when cutting, can mode to keep section smoothened The photosensitive layer volume cut.
Specific embodiment
The 1st embodiment of <: the double-deck photosensitive layer rolls up >
The photosensitive layer volume of 1st embodiment of the invention supports this two layers of body thin film and photosensitive layer and shape by stacking gradually At the photosensitive layer is formed by photosensitive polymer combination, and the photosensitive polymer combination, which contains, to be selected from by phenolic resin, gathers At least one kind of resin in the group of imide precursor, polybenzoxazoles precursor and soluble polyimide composition.
In present embodiment, photosensitive layer volume is without covering film.It is laminated with photosensitive layer in the single side of support body thin film, and is propped up Another face (that is, the supporter back side or the face of photosensitive layer is not laminated) of support body film is exposed, and therefore, supports the two sides of body thin film Become to contact with photosensitive layer.
Hereinafter, the photosensitive layer volume that the two sides without covering film and support body thin film is contacted with photosensitive layer is as double-deck Photosensitive layer volume is illustrated.
Previous photosensitive layer volume has covering film, and therefore, when cutting is easy to generate fold in covering film, especially In the case that the tooth of cutting machine is heated and cut, there are problems that being easy to produce big fold in covering film.
In order to solve the above problems, the double-deck photosensitive layer volume of the 1st embodiment is characterized in that, without covering film.
< supports body thin film >
It as the support body thin film of present embodiment, is not particularly limited, can be used for example poly- as long as smooth surface The thin polymer film of ethylene glycol terephthalate, polypropylene, polyethylene, polyester etc., wherein preferred poly terephthalic acid second two Alcohol ester film (hereinafter referred to as " PET film ").
When carrying out photoetching process, from the viewpoint of photosensitive layer is transferred to substrate from the double-deck photosensitive layer volume, body thin film is supported It is preferred that implementing demoulding processing at least one face.In present embodiment demoulding processing refers to, with silicone based surfactants, The release agents such as the fluorochemicals such as the silicon-type compounds such as organic siliconresin, fluorine system surfactant, fluororesin, alkyd resin The physical treatments such as sided corona treatment are carried out compared with the chemical treatment on the surface that unfertile land coats support body thin film or to support body thin film.
In the case where coating release agent on supporting body thin film, preferably with the limit of the effect of available demoulding compared with unfertile land Coating.After coating, is handled by heat or UV, release agent can be made to be fixed on support body thin film.It is more preferably right before coating release agent Body thin film is supported to implement priming coat.
< photosensitive layer >
Photosensitive layer is by being coated with photosensitive on support body thin film, preferably on the face through demoulding processing of support body thin film Property resin combination and formed, the photosensitive polymer combination include selected from by phenolic resin, polyimide precursor, polyphenyl simultaneously At least one kind of resin in the group of oxazole precursor and soluble polyimide composition.
Hereinafter, being illustrated to ingredient contained in photosensitive polymer combination.
[photosensitive polymer combination comprising phenolic resin] [(A) ingredient: phenolic resin]
In general, phenolic resin is the heat-curing resin formed by phenolic compounds and aldehyde compound.
In present embodiment, from the viewpoint of the hot melt property of photosensitive layer, phenolic resin (A) preferably has the following general formula (1) structure shown in as repetitive unit,
{ in formula (1), the integer that a is 1~3, the integer that b is 0~3 is 1≤(a+b)≤4, R1It indicates selected from by carbon number 1 The substituent group for 1 valence in group that organic group, halogen atom, nitro and the cyano of~20 1 valence form, when b is 2 or 3 Multiple R1It is optionally same or different to each other, and X indicates the chain selected from the divalent by the carbon number 2~10 optionally with unsaturated bond Aliphatic group, the ester ring type group of the divalent of carbon number 3~20, divalent shown in the following general formula (2) alkylidene oxide and have The organic group of divalent in the group of the organic group composition of the divalent of aromatic ring,
——CpH2pO --- (formula 2)
(in formula (2), p be 1~10 integer.).}.
The phenolic resin (A) of repetitive unit with structure shown in formula (1) for example with polyimide resin and polyphenyl simultaneously Oxazole resin is compared, the solidification being able to achieve under low temperature, and can form the cured film with good elongation, and then be conducive to feel The hot melt property of photosphere.
When the excellent photosensitive layer of hot melt property is heated and cut in cutting, particularly by the tooth of cutting machine, it is not easy It cracks, can be cut in the mode for keeping section smoothened in section, therefore it is preferred that.
In above-mentioned general formula (1), R1For organic group, halogen atom, nitro and cyano selected from 1 valence by carbon number 1~20 The substituent group of 1 valence in the group of composition, from the viewpoint of alkali-solubility, preferably halogen atom, nitro, cyano, optionally tool There are the aliphatic group of the carbon number 1~10 of unsaturated bond, the aromatic group of carbon number 6~20 and selected from by the following general formula (10) Shown in 4 groups composition group in 1 valence substituent group:
In formula (10), R14、R15And R16Each independently represent hydrogen atom, optionally with the carbon number 1~10 of unsaturated bond Chain fatty race group, the ester ring type group of carbon number 3~20 or the aromatic group of carbon number 6~20, and R17Indicate optional The ester ring type group or carbon of the chain fatty race group of the divalent of carbon number 1~10 with unsaturated bond, the divalent of carbon number 3~20 The aromatic group of the divalent of number 6~20.}.
In present embodiment, in above-mentioned general formula (1), the integer that a is 1~3 goes out from the viewpoint of alkali-solubility and elongation Hair, preferably 2.A be 2 in the case where, the mutual the position of substitution of hydroxyl can be ortho position, meta position and contraposition,.The case where a is 3 Under, the mutual the position of substitution of hydroxyl can be 1,2,3-, 1,2,4- and 1,3,5- etc.,.
In present embodiment, in above-mentioned general formula (1), the integer that b is 0~3 goes out from the viewpoint of alkali-solubility and elongation Hair, preferably 0 or 1.In the case that b is 2 or 3, multiple R1It is optionally identical or different.
In turn, in present embodiment, in above-mentioned general formula (1), the relationship of 1≤(a+b)≤4 of a and b satisfaction.
In present embodiment, in above-mentioned general formula (1), X is selected from the divalent by the carbon number 2~10 optionally with unsaturated bond Chain fatty race group, the ester ring type group of divalent of carbon number 3~20, alkylidene oxide and tool shown in above-mentioned general formula (2) The organic group of the divalent in group be made of the organic group of the divalent of aromatic ring.In the organic group of these divalents, from solidification From the perspective of the viewpoint and hot melt property of the obdurability of film afterwards, X be preferably selected from the group as shown in the following general formula (3) and Organic group in the group of the group composition of divalent shown in the following general formula (4),
In formula (3), R2、R3、R4With R5 be each independently hydrogen atom, carbon number 1~10 1 valence aliphatic group or The aliphatic group of 1 valence of carbon number 1~10 made of part or all of hydrogen atom is replaced with fluorine atom, n1 be 0~4 it is whole Number, works as n1For 1~4 integer when R6For the organic group of halogen atom, hydroxyl or 1 valence, at least one R6For hydroxyl, work as n1 For 2~4 integer when multiple R6Optionally it is same or different to each other.}
In formula (4), R7、R8、R9And R10Each independently represent hydrogen atom, carbon number 1~10 1 valence aliphatic group, Or part or all of hydrogen atom replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, and W be singly-bound, Selected from the carbon number 3~20 by optionally being replaced with the chain fatty race group of the carbon number 1~10 of fluorine atom substitution, optionally with fluorine atom Ester ring type group, divalent shown in the following general formula (2) alkylidene oxide and following formula (5) shown in divalent group composition Group in divalent organic group,
——CpH2pO --- (formula 2)
(in formula (2), p be 1~10 integer.)
As the W in formula (4), from the viewpoint of the elongation of cured film and hot melt property, preferably singly-bound, selected from by upper State the divalent in the group of alkylidene oxide shown in general formula (2) and the ester group in above-mentioned formula (5), amide groups and sulfonyl composition Organic group.
In present embodiment, in above-mentioned general formula (1), the organic group of divalent shown in the preferably above-mentioned general formula (3) of X or (4), Moreover, the good viewpoint of patternability and solidification of organic group from the resin combination of divalent shown in above-mentioned general formula (4) From the perspective of the elongation and hot melt property of cured film afterwards, more preferable following formula (6):
Shown in divalent organic group, the organic group of divalent shown in particularly preferred following formula (7):
About in general formula (1) the position containing phenolic hydroxyl group and X shown in position ratio, especially from elongation Viewpoint is set out, the ratio at position shown in the X in structure shown in general formula (1) preferably 20 mass % or more, more preferable 30 matter Measure % or more.
From the viewpoint of alkali solubility, above-mentioned ratio preferably 80 mass % are hereinafter, more preferable 70 mass % or less.In addition, From the viewpoint of the hot melt property of photosensitive layer and alkali solubility, phenolic resin (A) particularly preferably has in same resin matrix Both repetitive units shown in repetitive unit shown in the following general formula (8) and the following general formula (9),
In formula (8), R11For the group of 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy, n2 1 ~3 integer, the integer that n3 is 0~2, the integer that m1 is 1~500 is 2≤(n2+n3)≤4, the R when n3 is 211Optionally that This is identical or different.}
In formula (9), R12And R13It is each independently the carbon number 1~10 in the group being made of alkyl and alkoxy The group of 1 valence, n4 be 1~3 integer, n5 be 0~2 integer, n6 be 0~3 integer, m2 be 1~500 integer, be 2≤ (n4+n5)≤4, the R when n5 is 212Optionally it is same or different to each other, the R when n6 is 2 or 313It is optionally mutually the same or not Together.}.
The m1 of general formula (8) and the m2 of above-mentioned general formula (9) indicate the total of each repetitive unit in the main chain of phenolic resin (A) Number.That is, in phenolic resin (A), structure shown in the repetitive unit and general formula (9) in bracket in structure shown in general formula (8) In bracket in repetitive unit can be arranged with random, block or their combination.M1 and m2 is from alkali-solubility and admittedly From the perspective of the elongation of compound, it is each independently 1~500 integer, lower limit value preferably 2, more preferable 3, upper limit value is excellent Select 450, more preferable 400, further preferred 350.From the viewpoint of the obdurability of the film after solidification and hot melt property, m1 and m2 Each independently preferably 2 or more, from the viewpoint of the dissolubility in alkaline aqueous solution, each independently preferably 450 or less.
Phenolic aldehyde with both structures shown in structure shown in general formula (8) and general formula (9) in same resin matrix In resin (A), the molar ratio of structure shown in general formula (8) is higher, and the film physical property after solidification is the better, heat resistance and heat fusing Property is also more excellent, and the molar ratio of structure shown in general formula (9) is higher, and alkali-solubility is the better, and the pattern form after solidification is got over It is excellent.Therefore, the range as the ratio of structure shown in structure shown in general formula (8) and general formula (9), from the film object after solidification From the perspective of property, preferably m1: m2=90:10~20:80, from the viewpoint of film physical property, alkali-solubility and hot melt property after solidification It sets out, more preferable m1: m2=80:20~40:60, from the film physical property after solidification, pattern form, alkali-solubility and hot melt property Viewpoint is set out, particularly preferred m1: m2=70:30~50:50.
Phenolic resin (A) typically comprises: phenolic compounds；With, copolymer composition, specifically selected from by the change with aldehyde radical Close object (also including the compound that aldehyde compound is decomposed and generated as trioxane), the chemical combination with ketone group Compound with 2 methylols of object, intramolecular, intramolecular compound and intramolecular with 2 alkoxy methyls have 2 The compound of one or more of the group of compound composition of a halogenated alkyl, more typically can be by making these monomer components It carries out polymerization reaction and synthesizes.For example, making aldehyde compound, ketone compound, methylol compound, alkoxy methyl compound, two The copolymer compositions such as ene compound or halogenated alkyl compounds, with phenol shown in following and/or amphyl (hereinafter, also referred to collectively as " phenolic compounds ") it is polymerize, available phenolic resin (A).Under above situation, in above-mentioned general formula (1), OH base and arbitrary R1Base is bonded to and is partially originated from above-mentioned phenolic compounds shown in the structure of aromatic rings, is partially originated from above-mentioned copolymer composition shown in X. From the viewpoint of reaction controlling and gained phenolic resin (A) and the stability of photosensitive polymer combination, phenolic compounds with The investment molar ratio (phenolic compounds: copolymer composition) of above-mentioned copolymer composition preferably 5:1~1.01:1, more preferable 2.5:1~1.1: 1.In present embodiment, the weight average molecular weight preferably 700~100000 of phenolic resin (A), it is more preferable 1500~80000, into one Step preferably 2000~50000.Weight average molecular weight is from the viewpoint of the elongation of cured film, and preferably 700 or more, on the other hand, Weight average molecular weight is from the viewpoint of the alkali-solubility of photosensitive polymer combination, and preferably 100000 or less.
Weight average molecular weight is measured by gel permeation chromatography (GPC), can be made of using standard polystyren Standard curve calculates.
In present embodiment, as the phenolic compounds that can be used to obtain phenolic resin (A), for example, cresols, second Base phenol, propylphenol, butylphenol, amyl phenol, cyclohexylphenol, xenol, benzylphenol, nitrobenzyl phenol, Cyanobenzyls phenol, adamantane phenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifloro methyl phenol, N- (hydroxy benzenes Base) -5- norbornene -2,3- dicarboximide, N- (hydroxy phenyl) -5- methyl -5- norbornene -2,3- dicarboximide, Trifloro methyl phenol, hydroxybenzoic acid, methyl hydroxybenzoate, nipagin A, hydroxy benzoic acid benzyl ester, hydroxy benzenes first Amide, hydroxy benzaldehyde, hydroxy acetophenone, dihydroxy benaophenonel, hydroxy-phenylformonitrile, resorcinol, dimethlbenzene, catechol, Methyl catechol, ethylcatechol, hexyl catechol, benzyl catechol, nitrobenzyl catechol, methyl resorcinol, ethyl Resorcinol, hexyl resorcin, benzyl resorcinol, nitrobenzyl resorcinol, quinhydrones, caffeic acid, dihydroxy-benzoic acid, Methyl dihydroxy benzoate, dihydric ethyl benzoate, dihydroxy-benzoic acid butyl ester, dihydroxy-benzoic acid propyl ester, dihydroxy benzenes Benzyl formate, dihydroxy benzoyl amine, 4-dihydroxy benzaldehyde, resacetophenone, dihydroxy benaophenonel, dihydroxy benzenes first Nitrile, N- (dihydroxy phenyl) -5- norbornene -2,3- dicarboximide, N- (dihydroxy phenyl) -5- methyl -5- norbornene - 2,3- dicarboximide, Nitrocatechol, fluorine catechol, chlorine catechol, bromine catechol, trifluoromethyl catechol, nitro isophthalic Diphenol, fluorine resorcinol, chloro resorcinol, bromine resorcinol, trifluoromethyl resorcinol, pyrogallol, phloroglucin, 1,2, 4- trihydroxy benzene, trihydroxybenzoic acid, trihydroxybenzoate, trihydroxybenzoic acid ethyl ester, trihydroxybenzoic acid butyl ester, three Nipasol, trihydroxybenzoic acid benzyl ester, trihydroxy benzene formamide, tri hydroxybenzaldehyde, trihydroxy-acetophenone, three hydroxyls Base benzophenone, trihydroxy benzene formonitrile HCN etc..
As above-mentioned aldehyde compound, for example, acetaldehyde, propionic aldehyde, special valeral, butyraldehyde, valeral, hexanal, trioxa ring Hexane, glyoxal, hexamethylene aldehyde, diphenyl acetaldehyde, ethyl butyraldehyde, benzaldehyde, glyoxalic acid, 5- norbornene -2- formaldehyde, the third two Aldehyde, butanedial, glutaraldehyde, salicylide, naphthaldehyde, terephthalaldehyde etc..
As above-mentioned ketone compound, for example, acetone, methyl ethyl ketone, metacetone, dipropyl ketone, dicyclohexyl Ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3- crotonylene -one, 2- norborneol ketone, Buddha's warrior attendant ketone, 2, Bis- (4- oxocyclohexyl) propane of 2- etc..
As above-mentioned methylol compound, for example, 2,6- bis- (hydroxymethyl)-paracresol, the bis- (hydroxyls of 2,6- Methyl) -4- ethyl -phenol, bis- (the hydroxymethyl) -4- propylphenols of 2,6-, bis- (the hydroxymethyl) -4- normal-butyl phenol of 2,6-, 2, Bis- (the hydroxymethyl) -4-TBPs of 6-, bis- (the hydroxymethyl) -4- metoxyphenols of 2,6-, bis- (the hydroxymethyl) -4- of 2,6- Bis- (the hydroxymethyl) -4- propoxyl group phenol of thanatol, 2,6-, bis- (the hydroxymethyl) -4- n-butyloxyphenols of 2,6-, 2,6- Bis- (hydroxymethyl) -4- tert-butoxy phenol, bis- (hydroxymethyl) ureas of 1,3-, ribitol, arabitol, allitol, the bis- (hydroxyls of 2,2- Ylmethyl) butyric acid, 2- benzyl Oxy-1,3-propanediol, 2,2- dimethyl -1,3- propylene glycol, 2,2- diethyl -1,3- the third two Alcohol, acetin, 2- methyl -2- nitro -1,3- propylene glycol, 5- norbornene -2,2- dimethanol, norbornene -2 5-, 3- dimethanol, pentaerythrite, 2- phenyl -1,3- propylene glycol, trimethylolethane, trimethylolpropane, bis- (the hydroxyl first of 3,6- Base) durol, 2- nitro-terephthalyl alcohol, 1,10- dihydroxy decane, 1,12- dihydroxy dodecane, bis- (the hydroxyl first of 1,4- Base) hexamethylene, bis- (hydroxymethyl) cyclohexene of 1,4-, bis- (hydroxymethyl) adamantane of 1,6-, 1,4- benzene dimethanol, 1,3- benzene two Bis- (hydroxymethyl) naphthalenes of bis- (the hydroxymethyl) -1,4- dimethoxy benzenes of methanol, 2,6-, 2,3-, bis- (hydroxymethyl) naphthalenes of 2,6-, 1, Bis- (hydroxymethyl) anthracenes of 8-, 2,2 '-bis- (hydroxymethyl) diphenyl ether, 4,4 '-bis- (hydroxymethyl) diphenyl ether, 4,4 '-bis- (hydroxyls Methyl) diphenylsulfide, 4,4 '-bis- (hydroxymethyl) benzophenone, 4- hydroxymethylbenzoic acid -4 '-hydroxymethyl phenyl ester, 4- Hydroxymethylbenzoic acid -4 '-hydroxymethyl aniline, 4,4 '-bis- (hydroxymethyl) phenylureas, 4,4 '-bis- (hydroxymethyl) phenyl Bis- (hydroxymethyl) anthracenes of carbamate, 1,8-, 4,4 '-bis- (hydroxymethyl) biphenyl, 2,2 '-dimethyl -4,4 '-bis- (hydroxyls Methyl) biphenyl, bis- (4- hyd roxymethyl phenyl) propane of 2,2-, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, the third two Alcohol, dipropylene glycol, tripropylene glycol, four propylene glycol etc..
As above-mentioned alkoxy methyl compound, for example, 2,6- bis- (methoxy)-paracresol, 2,6- are bis- Bis- (the methoxy) -4- of bis- (the methoxy) -4- propylphenols of (methoxy) -4- ethyl -phenol, 2,6-, 2,6- are just Bis- (the methoxy) -4-TBPs of butylphenol, 2,6-, bis- (the methoxy) -4- metoxyphenols of 2,6-, 2,6- Bis- (the methoxy) -4- propoxyl group phenol of bis- (methoxy) -4- thanatols, 2,6-, the bis- (methoxy methyls of 2,6- Base) -4- n-butyloxyphenol, bis- (the methoxy) -4- tert-butoxy phenol of 2,6-, bis- (methoxy) ureas of 1,3-, 2, Ice drops in bis- (the methoxy) -5- of bis- (methoxy) butyric acid of 2-, bis- (the methoxy) -5- norbornene of 2,2-, 2,3- Bis- (methoxy) hexamethylenes of piece alkene, 1,4-, bis- (methoxy) cyclohexene of 1,4-, bis- (methoxy) Buddha's warrior attendants of 1,6- Bis- (methoxy) benzene of alkane, 1,4-, bis- (methoxy) benzene of 1,3-, bis- (the methoxy) -1,4- dimethoxys of 2,6- Bis- (methoxy) naphthalenes of benzene, 2,3-, bis- (methoxy) naphthalenes of 2,6-, bis- (methoxy) anthracenes of 1,8-, 2,2 '-bis- (first Oxygroup methyl) diphenyl ether, 4,4 '-bis- (methoxy) diphenyl ether, 4,4 '-bis- (methoxy) diphenylsulfides, 4,4 '- Bis- (methoxy) benzophenone, 4- methoxy methyl yl benzoic acid -4 '-methoxy phenyl ester, 4- methoxy benzene first Sour -4 '-methoxymethylanilinepers, 4,4 '-bis- (methoxy) phenylureas, 4,4 '-bis- (methoxy) phenyl amino first Bis- (methoxy) anthracenes of acid esters, 1,8-, 4,4 '-bis- (methoxy) biphenyl, 2,2 '-dimethyl -4,4 '-bis- (methoxyl groups Methyl) biphenyl, bis- (4- methoxymethylphenyl) propane of 2,2-, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol two Methyl ether, tetraethyleneglycol dimethyl ether, Propylene Glycol Dimethyl Ether, dimethyl ether, tripropylene glycol dimethyl ether, four Propylene Glycol Dimethyl Ethers Deng.
As above-mentioned diolefin compound, for example, butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3- Methyl-1,3- butadiene, 1,3 butylene glycol-dimethylacrylate, 2,4- hexadiene -1- alcohol, methyl cyclohexadiene, ring penta 2 Alkene, cyclohexadiene, cycloheptadiene, cyclo-octadiene, bicyclopentadiene, 1- hydroxyl bicyclopentadiene, 1- methyl cyclopentadiene, methyl Bicyclopentadiene, diallyl ether, allyl sulfide, diallyl adipate, 2,5- norbornadiene, tetrahydroindene, 5- ethylidene Base -2- norbornene, 5- vinyl -2- norbornene, triallyl cyanurate, diallyl isocyanurate, isocyanuric acid three Allyl ester, isocyanuric acid diallyl propyl ester etc..
As above-mentioned halogenated alkyl compounds, for example, xylene dichloride, dichloride methyl dimethoxy benzene, double chlorine Methyl durol, dichloride methyl biphenyl, dichloride methyl-biphenyl carboxylic acids, dichloride methyl-diphenyl dicarboxylic acid, dichloride methyl-methyl Bis- (chloroethyl) ethers of biphenyl, dichloride methyl-dimethyl diphenyl, dichloride methyl anthracene, ethylene glycol, bis- (chloroethyl) ethers of diethylene glycol, Bis- (chloroethyl) ethers of triethylene glycol, bis- (chloroethyl) ethers of tetraethylene glycol etc..
Make above-mentioned phenolic compounds and copolymer composition by dehydration, dehydrohalogenation or dealcoholysis is condensed or side makes unsaturation Bond cleavage solution side is polymerize, so as to obtain phenolic resin (A).Catalysis can be used when phenolic compounds polymerize with copolymer composition Agent.
As acid catalyst, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, to toluene It is sulfonic acid, dimethyl suflfate, dithyl sulfate, acetic acid, oxalic acid, 1- hydroxy ethylidene base -1,1 '-di 2 ethylhexyl phosphonic acid, zinc acetate, borontrifluoride Boron, boron trifluoride-phenol complex, boron trifluoride ether complex etc..
As the catalyst of alkalinity, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrogen-oxygen Change barium, sodium carbonate, triethylamine, pyridine, 4-N, N- dimethyl aminopyridine, piperidines, piperazine, 1,4- diazabicyclo [2.2.2] Octane, 1,8- diazabicyclo [5.4.0] -7- endecatylene, 1,5- diazabicyclo [4.3.0] -5- nonene, ammonia, six methylenes Urotropine etc..
In present embodiment, relative to copolymer composition total molal quantity, preferably with respect to aldehyde compound, ketone compound, Methylol compound, alkoxy methyl compound, diolefin compound and halogenated alkyl compounds total molal quantity 100 rub You are %, and the amount of the catalyst for obtaining phenolic resin (A) is preferably the range of 0.01 mole of %~100 mole %.
When carrying out the synthetic reaction of phenolic resin (A), organic solvent can be used as needed.It is organic as what can be used The concrete example of solvent, does not limit, and can enumerate bis- (2- methoxy ethyl) ethers, methyl cellosolve, ethyl cellosolve, propylene glycol Monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, dimethyl ether, cyclohexanone, cyclopentanone, toluene, two Toluene, gamma-butyrolacton, n-methyl-2-pyrrolidone etc..When the gross mass for putting into raw material is set as 100 mass parts, these are organic The dosage of solvent is usually 10 mass parts~1000 mass parts, preferably 20 mass parts~500 mass parts.In addition, phenolic resin (A) Synthetic reaction in, preferably 40 DEG C~250 DEG C of reaction temperature, more preferable 100 DEG C~200 DEG C of range, moreover, the reaction time is excellent Choosing substantially 1 hour~10 hours.
It should be noted that phenolic resin (A) can be in the range of not impairing the effect of the present invention, such as to become The 30% of the phenolic compounds total mole number of the raw material of phenolic resin (A) is further below using the knot for not becoming above-mentioned general formula (1) The phenolic compounds of the raw material of structure carries out the person of being polymerized.
In present embodiment, in above-mentioned general formula (1), a be 1 in the case where, in order to improve alkali-solubility, can will selected from by Novolac resin and polyhydroxystyrene resin composition group in phenolic resin (hereinafter also referred to as phenolic resin (A ')) with Phenolic resin (A) mixing.
The mixing ratio of phenolic resin (A) and phenolic resin (A ') preferably (A)/(A ')=10/90~90/10 by quality ratio Range.The mixing ratio is from the viewpoint of the elongation of dissolubility and cured film in alkaline aqueous solution, preferably (A)/(A ') =10/90~90/10, more preferable (A)/(A ')=20/80~80/20, further preferred (A)/(A ')=30/70~70/30.
Above-mentioned novolac resin can be by obtaining phenols and formaldehyde and being condensed in the presence of acidic catalysts It arrives.As above-mentioned phenols, for example, phenol, o-cresol, metacresol, paracresol, o-ethyl phenol, m-ethylphenol, Paraethyl phenol, adjacent butylphenol, butylphenol, p-butylphenol, 2,3 xylidine phenol, 2,4- dimethlbenzene, 2,5- bis- Cresols, 2,6- dimethlbenzene, 3,4- dimethlbenzene, 3,5- dimethlbenzene, 2,3,5- pseudocuminol, 3,4,5- trimethylbenzene Phenol, catechol, resorcinol, pyrogallol, alpha-Naphthol, betanaphthol etc..As specific novolac resin, such as can lift Phenol/formaldehyde condensation novolac resin, cresol/formaldehyde are condensed novolac resin, phenol-naphthols/formaldehyde condensation phenolic aldehyde out Varnish gum etc..
As above-mentioned polyhydroxystyrene resin, preferably poly- 4-Vinyl phenol.As long as poly- 4-Vinyl phenol be containing 4-Vinyl phenol is just not particularly limited as the polymer of polymerized unit.Can constitute poly- 4-Vinyl phenol, to ethylene Polymerized unit other than base phenol can be with any for that can be copolymerized with 4-Vinyl phenol without departing from the purpose of the present invention Compound.Can with 4-Vinyl phenol be copolymerized compound for example: methyl acrylate, methyl methacrylate, Hydroxyethyl Acrylate, butyl methacrylate, 2-ethyl hexyl acrylate, acrylic acid 2- ethoxy ethyl ester, tert-butyl acrylate, 1,5- Diacrylate, acrylic acid N, N- diethylamino ethyl ester, glycol diacrylate, 1,3- propylene glycol diacrylate Ester, decanediol diacrylate, decanediol dimethylacrylate, 1,4- cyclohexanediol diacrylate, 2,2- dihydroxymethyl Propane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, three glycerol acrylates, 2,2- bis- are (to hydroxyl Phenyl)-propane dimethylacrylate, triethylene glycol diacrylate, two (p-hydroxybenzenes)-the third of polyoxy ethyl -2-2- Alkane dimethylacrylate, triethylene glycol dimethacrylate, polyoxy propyl trimethylolpropane trimethacrylate, second two Alcohol dimethylacrylate, butanediol dimethylacrylate, 1,3- dimethacrylate, butanediol dimethyl propylene Olefin(e) acid ester, 1,3- dimethacrylate, 1,2,4- butantriol trimethyl acrylic ester, 2,2,4- trimethyl -1,3- Dimethacrylate, pentaerythritol acrylate trimethyl, 1- phenyl-ethylene -1,2- dimethylacrylate, Pentaerythritol tetramethylacrylate, trimethylol-propane trimethacrylate, 1,5- dimethacrylate and The ester of acrylic acid as 1,4- Benzenediol dimethylacrylate；Styrene and, for example, 2-methyl styrene and vinyl Substituted phenylethylene as toluene；Vinyl esters as vinyl acrylate and metering system ethylene acid esters；Adjacent vinyl benzene Phenol and the such vinylphenol in addition to 4-Vinyl phenol of vinylphenol；Equal monomers, but it is not limited to these.
Phenolic resin (A ') is (that is, the phenolic aldehyde in the group being made of novolac resin and polyhydroxystyrene resin Resin) weight average molecular weight preferably 700~100000, more preferable 1500~80000, further preferred 2000~50000.Weight is equal Molecular weight is from the viewpoint of the elongation of cured film, and preferably 700 or more, on the other hand, from the alkali of photosensitive polymer combination From the perspective of dissolubility, preferably 100000 or less.
It should be noted that the phenolic resin in the group being made of novolac resin and polyhydroxystyrene resin It can be used alone, two or more can also be mixed and used.
[photoacid generator (B)]
In present embodiment, photosensitive polymer combination is representative for that can incude with ultraviolet light, electron beam, X-ray etc. Active ray (that is, radiation) and form the composition of resin pattern.Photosensitive polymer combination can be minus (that is, not Irradiation portion passes through the dissolution person that develops) or eurymeric (that is, irradiation portion passes through the dissolution person that develops),.
In present embodiment, in the case that photosensitive polymer combination is used as the photosensitive polymer combination of minus, Photoacid generator (B) is generated acid by irradiation with radiation, and the acid of generation causes above-mentioned phenolic resin (A) and the crosslinking of crosslinking agent anti- It answers, so that irradiation with radiation portion becomes insoluble in developer solution.The photoacid generator (B) that can be used as minus, such as can lift Compound below out:
(i) trichloromethyl-s-triazine
Three (2,4,6- trichloromethyl)-s-triazine, 2- phenyl-bis- (4,6- trichloromethyl)-s-triazine, 2- (3- chlorobenzene Base)-bis- (4,6- trichloromethyl)-s-triazine, 2- (2- chlorphenyl)-bis- (4,6- trichloromethyls)-s-triazine, 2- (4- methoxyl group Phenyl)-bis- (4,6- trichloromethyl)-s-triazine, 2- (3- methoxyphenyl)-bis- (4,6- trichloromethyls)-s-triazine, 2- (2- Methoxyphenyl)-bis- (4,6- trichloromethyl)-s-triazine, 2- (4- methylthiophenyi)-bis- (4,6- trichloromethyl)-equal three Bis- (4,6- trichloromethyl-s-triazine, 2- (2- methylthiophenyi)-bis- (tri- chloromethanes of 4,6- of piperazine, 2- (3- methylthiophenyi) Base)-s-triazine, 2- (4- methoxyl group naphthalene)-bis- (4,6- trichloromethyls)-s-triazine, 2- (3- methoxyl group naphthalene)-bis- (4,6- Trichloromethyl)-s-triazine, 2- (2- methoxyl group naphthalene)-bis- (4,6- trichloromethyls)-s-triazine, 2- (3,4,5- trimethoxy- β-styryl)-bis- (4,6- trichloromethyl)-s-triazine, 2- (4- methyl thio-β-styryl)-bis- (tri- chloromethanes of 4,6- Base)-s-triazine, 2- (3- methyl thio-β-styryl)-bis- (4,6- trichloromethyls)-s-triazine, 2- (2- methyl thio-β- Styryl)-bis- (4,6- trichloromethyl)-s-triazine etc.；
(ii) Diaryl iodonium salt
Diphenyl iodine tetrafluoroborate, four fluorophosphate of diphenyl iodine, diphenyl iodine tetrafluoro arsenate, diphenyl Iodine fluoroform sulphonate, diphenyl iodine trifluoroacetate, the iodo- tosilate of diphenyl, 4- methoxyphenyl benzene Base iodine tetrafluoroborate, 4- methoxyphenyl phenyl-iodide hexafluorophosphonate, 4- methoxyphenyl phenyl-iodide hexafluoroarsenate Salt, 4- methoxyphenyl phenyl-iodide fluoroform sulphonate, 4- methoxyphenyl phenyl-iodide trifluoroacetate, 4- methoxybenzene The iodo- tosilate of base phenyl, bis- (4- tert-butyl-phenyl) iodine tetrafluoroborates, bis- (4- tert-butyl-phenyl) iodine six It is fluorine arsenate, bis- (4- tert-butyl-phenyl) iodine fluoroform sulphonates, bis- (4- tert-butyl-phenyl) iodine trifluoroacetates, double (4- tert-butyl-phenyl) iodo- tosilate etc.；
(iii) triaryl matte salt
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium methylsulphur Hydrochlorate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-tosilate, 4- methoxyphenyl diphenyl sulfonium tetrafluoroborate, 4- methoxyphenyl diphenyl sulfonium hexafluorophosphonate, 4- methoxyphenyl diphenyl sulfonium hexafluoro arsenate, 4- methoxyphenyl two Phenyl sulfonium mesylate, 4- methoxyphenyl diphenyl sulfonium trifluoroacetate, 4- methoxyphenyl diphenyl sulfonium-p-methyl benzenesulfonic acid Salt, 4- phenylthiophenyl diphenyl tetrafluoroborate, 4- phenylthiophenyl diphenyl hexafluorophosphonate, 4- phenyl benzene Base diphenyl hexafluoro arsenate, 4- phenylthiophenyl diphenylsulfonium mesylate, 4- phenylthiophenyl diphenylsulfonium Acetate, 4- phenylthiophenyl diphenyl-tosilate etc..
Among these compounds, as trichloromethyl-s-triazine, preferably 2- (3- chlorphenyl)-bis- (4,6- tri- chloromethanes Base)-s-triazine, 2- (4- chlorphenyl)-bis- (4,6- trichloromethyls)-s-triazine, 2- (4- methylthiophenyi)-bis- (4,6- tri- Chloromethyl)-s-triazine, 2- (4- methoxyl group-β-styryl)-bis- (4,6- trichloromethyls)-s-triazine, 2- (4- methoxynaphthalene Base)-bis- (4,6- trichloromethyl)-s-triazine etc..
As Diaryl iodonium salt, preferably diphenyl iodine trifluoroacetate, diphenyl iodine fluoroform sulphonate, 4- Methoxyphenyl phenyl-iodide fluoroform sulphonate, 4- methoxyphenyl phenyl-iodide trifluoroacetate etc..
As triaryl matte salt, preferably triphenylsulfonium mesylate, triphenylsulfonium trifluoroacetate, 4- methoxyphenyl Diphenyl sulfonium mesylate, 4- methoxyphenyl diphenyl sulfonium trifluoroacetate, 4- phenylthiophenyl diphenylsulfonium methylsulphur Hydrochlorate, 4- phenylthiophenyl diphenylsulfonium acetate etc..
In addition, compound shown below also can be used as photoacid generator (B).
(1) diazonium ketone compound
As diazonium ketone compound, for example, 1,3- diketone -2- diazonium compound, diazoquinone compound, again Quinoline naphtoquinone compounds etc..As concrete example, 1,2- naphthoquinones, the two nitrine -4- sulfonate compound of phenols can be enumerated.
(2) sulphones
As sulphones, for example, β -one sulphones, 'Beta '-sulfonyl sulphones and these compounds α-diazonium compound.As concrete example, 4- tri-benzoyl methyl sulfone, mesitylene base phenacyl sulfone, bis- (benzene can be enumerated Formyl methyl sulfonyl) methane etc..
(3) sulfoacid compound
As sulfoacid compound, for example, alkyl sulfonates, haloalkyl sulfonate class, aromatic yl sulphonate Class, iminosulfonate class etc..As the preferred concrete example of sulfoacid compound, benzoin tosylate, even benzene can be enumerated Triphenol three (trifluoromethayl sulfonic acid ester), adjacent nitro benzyl trifluoromethayl sulfonic acid ester, adjacent nitro benzyl-p-methyl benzenesulfonic acid ester etc..
(4) sulfimine compound
As sulfimine compound, for example, N- (trifluoromethyl sulfonyl oxygroup) succinimide, N- (three Methyl fluoride sulfonyl oxygroup) phthalimide, N- (trifluoromethyl sulfonyl oxygroup) diphenylmaleimide, N- (three Methyl fluoride sulfonyl oxygroup) bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide, N- (trifluoromethyl sulfonyl oxygroup) naphthalene Acid imide etc..
(5) oxime ester compound
As oxime ester compound, specifically, 2- [2- (4- methylphenylsulfonyl oxygroup imino group) 2,3- can be enumerated Dihydro-thiophene -3- pitches base] -2- (2- aminomethyl phenyl) acetonitrile (Ciba Specialty Chemicals Corporation commodity Name " IRGACURE PAG121 "), [2- (sulfonyl propyl base oxygroup imino group) -2,3- dihydro-thiophene -3- pitch base] -2- (2- methyl Phenyl) acetonitrile (Ciba Specialty Chemicals Corporation trade name " IRGACURE PAG103 "), [2- is (just Perfluorooctane sulfonyl base oxygroup imino group) -2,3- dihydro-thiophene -3- fork base] -2- (2- aminomethyl phenyl) acetonitrile (Ciba Specialty Chemicals Corporation trade name " IRGACURE PAG108 "), α-(normal octane sulfonyl oxygroup imino group) -4- first Oxy-benzyl cyanogen (Ciba Specialty Chemicals Corporation trade name " CGI725 ") etc..
(6) diazomethane compound
As diazomethane compound, specifically, bis- (trifluoromethyl sulfonyl) diazomethanes, bis- (rings can be enumerated Hexyl sulfonyl) diazomethane, bis- (phenyl sulfonyl) diazomethanes etc..
From the viewpoint of sensitivity, particularly preferred above-mentioned (5) oxime ester compound.
In present embodiment, in the case that photosensitive polymer combination is minus, photoacid generator (B) is relative to phenolic resin (A) compounding amount of 100 mass parts preferably 0.1~50 mass parts, more preferable 1~40 mass parts.The compounding amount is if it is 0.1 mass Part or more, then can obtain the improvement effect of sensitivity well, the compounding amount if it is 50 below the mass, cured film Mechanical properties are good.
In present embodiment, the photosensitive polymer combination that photosensitive polymer combination can also be used as eurymeric is used.On In the case of stating, two nitrine chemical combination of photoacid generator shown in above-mentioned (i)~(iii) and (1)~(6) and/or quinone can be used Object.Wherein, from the viewpoint of the physical property after solidification, preferred quinone di-azido compound.This is because, quinone di-azido compound exists It is thermally decomposed when solidification, the amount remained in the film after solidifying is extremely low.Therefore, the photoacid generator (B) of eurymeric preferably quinone two is folded Nitrogen compound.
As quinone di-azido compound, can enumerate with 1,2- benzoquinones, two nitrine structure or 1, two nitrine structure of 2- naphthoquinones The compound of (hereinafter, the compound of the structure with the latter is also referred to as " NQD compound ").These compounds are for example recorded in No. 2,772,972 specifications of U.S. Patent No., No. 2,797,213 specifications of U.S. Patent No., U.S. Patent No. 3,669,658 Specification etc..The NQD compound is selected from (hereinafter also referred to " more by the compound with multiple phenolic hydroxyl group described below Hydroxy compounds ") two nitrine -4- sulphonic acid ester of 1,2- naphthoquinones and the polyol two nitrine -5- sulfonic acid of 1,2- naphthoquinones At least one kind of compound in the group of ester composition.
NQD compound can obtain as follows: according to conventional method, by two nitrine sulfonic acid chlorosulfonic acid of naphthoquinones or thionyl chloride Etc. being converted into sulfonic acid chloride, makes two nitrine sulfonic acid chloride of gained naphthoquinones, carries out condensation reaction with polyol, to obtain.Example It can such as obtain: be folded by polyol, with the two nitrine -5- sulfonic acid chloride of 1,2- naphthoquinones or 1,2- naphthoquinones two of specified amount as follows Nitrogen -4- sulfonic acid chloride in dioxane, acetone or tetrahydrofuran equal solvent, in the presence of the basic catalysts such as triethylamine Under reacted and be esterified, products therefrom is washed and is dried, so as to obtain.
It, can be with as the example of preferred NQD compound from the viewpoint of the cured films physical property such as sensitivity and elongation Enumerate substance shown in the following general formula group:
{ in formula, Q is two nitrine sulfonate group of naphthoquinones shown in any one of hydrogen atom or following formula group, but whole Q It is not simultaneously hydrogen atom,
In addition, also can be used has two nitrine sulfonyl of 4- naphthoquinones and 5- naphthoquinones as NQD compound in same molecule The two nitrine sulfonyl ester compounds of naphthoquinones of two nitrine sulfonyls, or can also be by two nitrine sulfonyl ester compounds of 4- naphthoquinones It mixes and uses with two nitrine sulfonyl ester compounds of 5- naphthoquinones.
Above-mentioned NQD compound, which can be used alone, can also mix two or more and be used.
In present embodiment, the dosage of the photoacid generator (B) when photosensitive polymer combination is eurymeric is relative to this combination 100 mass parts of phenolic resin (A) of object, preferably 0.1~70 mass parts, more preferable 1~40 mass parts, further preferred 5~30 Mass parts.The dosage if it is 0.1 mass parts more than, available good sensitivity, below the mass if it is 70, The mechanical properties of cured film are good.
[solvent (C)]
As solvent (C), amides, sulfoxide type, ureas, ketone, esters, lactone, ethers, halogenated hydrocarbon can be enumerated N-methyl-2-pyrrolidone, n,N-dimethylacetamide, n,N-Dimethylformamide, two can be used for example in class, hydro carbons etc. Methyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, second Acid butyl ester, diethy-aceto oxalate, ethyl lactate, methyl lactate, butyl lactate, gamma-butyrolacton, propylene glycol methyl ether acetate, third Glycol monomethyl ether, benzylalcohol, styrene glycol, tetrahydrofurfuryl alcohol, the tert-butyl alcohol, glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydro furan Mutter, morpholine, methylene chloride, 1,2- dichloroethanes, 1,4- dichloroetane, chlorobenzene, o-dichlorohenzene, methyl phenyl ethers anisole, hexane, heptane, benzene, Toluene, dimethylbenzene, mesitylene etc..Wherein, from the dissolubility of resin, the stability of resin combination, to the cementability of substrate, From the perspective of hot melt property, storage stability and adhesive, preferably gamma-butyrolacton, acetone, methyl ethyl ketone, N- methyl -2- pyrrole Pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, the tert-butyl alcohol and tetrahydrofurfuryl alcohol, wherein particularly preferred gamma-butyrolacton, acetone, Methyl ethyl ketone, n-methyl-2-pyrrolidone and dimethyl sulfoxide.
[organic silicon type surfactant (D)]
Organic silicon type surfactant refers to that intramolecular has the surfactant of siloxanes key and silicon-carbon bond.Such as it can To enumerate dimethyl siloxane ethyleneoxy group graft compound, dimethyl siloxane propylidene oxygroup graft compound, (hydroxyl Ethyleneoxy group propyl) methylsiloxane-dimethyl silica hydride compounds etc..
As the concrete example of organic silicon type surfactant, can enumerate organic siloxane polymer KF-640,642, 643, KP341, X-70-092, X-70-093 (more than, trade name, Shin-Etsu Chemial Co., Ltd's system), SH-28PA, SH- 190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (more than, trade name, Dow Corning Toray Silicone Co Ltd system), SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ- 2166, L-7604 (more than, trade name, Nippon Unicar Co.Ltd. system), DBE-814, DBE-224, DBE-621, CMS- 626、CMS-222、KF-352A、KF-354L、KF-355A、KF-6020、DBE-821、DBE-712(Gelest)、BYK-307、 BYK-310, BYK-378, BYK-333 (more than, trade name, BYK JAPAN KK system), Glanol (trade name, common prosperity society chemistry Co. Ltd. system) etc..Wherein, from the viewpoint of the coating of composition varnish, preferred dimethyl siloxane ethyleneoxy group Graft compound and dimethyl siloxane propylidene oxygroup graft compound.These organic silicon type surfactants can be independent Using a kind or combines two or more and use.
The dosage of organic silicon type surfactant (D) is from the viewpoint of composition varnish is to the coating of supporter, phase For 100 mass parts of phenolic resin (A), preferably 0.01~30 mass parts, more preferable 0.02~10 mass parts.Organic silicon type surface The dosage of activating agent (D) below the mass, can inhibit residue and pattern when development to float if it is 30.
[other compositions]
In the photosensitive polymer combination of present embodiment, crosslinking agent (E), thermal acid generator, silicon can be contained as needed Alkane coupling agent, dyestuff, dissolution accelerator etc..
Crosslinking agent (E) is following compound: the embossment figure that the photosensitive polymer combination of present embodiment will be used to be formed When case is heating and curing, the compound of cross-linked network can be formed with phenolic resin (A) crosslinking or crosslinking agent itself.Crosslinking agent (E) as long as there is no limit to can be carried out the compound of heat cross-linking.In general, crosslinking agent has 2 or more in the molecule Crosslinked group, and can be further improved the thermal characteristics of the cured film formed by photosensitive polymer combination, mechanical property and resistance to Chemicals.
As crosslinking agent (E), for example: as the compound containing methylol and/or alkoxy methyl, CYMEL (registered trademark) 300,301,303,370,325,327,701,266,267,238,1141,272,202,1156, 1158,1123,1170,1174, UFR65,300, MYCOAT102,105 (more than, Mitsui-Cytec Ltd. system), Nikalac (registered trademark) MX-270, -280, -290, Nikalac MS-11, Nikalac MW-30, -100, -300, -390, -750 (with On, SANWA Chemical Co., Ltd. system), DML-OCHP, DML-MBPC, DML-BPC, DML-PEP, DML-34X, DML- PSBP、DML-PTBP、DMLPCHP、DML-POP、DML-PFP、DML-MBOC、BisCMP-F、DML-BisOC-Z、DML- BisOCHP-Z, DML-BisOC-P, DMOM-PTBT, TMOM-BP, TMOM-BPA, TML-BPAF-MF (more than, Honshu chemistry work Industry Co. Ltd. system), benzene dimethanol, bis- (hydroxymethyl) cresols, bis- (hydroxymethyl) dimethoxy benzenes, bis- (hydroxymethyls) two Phenylate, bis- (hydroxymethyl) benzophenone, hydroxymethylbenzoic acid hydroxymethyl phenyl ester, bis- (hydroxymethyl) biphenyl, dimethyl Bis- (hydroxymethyl) biphenyl, bis- (methoxy) benzene, bis- (methoxy) cresols, bis- (methoxy) dimethoxys Benzene, bis- (methoxy) diphenyl ether, bis- (methoxy) benzophenone, methoxy methyl yl benzoic acid methoxy benzene Ester, bis- (methoxy) biphenyl, bis- (methoxy) biphenyl of dimethyl etc..
In addition, can be enumerated as crosslinking agent (E): as oxirane compound, phenol novolak-type epoxy tree Rouge, cresol novolak type epoxy resin, bisphenol-type epoxy resin, tris phenol type epoxy, four phenol-type epoxy resins, phenol- Phenylenedimethylidyne type epoxy resin, naphthols-phenylenedimethylidyne type epoxy resin, phenol-naphthol type epoxy resin ,-two ring of phenol Pentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, diethylene glycol diglycidyl glycerin ether, D-sorbite Polyglycidyl ether, propylene glycol diglycidylether, trimethylolpropane polyglycidylether, tetra- (para hydroxybenzene of 1,1,2,2- Base) four glycidol ether of ethane, T 55, o-sec-butyl phenyl glycidol ether, bis- (the 2,3- epoxies third of 1,6- Oxygroup) naphthalene, two glycerol polyglycidyl ethers, Polyethylene Glycol Bisglycidyl Ether, YDB-340, YDB-412, YDF-2001, YDF- 2004 (more than, trade name, NIPPON STEEL Chemical&Material Co., Ltd. system), NC-3000-H, EPPN- 501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (more than, trade name, Nippon Kayaku Co., Ltd. system), Epikote (registered trademark) 1001, Epikote 1007, Epikote 1009, Epikote 5050, Epikote 5051, Epikote 1031S, Epikote 180S65, Epikote 157H70, YX-315-75 (more than, commodity Name, Japan Epoxy Resins Co.Ltd., system), EHPE3150, PLACCEL G402, PUE101, PUE105 (more than, quotient The name of an article, Daicel Chemical Industries Ltd. system), Epiclon (registered trademark) 830,850,1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (more than, trade name, Dainippon Ink Chemicals's system), Denacol (registered trademark) EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX- 512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (more than, trade name, Nagase ChemteX Corporation system), Epolight (registered trademark) 70P, Epolight 100MF (more than, commodity Name, Kyoeisha Chemical Co.Ltd. system) etc..
In addition, as crosslinking agent (E), can enumerate it is as the compound containing isocyanate group, 4,4 '-diphenyl methanes Diisocyanate, toluene di-isocyanate(TDI), 1,3- phenylene dimethylene diisocyanate, dicyclohexyl methyl hydride -4,4 '-two are different Cyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, Takenate (registered trademark) 500,600, COSMONATE (registered trademark) NBDI, ND (more than, trade name, Mitsui Chemicals, Inc's system) Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (more than, trade name, Asahi Kasei Chemicals Corporation system) etc..
In addition, as crosslinking agent (E), can enumerate it is as bismaleimide compound, 4,4 '-diphenyl methanes are double Maleimide, phenylmethane maleimide, meta-phenylene bismaleimide, bisphenol-A Diphenyl Ether Bismaleimide, 3, 3 '-dimethyl -5,5 '-diethyl -4,4 '-diphenyl methane bismaleimide, 4- methyl-1,3- phenylene bismaleimide Amine, 1,6 '-bismaleimide-(2,2,4- trimethyl) hexane, 4,4 '-Diphenyl Ether Bismaleimides, 4,4 '-diphenyl sulfones Bis- (3- maleimidephenoxy) benzene of bismaleimide, 1,3-, 1,3- bis- (4- maleimidephenoxy) benzene, BMI- 1000、BMI-1100、BMI-2000、BMI-2300、BMI-3000、BMI-4000、BMI-5100、BMI-7000、BMI-TMH、 BMI-6000, BMI-8000 (more than, trade name, Daiwa Kasei Industry Co., Ltd.'s system) etc..
As compounding amount when using crosslinking agent (E), relative to 100 mass parts of phenolic resin (A), preferably 0.1~40 matter Measure part, more preferable 1~30 mass parts.The compounding amount if it is 0.1 mass parts more than, the hot physical property and machinery of heat cured film are strong Degree is good, and below the mass if it is 40, the elongation of stability and heat cured film under the varnish state of composition is good.
The hot physical property of good solidfied material and the viewpoint of mechanical properties are embodied from reducing in the case where solidification temperature It sets out, thermal acid generator, which is preferably matched, is mixed in resin combination.
As thermal acid generator, as long as to generate the compound of acid by heat, there is no limit, for example, chlorine Allyl acetate, Solid acid n-butyl chloroacete, chloroacetic acid tert-butyl ester, ethyl chloroacetate, methyl chloroacetate, benzyl chloracetate, monoxone Isopropyl ester, monoxone 2- methoxy acrylate, methyl dichloroacetate, methyl trichloroacetate, ethyl trichloroacetate, trichloroacetic acid 2- second Oxygroup ethyl ester, t-butylcyanoacetate, Tert-butyl Methacrylate, Trifluoroacetic Acid Ethyl Ester, trifluoro-acetate, trifluoroacetic acid benzene Ester, vinyl trifluoroacetate, trifluoroacetic acid isopropyl ester, trifluoroacetic acid allyl ester, ethyl benzoate, methyl benzoate, benzoic acid The tert-butyl ester, 2- chloro benzoic ether, 2- chlorobenzoic acid ethyl ester, 4- chlorobenzoic acid ethyl ester, 2,5- ethyl dichloro-benzoate, 2,4- bis- Chloro benzoic ether, parafluorobenzoic acid ethyl ester, parafluorobenzoic acid methyl esters, five chlorophenyl carboxylic acid tert-butyl ester, five fluorine methyl propionates, five The carboxylic acid esters such as fluorine ethyl propionate, crotons tert-butyl acrylate；The cyclic carboxylic acids esters such as phenolphthalein, thymolphthalein；Ethyl methane sulfonate, methylsulphur Sour methyl esters, methanesulfonic acid 2- methoxy acrylate, methanesulfonic acid 2- isopropoxyethyl cyanoacrylate, p-methyl benzenesulfonic acid phenyl ester, ethyl p-toluenesulfonate, P-TOLUENE SULFO ACID 99's methyl esters, p-methyl benzenesulfonic acid 2- phenyl chlorocarbonate, p-methyl benzenesulfonic acid n-propyl, p-methyl benzenesulfonic acid N-butyl, to toluene sulphur The just own ester of tert-butyl acrylate, p-methyl benzenesulfonic acid, the positive heptyl ester of p-methyl benzenesulfonic acid, p-methyl benzenesulfonic acid n-octyl, p-methyl benzenesulfonic acid 2- methoxy It is base ethyl ester, p-methyl benzenesulfonic acid alkynes propyl ester, p-methyl benzenesulfonic acid 3- butine ester, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid N-butyl, complete Fluorine butane sulfonic acid, perfluorobutane methyl esters, benzyl (4- hydroxy phenyl) methyl sulfonium hexafluoro antimonate, benzyl (4- hydroxyl Phenyl) methyl sulfonium hexafluorophosphate, trimethylsulfonium Methylsulfate, three-p- sulfonium trifluoro-methanyl sulfonates, trimethylsulfonium trifluoro The sulfonic acid esters such as mesylate, pyridine-tosilate, perfluorooctane sulfonate ethyl ester；1,4- butyl sultone, 2,4- fourth The cyclic sulfonic acid esters classes such as sultones, 1,3- propane sultone, phenol red, bromocresol green, bromocresol purple；2- sulfosalicylic acid acid anhydride, Aromatic carboxylic acids acid anhydride such as p-toluenesulfonic anhydride, phthalic anhydride etc..
As compounding amount when using thermal acid generator, relative to 100 mass parts of (A) phenolic resin, preferably 0.1~30 mass Part, more preferable 0.5~10 mass parts, further preferred 1~5 mass parts.Compounding amount if it is 0.1 mass parts more than, keep Pattern form after heat cure works well, on the other hand, compounding amount if it is 30 below the mass, to lithography performance without Adverse effect, and composition has good stability.
As silane coupling agent, for example, 3-mercaptopropyi trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry strain formula meeting Society's system: trade name KBM803, Chisso corporation system: trade name Silaace S810), 3- mercaptopropyi triethoxy Silane (Azmax Co. Ltd. system: trade name SIM6475.0), 3- mercapto propyl methyl dimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry Co. Ltd. system: trade name LS1375, Azmax Co. Ltd. system: trade name SIM6474.0), mercapto methyl trimethoxy silane (Azmax Co. Ltd. system: trade name SIM6473.5C), mercapto methyl methyl dimethoxysilane (Azmax Co. Ltd. system: Trade name SIM6473.0), 3- mercaptopropyi diethoxy methoxy silane, 3- mercaptopropyi ethyoxyl dimethoxysilane, 3- Mercaptopropyi tripropoxy silane, 3- mercaptopropyi diethoxy npropoxysilane, 3- mercaptopropyi ethyoxyl dipropoxy silicon Alkane, 3- mercaptopropyi dimethoxy npropoxysilane, 3- mercaptopropylmethoxy dipropoxy silane, 2- mercaptoethyl trimethoxy Base silane, 2- mercaptoethyl diethoxy methoxy silane, 2- mercaptoethyl ethyoxyl dimethoxysilane, 2- mercaptoethyl three Npropoxysilane, 2- mercaptoethyl tripropoxy silane, 2- mercaptoethyl ethyoxyl dipropoxy silane, 2- mercaptoethyl diformazan Oxygroup npropoxysilane, 2- mercaptoethyl methoxyl group dipropoxy silane, 4- mercaptobutyl trimethoxy silane, 4- mercaptobutyl Triethoxysilane, 4- mercaptobutyl tripropoxy silane, N- (3- triethoxysilylpropyltetrasulfide) urea (SHIN-ETSU HANTOTAI's chemical industry Co. Ltd. system: trade name LS3610, Azmax Co. Ltd. system: trade name SIU9055.0), N- (3- trimethyoxysilane Base propyl) urea (Azmax Co. Ltd. system: trade name SIU9058.0), N- (3- diethoxy trimethoxysilylpropyl) Urea, N- (3- ethyoxyl dimethoxysilyl propyl) urea, N- (3- tripropoxy-silicane base propyl) urea, N- (3- diethyl Oxygroup isopropoxysilyl group propyl) urea, N- (3- ethyoxyl dipropoxy silylpropyl) urea, N- (3- dimethoxy third Oxygroup silylpropyl) urea, N- (3- methoxyl group dipropoxy silylpropyl) urea, N- (3- trimethoxysilyl Ethyl) urea, N- (3- ethyoxyl dimethoxysilyl ethyl) urea, N- (3- tripropoxy-silicane base ethyl) urea, N- (3- Tripropoxy-silicane base ethyl) urea, N- (3- ethyoxyl dipropoxy silyl ether) urea, N- (the third oxygen of 3- dimethoxy Base silyl ether) urea, N- (3- methoxyl group dipropoxy silyl ether) urea, N- (3- trimethoxysilyl fourth Base) urea, N- (3- triethoxysilyl butyl) urea, N- (3- tripropoxy-silicane base butyl) urea, 3- (m-aminophenyl oxygen Base) propyl trimethoxy silicane (Azmax Co. Ltd. system: trade name SLA0598.0), m-aminophenyl base trimethoxy silane (Azmax Co. Ltd. system: trade name SLA0599.0), p-aminophenyl trimethoxy silane (Azmax Co. Ltd. system: commodity Name SLA0599.1) aminophenyl trimethoxy silane (Azmax Co. Ltd. system: trade name SLA0599.2), 2- (trimethoxy Silyl ether) pyridine (Azmax Co. Ltd. system: trade name SIT8396.0), 2- (triethoxysilylethyl) pyrrole Pyridine, 2- (dimethoxysilyl Methylethyl) pyridine, 2- (diethoxy silyl methyl ethyl) pyridine, (tri- second of 3- Oxygroup silylpropyl)-t-butylcarbamate, (3- glycidoxypropyl group) triethoxysilane, tetramethoxy-silicane Alkane, tetraethoxysilane, four-positive propoxy silane, four-isopropoxy silane, four-n-butoxy silanes, four-isobutoxy silicon Alkane, four-tert-butoxy silanes, four (methoxy-ethoxy-silanes), four (methoxyl groups-positive propoxy silane), four (ethoxy ethoxies Base silane), four (methoxyethoxyethoxy silane), bis- (trimethoxysilyl) ethane, bis- (trimethyoxysilanes Base) hexane, bis- (triethoxysilyl) methane, bis- (triethoxysilyl) ethane, bis- (triethoxy-silicanes Base) ethylene, bis- (triethoxysilyl) octanes, bis- (triethoxysilyl) octadienes, bis- [3- (triethoxy first Silylation) propyl] disulfide, bis- [3- (triethoxysilyl) propyl] four thioethers, two tert-butoxy diacetoxy silicon Alkane, two-isobutoxy alumina triethoxysilanes, bis- three ethoxies of (oxygroup ethyl)-aminopropyl of bis- (pentanedione) titanium-O, O '- Base silane, phenyl silane triol, aminomethyl phenyl silane glycol, ethylphenyl silandiol, n-propylbenzene base silane glycol, isopropyl Base phenyl silane glycol, normal-butyl diphenyl silanodiol, isobutyl phenenyl silandiol, tert-butyl-phenyl silandiol, two Phenyl silane glycol, dimethoxydiphenyl silane, diethoxy diphenyl silane, dimethoxy di-p-tolyl silane, second Yhnethylphenyl silanol, n-propyl aminomethyl phenyl silane alcohol, isopropyl methyl phenyl silane alcohol, normal-butyl aminomethyl phenyl silane Alcohol, isobutyl methyl phenyl silane alcohol, tertbutyl methyl phenyl silane alcohol, ethyl n-propylbenzene base silane alcohol, ethylisopropyl base Phenyl silane alcohol, normal-butyl ethylphenyl silanol, isobutyl group ethylphenyl silanol, t-butylethyl phenyl silane alcohol, first Base diphenyl silane alcohol, ethyl diphenyl silanol, n-propyl diphenyl silane alcohol, isopropyl diphenyl base silane alcohol, normal-butyl Diphenyl silane alcohol, isobutyl diphenyl silanol, t-butyl diphenylsilane alcohol, tri-phenyl-silane alcohol etc..They can be single Solely using can also combine a variety of and use.
As silane coupling agent, in aforementioned silane coupling agent, from the viewpoint of storage stability, preferred phenyl silane three Alcohol, trimethoxy-benzene base silane, trimethoxy (p-methylphenyl) silane, diphenyl silanodiol, dimethoxydiphenyl silane, Diethoxy diphenyl silane, dimethoxy di-p-tolyl silane, tri-phenyl-silane alcohol and following formula compound represented,
As compounding amount when using silane coupling agent, relative to 100 mass parts of phenolic resin (A), preferably 0.01~20 Mass parts.
As dyestuff, for example, crystal violet, crystal violet, malachite green etc..As the compounding amount of dyestuff, relative to 100 mass parts of phenolic resin (A), preferably 0.1~30 mass parts.
As dissolution accelerator, preferably with the compound of hydroxy or carboxy.As the example of the compound with hydroxyl, Can enumerate ballast agent used in aforementioned naphthalene quinone di-azido compound and p -cumylphenol, bisphenols, resorcinol class, With the non-straight chain phenol such as straight-chains phenolic compounds, TrisP-HAP, TrisP-PHBA, TrisP-PA such as MtrisPC, MtetraPC 2~5 phenol the substitution body, 3,3- hexichol of compound (all Honshu Chemical Ind's systems), diphenyl methane 1~5 phenol of base propane replace body, make 2,2- it is bis--(3- amino-4-hydroxylphenyl) hexafluoropropane and 5- norbornene- Compound obtained from 2,3- dicarboxylic anhydride is reacted with molar ratio 1:2 makes double-(3- amino-4-hydroxylphenyl) sulfone and 1,2- ring Compound obtained from hexyl dicarboxylic anhydride is reacted with molar ratio 1:2, n-hydroxysuccinimide, N- hydroxyl phthalyl are sub- Amine, N- hydroxyl 5- norbornene -2,3- dicarboximide etc..As the example of the compound with carboxyl, 3- benzene can be enumerated Base lactic acid, 4- hydroxy phenyl lactic acid, 4- hydroxy mandelic acid, 3,4- dihydroxy mandelic acid, 4- hydroxy-3-methoxy semen armeniacae amarae Acid, 2- methoxyl group -2- (1- naphthalene) propionic acid, mandelic acid, 2- phenyl-lactic acid, α-methoxyphenyl acetic acid, O- acetyl group hardship apricot Benevolence acid, itaconic acid etc..
As compounding amount when using dissolution accelerator, relative to 100 mass parts of (A) phenolic resin, preferably 0.1~30 matter Measure part.
[photosensitive polymer combination comprising polyimide precursor and/or alkaline soluble polyimide]
(A) polyimide precursor
As photoresist used in polyimide precursor composition, polyamide, poly amic acid ester etc. can be enumerated. For example, the poly amic acid ester comprising repetitive unit shown in the following general formula (11) can be used as poly amic acid ester:
In formula (11), R1And R2It is each independently hydrogen atom, the saturated aliphatic groups of carbon number 1~30, aromatic series base The ion of group, the organic group of monovalence with carbon-to-carbon unsaturated double-bond or the monovalence with carbon-to-carbon unsaturated double-bond, X1For The organic group of 4 valences, Y1For the organic group of divalent, the integer that m is 1 or more, and m preferably 2 or more, more preferable 5 or more.}.
Above-mentioned general formula (11), R1And R2In the presence of the form of the cation of monovalence, O is with negative charge (that is, with-O- Form presence).In addition, X1And Y1It may include hydroxyl.
R in general formula (11)1And R2The more preferably organic group or the following general formula of 1 valence shown in the following general formula (12) (13) end of the organic group of 1 valence shown in has the structure of ammonium ion,
In general formula (12), R3、R4And R5It is each independently the organic group of hydrogen atom or carbon number 1~5, and m1It is 1 ~20 integer.}
In general formula (13), R6、R7And R8It is each independently the organic group of hydrogen atom or carbon number 1~5, and m2It is 1 ~20 integer.}.
It can be by a variety of mixing of poly amic acid ester shown in general formula (11).Alternatively, it is also possible to use shown in general formula (11) Poly amic acid ester be copolymerized each other made of poly amic acid ester.
X from the viewpoint of hot melt property, in formula (11)1The preferably organic group of 4 valences comprising aromatic group. Specifically, X1The organic group of 4 valences preferably comprising at least one structure shown in the following general formula (2)~(4),
In formula (4), R9For any one of oxygen atom, sulphur atom, the organic group of divalent.}.
R in general formula (4)9The for example, organic group or halogen atom of the divalent of carbon number 1~40.R9It may include hydroxyl.
From the viewpoint of hot melt property, X1The organic group of 4 valences particularly preferably comprising structure shown in the following general formula (5) Group,
Y from the viewpoint of the adaptation of interlayer dielectric and sealing material, in formula (11)1It preferably include aromatic series The organic group of the divalent of group.Specifically, Y12 preferably comprising at least one structure shown in the following general formula (6)~(8) The organic group of valence,
In formula (6), R10、R11、R12And R13For the aliphatic group for 1 valence that hydrogen atom, carbon number are 1~5, it is optionally identical or It is different.}
In formula (7), R14~R21It, each other can be with for the organic group for 1 valence that hydrogen atom, halogen atom, carbon number are 1~5 Difference can also be identical.}
In formula (8), R22For the group of divalent, R23~R30For the fat for 1 valence that hydrogen atom, halogen atom, carbon number are 1~5 Race's group, it is optionally identical or different.).
R in general formula (8)22The for example, organic group of the divalent of carbon number 1~40, halogen atom.
From the viewpoint of hot melt property, as Y1, particularly preferably include the divalent of structure shown in the following general formula (9) Organic group,
X in above-mentioned poly amic acid ester, in repetitive unit1From the tetracarboxylic dianhydride for being used as raw material, Y1It is former from being used as The diamines of material.
As the tetracarboxylic dianhydride for being used as raw material, do not limit, for example, pyromellitic dianhydride, diphenyl ether -3,3 ', 4,4 '-tetracarboxylic dianhydrides, benzophenone-3,3 ', 4,4 '-tetracarboxylic dianhydrides, biphenyl -3,3 ', 4,4 '-tetracarboxylic dianhydrides, hexichol Base sulfone -3,3 ', 4,4 '-tetracarboxylic dianhydrides, diphenyl methane -3,3 ', bis- (the 3,4- O-phthalics of 4,4 '-tetracarboxylic dianhydrides, 2,2- Acid anhydrides) propane, bis- (3,4- the phthalic anhydride) -1,1,1,3,3,3- hexafluoropropane of 2,2- etc..In addition, they can individually make It is used with two or more can also be mixed.
As the diamines for being used as raw material, for example, p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diaminodiphenyl ethers, 3, 4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, 4,4 '-diamino diphenyl sulfides, 3,4 '-diamino-diphenyl sulphur Ether, 3,3 '-diamino diphenyl sulfides, 4,4 '-diamino diphenyl sulfones, 3,4 '-diamino diphenyl sulfones, 3,3 '-diamino Diphenyl sulfone, 4,4 '-benzidines, 3,4 '-benzidines, 3,3 '-benzidines, 4,4 '-diaminobenzophenones, 3,4 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 4,4 '-diaminodiphenyl-methanes, 3,4 '-diamino hexichol Bis- (4- amino-benzene oxygen) benzene of methylmethane, 3,3 '-diaminodiphenyl-methanes, 1,4-, 1,3- bis- (4- amino-benzene oxygen) benzene, 1, Bis- (3- amino-benzene oxygen) benzene of 3-, bis- (4- (4- amino-benzene oxygen) phenyl) sulfones, bis- (4- (3- amino-benzene oxygen) phenyl) sulfones, 4, It is bis- (4- amino-benzene oxygen) biphenyl of 4-, bis- (3- amino-benzene oxygen) biphenyl of 4,4-, bis- (4- (4- amino-benzene oxygen) phenyl) ethers, double (4- (3- amino-benzene oxygen) phenyl) ether, bis- (4- aminophenyl) benzene of 1,4-, bis- (4- aminophenyl) benzene of 1,3-, the bis- (4- of 9,10- Aminophenyl) anthracene, bis- (4- aminophenyl) propane of 2,2-, bis- (4- aminophenyl) hexafluoropropane of 2,2-, bis- (4- (the 4- ammonia of 2,2- Phenoxyl) phenyl) propane, bis- (4- (4- amino-benzene oxygen) phenyl) hexafluoropropane of 2,2-, bis- (the 3- aminopropyl diformazans of 1,4- Base silicyl) benzene, o-tolidine sulfone, bis- (4- aminophenyl) fluorenes of 9,9- etc..One of hydrogen atom on their phenyl ring Dividing can be substituted.In addition, they, which can be used alone, can also mix two or more and use.
It, usually can it is preferable to use following methods: aftermentioned tetracarboxylic dianhydride will be carried out in the synthesis of poly amic acid ester (A) Esterification obtained from condensation reaction of the tetracarboxylic acid acid diesters directly for itself and diamines.
Alcohols used in the esterification of above-mentioned tetracarboxylic dianhydride is the alcohol with olefinic double bond, specifically, can be with Enumerate 2-hydroxyethyl methacrylate, 2- methacryloxy ethyl alcohol, glycerol diacrylate, dimethyl allene acid glycerol Ester etc., but it is not limited to these.These alcohols can be used alone or mix two or more and use.
The specific synthetic method of the poly amic acid ester used in present embodiment (A), can be using previous known Method.For synthetic method, for example, method shown in No. 00/43439 pamphlet of International Publication No..That is, by four Carboxylic acid diesters are temporarily converted into tetracarboxylic acid acid diesters diacid chloride, make the tetracarboxylic acid acid diesters diacid chloride and diamines depositing in alkali compounds For condensation reaction under, manufacture poly amic acid ester (A).In addition, following method can be enumerated as synthetic method: pass through by Tetracarboxylic acid acid diesters and diamines, for the method for condensation reaction, manufacture poly amic acid ester (A) in the presence of organic dehydrating agent.
As the example of organic dehydrating agent, dicyclohexylcarbodiimide (DCC), diethyl carbodiimide, two can be enumerated Diisopropylcarbodiimide, ethylcyclohexyl carbodiimide, diphenyl carbodiimide, 1- ethyl -3- (3- dimethylaminopropyl) Carbodiimide, 1- cyclohexyl -3- (3- dimethylaminopropyl) carbodiimide hydrochloride etc..
The weight average molecular weight preferably 6000~150000 of poly amic acid ester used in present embodiment (A), more preferably 7000~50000, more preferable 7000~20000.
(B1) photoinitiator
In the case where the photoresist of minus, photoinitiator is added in resin combination.As photoinitiator, such as Can be used benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- benzoyl -4 '-methyldiphenyl base ketone, dibenzyl ketone and The benzophenone derivates such as Fluorenone；The acetophenone derivs such as 2,2 '-diethoxy acetophenones and 2- hydroxy-2-methyl acetone；1- The thioxanthones such as hydroxycyclohexylphenylketone, thioxanthones, 2- methyl thioxanthones, 2-isopropylthioxanthone and diethyl thioxanthone spread out Biology；The benzil derivatives such as benzil, benzil dimethyl ketal, benzil-'beta '-methoxy ethyl acetals；Benzoin methylether Etc. benzoin derivatives；(4 '-two nitrine the benzylidene) -4- methyl cyclohexanone of 2,6- bis- and 2,6 '-two (4 '-two phenylazides Asias Methyl) the nitrine class such as cyclohexanone；1- phenyl -1,2- diacetyl -2- (O- methoxycarbonyl) oxime, 1- phenylpropanedione -2- (O- first Epoxide carbonyl) oxime, 1- phenylpropanedione -2- (O- ethoxy carbonyl) oxime, 1- phenylpropanedione -2- (O- benzoyl) oxime, 1, The oximes such as 3- diphenylprop triketone -2- (O- ethoxy carbonyl) oxime, 1- phenyl -3- ethoxy-c triketone -2- (O- benzoyl) oxime Class；The N- aryl glycine class such as N-phenylglycine；The peroxides such as benzoyl peroxide；Aromatic series diimidazole class；And Luxuriant titanium class etc..Wherein, in terms of luminous sensitivity, preferably above-mentioned oximes.
The additive amount of photoinitiator is relative to 100 mass parts of poly amic acid ester (A), preferably 1~40 mass parts, more preferable 2 ~20 mass parts.By add relative to 100 mass parts of poly amic acid ester (A) be 1 mass parts more than photoinitiator, thus light Sensitivity is excellent.In addition, the photoinitiator by addition 40 below the mass, so that thick film curability is excellent.
(B2) photoacid generator
In the case where the photoresist of eurymeric, photoacid generator is added in resin combination.Resin combination contains light Acid agent, to generate acid in ultraviolet exposure portion, exposure portion increases the dissolubility of alkaline aqueous solution.Thus, it is possible to will tree Rouge is used as positive type photosensitive organic compound.
As photoacid generator, for example, quinone di-azido compound, sulfonium salt, phosphonium salt, diazonium salt, salt compounded of iodine etc..Its In, from the viewpoint of the positive type photosensitive organic compound for embodying excellent inhibition solute effect, available high sensitivity, It is preferable to use quinone di-azido compounds.Furthermore it is possible to contain photoacid generator of more than two kinds.
(C) solvent
(C) solvent is identical as the solvent illustrated in above-mentioned project [photosensitive polymer combination comprising phenolic resin].It closes In the type and amount of preferred solvent, also with above-mentioned project [photosensitive polymer combination comprising phenolic resin] in illustrate kind Class is identical with amount.
< polyimides >
Shown in structure such as the following general formula (1) of the cured relief pattern formed by above-mentioned polyimide precursor composition,
In formula (1), X1、Y1It can be with X defined in above-mentioned general formula (11) with m1、Y1It is identical with m, such as X1For having for 4 valences Machine group, Y1For the organic group of divalent, the integer that m is 1 or more.}.
Preferred X in general formula (11)1、Y1With m for the reason identical as the reasons why explanation about general formula (11), logical In polyimides shown in formula (1) it is also preferred that.
In the case where alkaline soluble polyimide, the end of polyimides can be substituted by hydroxyl.
[photosensitive polymer combination comprising polybenzoxazoles precursor]
(A) polybenzoxazoles precursor
As photoresist used in polybenzoxazoles precursor composition, can be used comprising the following general formula (14) institute Poly- (the adjacent hydroxy amide) of the repetitive unit shown,
{ in formula (14), U and V are each independently the organic group of divalent.}.
From the viewpoint of hot melt property, the organic group of the divalent of the preferred carbon number 1~30 of U in formula (14), more preferable carbon The chain alkylidene (wherein, the hydrogen atom of chain alkylidene is optionally substituted with halogen atoms) of number 1~15, particularly preferred carbon number 1 ~8 and hydrogen atom part or all of chain alkylidene being replaced by fluorine atoms.
In addition, the V in formula (14) preferably includes the organic of the divalent of aromatic group from the viewpoint of hot melt property Group, the organic group of the divalent more preferably comprising at least one structure shown in the following general formula (6)~(8),
In formula (6), R10、R11、R12And R13For the aliphatic group for 1 valence that hydrogen atom, carbon number are 1~5, it is optionally identical or It is different.}
In formula (7), R14~R21It, each other can be with for the organic group for 1 valence that hydrogen atom, halogen atom, carbon number are 1~5 Difference can also be identical.}
In formula (8), R22For the group of divalent, R23~R30For the fat for 1 valence that hydrogen atom, halogen atom, carbon number are 1~5 Race's group, it is optionally identical or different.}.
R in general formula (8)22The for example, organic group or halogen atom of the divalent of carbon number 1~40.
From the viewpoint of hot melt property, V particularly preferably includes the organic of the divalent of structure shown in the following general formula (9) Group,
From the viewpoint of hot melt property, as V, the preferably organic group of the divalent of carbon number 1~40, more preferable carbon number 1~ The chain fatty race group of 40 divalent, the chain fatty race group of the divalent of particularly preferred carbon number 1~20.
In general polybenzoxazoles precursor can be synthesized by the Diamines of dicarboxylic acid derivatives and hydroxyl.It is specific and Speech after converting dihalide derivative for dicarboxylic acid derivatives, carries out its reacting with Diamines, so as to synthesize polyphenyl And oxazole precursor.As dihalide derivative, preferably dichloride derivative.
Dichloride derivative can be synthesized and making halogenating agent act on dicarboxylic acid derivatives.It, can as halogenating agent To use used in the acyl chloride reaction of common carboxylic acid, thionyl chloride, phosphoryl chloride phosphorus oxychloride, phosphorus oxychloride, phosphorus pentachloride etc..
As the method for synthesis dichloride derivative, has: keeping dicarboxylic acid derivatives and above-mentioned halogenating agent anti-in a solvent The method answered；After being reacted in superfluous halogenating agent, by the method etc. of excess components distillation removal.
As dicarboxylic acids used in dicarboxylic acid derivatives, for example, M-phthalic acid, terephthalic acid (TPA), 2,2- Bis- (4- carboxyl phenyl) -1,1,1,3,3,3- hexafluoropropane, 4,4 '-dicarboxylate biphenyls, 4,4 '-dicarboxydiphenyl ethers, 4,4 '-two Carboxyl tetraphenyl silane, bis- (4- carboxyl phenyl) sulfones, bis- (to the carboxyl phenyl) propane of 2,2-, 5- tert-butyl isophthalic acid, 5- Bromine M-phthalic acid, 5- fluorine M-phthalic acid, 5- chlorine M-phthalic acid, 2,6 naphthalene dicarboxylic acid, malonic acid, dimethyl malonic acid, Ethyl malonic acid, isopropyl-malonic acid, di-n-butyl malonic acid, succinic acid, tetrafluoro succinic acid, methylsuccinic acid, 2,2- diformazan Base succinic acid, 2,3- dimethyl succinate, dimethyl methylsuccinic acid, glutaric acid, hexafluoro glutaric acid, 2- methylglutaric acid, 3- Methylglutaric acid, 2,2- dimethylated pentanedioic acid, 3,3- dimethylated pentanedioic acid, 3- ethyl -3- methylglutaric acid, adipic acid, octafluoro Adipic acid, 3- methyl adipic acid, octafluoro adipic acid, pimelic acid, 2,2,6,6- tetramethyl pimelic acid, suberic acid, ten difluoros pungent two Acid, azelaic acid, decanedioic acid, ten hexafluoro decanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, ten Five docosandioic acids, hexadecandioic acid (hexadecane diacid), heptadecane diacid, octadecane diacid, nonadecandioic acid, eicosane diacid, heneicosanedioic acid, Docosandioic acid, tricosane diacid, tetracosandioic acid, pentacosandioic acid, hexacosandiacid, heptacosane two Acid, Octacosanedioic Acid, nonacosane diacid, triacontanedioic acid, hentriacontane diacid, dotriacontane diacid, diglycolic acid etc.. They can also be mixed and be used.
As the diamines of hydroxyl, for example, 3,3 '-diamino -4,4 '-dihydroxybiphenyls, 4,4 '-diamino - 3,3 '-dihydroxybiphenyls, bis- (3- amino-4-hydroxylphenyl) propane, bis- (4- amino-3-hydroxy base) propane, bis- (3- ammonia Base -4- hydroxy phenyl) sulfone, bis- (4- amino-3-hydroxy base) sulfones, bis- (the 3- amino-4-hydroxylphenyls) -1,1,1,3,3 of 2,2-, Bis- (4- amino-3-hydroxy base) -1,1,1,3,3,3- hexafluoropropane of 3- hexafluoropropane, 2,2- etc..They can also be mixed And it uses.
(B2) photoacid generator
Photoacid generator has the function of making the alkaline aqueous solution solubility of illumination part to increase.As photoacid generator, such as Diazo naphthoquinone compound, aryl diazonium salts, diaryl iodonium salt, triarylsulfonium salt etc. can be enumerated.Wherein, diazo naphthoquinone chemical combination The high sensitivity of object and it is preferred that.
(C) solvent
(C) solvent is identical as the solvent illustrated in above-mentioned project [photosensitive polymer combination comprising phenolic resin].It closes In the type and amount of preferred solvent, also with above-mentioned project [photosensitive polymer combination comprising phenolic resin] in illustrate kind Class is identical with amount.
< polybenzoxazoles >
Shown in structure such as the following general formula (10) of the cured relief pattern formed by above-mentioned polybenzoxazoles precursor composition,
{ in formula (10), U and V are identical as U and V defined in above-mentioned general formula (14).}.
Preferred U and V in general formula (14) is for the reason identical as the reasons why explanation about general formula (14), in general formula (10) in polybenzoxazoles it is also preferred that.
The photosensitive polymer combination of 1st embodiment may include selected from by phenolic resin, polyimide precursor, polyphenyl And it is at least one kind of in the group of oxazole precursor and soluble polyimide composition, from the viewpoint of hot melt property, preferably comprise Phenolic resin.
The 2nd embodiment of <: low melting viscosity photosensitive layer rolls up >
The photosensitive layer volume of 2nd embodiment of the invention includes
Support body thin film；With,
Photosensitive layer is set on aforementioned support body thin film and includes photosensitive polymer combination,
Photosensitive resin combination include selected from by phenolic resin, polyimide precursor, polybenzoxazoles precursor and At least one kind of resin in the group of soluble polyimide composition, and aforementioned photosensitive layer is to become 500Pas with melt viscosity The layer of temperature spot below.
The melt viscosity of the photosensitive layer of previous photosensitive layer volume is high, though accordingly, there exist in cutting by the tooth of cutting machine In the case where heating and cutting, the problem of being also easy to produce crackle.
In order to solve the above problems, the photosensitive layer volume of the 2nd embodiment is characterized in that photosensitive layer is with melt viscosity Layer as 500Pas temperature spot below.
The photosensitive layer of present embodiment is the layer for becoming 500Pas temperature spot below with melt viscosity.Photosensitive layer is excellent The layer that there is melt viscosity to become 450Pas temperature spot below is selected, preferably there is melt viscosity to become 400Pas below The layer of temperature spot preferably becomes the layer of 350Pas temperature spot below with melt viscosity, preferably becomes with melt viscosity The layer of 300Pas temperature spot below preferably becomes the layer of 250Pas temperature spot below with melt viscosity, preferably has There is melt viscosity to become the layer of 200Pas temperature spot below.By reduce photosensitive layer melt viscosity, cutting, particularly In the case where heating and cutting the tooth of cutting machine, the generation of crackle can be inhibited.
Melt viscosity preferred 500Pas or less, preferably 450Pas at 100 DEG C of the photosensitive layer of present embodiment with Under, preferably 400Pas or less, preferably 350Pas or less, preferably 300Pas or less, preferably 250Pas or less, preferably 200Pas or less, preferably 150Pas or less, preferably 100Pas or less.
The photosensitive layer volume of 2nd embodiment can have in the opposite side equipped with aforementioned supporter film side of photosensitive layer Cover film.
If having covering film, in the case where heating and cut when cutting, particularly by the tooth of cutting machine, there is generation A possibility that fold, it is therefore preferable that not providing covering film or the covering film high using softening temperature.
Preferably 90 DEG C or more, preferably 100 DEG C or more, preferably 110 DEG C or more of the softening point temperature of covering film, preferably 120 DEG C or more, preferably 130 DEG C or more.The material of covering film is not particularly limited as long as meeting above-mentioned softening point temperature.
The melt viscosity of photosensitive layer can be with the type of organic solvent contained in photosensitive layer and/or amount adjustment.Remember below Carry its details.For other aspects, the composition illustrated in > is rolled up with above-mentioned the 1st embodiment of project <: the double-deck photosensitive layer It is identical.
The production and use > that < photosensitive layer is rolled up
The production method of the photosensitive film of present embodiment is illustrated.
Photosensitive layer can be formed: by above-mentioned photosensitive polymer combination in the form of liquid photosensitive resin combination It is coated on support body thin film, so as to be formed.
As the method for coating, for example, roll coater, comma coater, gravure coater, Kohler coater, mould The methods of painting machine, bar coater.In addition, the removal of solvent (C) can for example be carried out by heating.From organic molten in photosensitive layer It is preferably from about 70~150 DEG C of heating temperature, 100~140 DEG C more preferable when removing organic solvent from the perspective of the residual quantity of agent, And/or preferably from about 1 minute~30 minutes, more preferably from about 3 minutes~20 minutes heating time, further preferably about 4 minutes~10 Minute.
In addition, the thickness of photosensitive layer is different depending on the application, after preferably eliminating solvent with a thickness of 1~30 μm or so. Photosensitive film can be further equipped with buffer layer, adhesive layer, light absorbing layer, gas barrier layer between support body thin film and photosensitive layer Etc. middle layers or covering film.
Photosensitive film can for example be batched in the core with forms such as cylindrical shapes, photosensitive layer volume be made, with web-like Form storage.As core, it is not particularly limited as long as previous user, as its material, for example, poly- second Olefine resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-styrene (ABS) copolymerization Object) etc. plastics etc..When storage, preferably batched in a manner of supporting body thin film to become outermost.In addition, from protection end face Viewpoint is set out, and end face separator preferably is arranged in the end face for batching the photosensitive film (photosensitive film volume) for web-like, in addition, From the viewpoint of resistance to Fusion Edges, it is preferably provided with damp proof end face separator.In addition, packaging photosensitive film or photosensitive layer volume When, it is preferably wrapped up and is packed by the small black sheet of penetrability (black sheet).
The cutting > of < photosensitive layer volume
The photosensitive layer made volume is cut into desired width with cutting machine, so as to manufacture cutting photosensitive layer volume.
From the viewpoint of the section of cutting machine inhibits fold or crackle, preferably the tooth of cutting machine is heated.Cutting The heating temperature of the tooth of machine can be 80 DEG C or more, can be 90 DEG C or more, can be 100 DEG C or more, can for 110 DEG C with On, it can be 120 DEG C or more, can be 130 DEG C or more.
In the case that photosensitive layer volume has covering film, when cutting, has a possibility that generating fold on covering film, special It is not to have a possibility that generating big fold on covering film in the case that the tooth of cutting machine is heated and cut.From inhibition From the perspective of the fold of the covering film generated when cutting, the manufacturing method of cutting photosensitive layer volume preferably includes work below Sequence:
Opposite side of the aforementioned photosensitive layer volume in the side for being equipped with aforementioned support body thin film of aforementioned photosensitive layer has covering thin In the case where film, by the process of aforementioned covering film removing；
The process for being cut the aforementioned photosensitive layer volume for not having aforementioned covering film with cutting machine；With,
On the aforementioned photosensitive layer volume of aforementioned cutting, the covering film or thin with the covering of aforementioned removing of aforementioned removing is attached The process of other different covering films of film.
Stacking > of the < photosensitive layer to substrate
It is laminated in the method on substrate as by the photosensitive layer for cutting photosensitive layer volume, can be enumerated: while photosensitive layer is heated To 70~130 DEG C of left and right side laminating machinees etc. with 0.1~1MPa or so (that is, 1~10kgf/cm2Left and right) pressure crimping to base Method etc. on material.Lamination process can carry out under reduced pressure.The surface for being laminated with the substrate of photosensitive layer is not particularly limited.
In the case where the double-deck photosensitive layer volume of 1st embodiment, therefore not having covering film has photosensitive layer to be adhered to Support the worry (worry of adhesion) of body thin film.On the other hand, if reducing the adhesiveness of photosensitive layer, photosensitive layer is laminated in When on substrate, there is not closely sealed worry.That is, the 1st embodiment the double-deck photosensitive layer volume it is desirable that keeping state room temperature Lower adhesiveness is low, and when heating when being layered on substrate plays high adaptation.
Residual organic solvent amount in photosensitive layer from the adhesiveness taken into account at room temperature and is easy photonasty that is heated and melting From the perspective of the formation of film, relative to the total amount of photosensitive layer, preferably 0.1 mass % or more and 15 mass % or less, preferably 0.3 mass % or more and 15 mass % or less, preferably 0.5 mass % or more and 15 mass % or less, preferably 0.8 mass % or more And 15 below mass %, preferably 1 mass % or more and 15 mass % or less, preferably 3 mass % or more and 14 mass % or less, excellent Select 3 mass % or more and 13 mass % or less, more preferable 5 mass % or more and 13 mass % or less.Remaining in photosensitive layer Solvent amount is if it is above range, and adhesiveness is low at room temperature, and photosensitive layer is adhered to support body thin film when production photosensitive layer is rolled up The case where it is few, photosensitive layer is heated to and is embodied when being laminated on substrate high meltbility, plays high adaptation.
The organic solvent remained in photosensitive layer can be the solvent (C) illustrated among the above, dissolubility, resin from resin From the perspective of the stability of composition, the cementability to substrate, hot melt property, storage stability and adhesive, preferred γ-fourth Lactone, acetone, methyl ethyl ketone, n-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, the tert-butyl alcohol and tetrahydrofurfuryl alcohol, Wherein, particularly preferred gamma-butyrolacton, acetone, methyl ethyl ketone, n-methyl-2-pyrrolidone, dimethyl sulfoxide.
In the case where the low melting viscosity photosensitive layer volume of 2nd embodiment, similarly, it is generally desirable to, have in room temperature There is high melt viscosity, the adhesiveness of photosensitive layer is low, in the case where cutting, particularly the tooth of cutting machine being heated and cut, is Low melt viscosity and it is not likely to produce crackle.Residual organic solvent amount in preferred photosensitive layer is identical as above range.It is photosensitive The melt viscosity of layer can be adjusted with the amount of organic solvent contained in photosensitive layer.The amount of organic solvent contained in photosensitive layer is got over More, the melt viscosity of photosensitive layer becomes lower.The amount of organic solvent in photosensitive layer can be by adjusting organic molten for removing Heating temperature and/or the heating time of agent and control.In addition, heat does not occur using reducing the method for polymer molecular weight, increasing Also the melt viscosity of the adjustable photosensitive layer such as method of the low molecular compositions such as cured plasticizer.
For the photosensitive layer being so laminated on substrate, by negative or positive mask pattern, active ray is irradiated with image shape And form exposure portion.At this point, can pass through in the case that the supporter being present on photosensitive layer is transparent relative to active ray Supporter irradiates active ray, in the case that supporter embodies light-proofness relative to active ray, after supporter is removed, to sense Photosphere irradiates active ray.
As the light source of active ray, X-ray, electron beam, ultraviolet light, luminous ray etc., optimal wavelength 200 can be used The light source of~500nm.From the aspect of the resolution ratio of pattern and operability, g ray, the h ray of the preferred mercury lamp of optical source wavelength Or the region of i ray, can be used alone can also mix chemical ray of more than two kinds.As exposure device, preferred alignment Device, parallel exposing machine, mirror projection machine and stepping exposure device.After exposure, can according to need again will with 80~140 DEG C Film heating.
Then, developer solution can be used, and select and develop from the methods of infusion process, paddle method, spray coating method.Pass through Development, can from be coated with photo-sensitive resin dissolution removal exposure portion (in the case where eurymeric) or unexposed portion (minus In the case of), obtain embossing pattern.
As developer solution, it can be used for example: the inorganic bases such as sodium hydroxide, sodium carbonate, sodium metasilicate, ammonium hydroxide, ethamine, two The water of the quaternary ammonium salts such as the organic amines such as ethamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide etc. It solution and is added as needed water-soluble made of the water-miscible organic solvents such as the methanol of appropriate amount, ethyl alcohol or surfactant Liquid.Wherein, preferred tetramethylammonium hydroxide aqueous solution.The concentration of tetramethylammonium hydroxide preferably 0.5~10 mass %, more preferably 1~5 mass %.
It after development, is cleaned using flushing liquor and is removed developer solution, so as to obtain being formed with embossing pattern Substrate.As flushing liquor, distilled water, methanol, ethyl alcohol, isopropanol etc. can be used for example, it can be by their exclusive uses or group It closes two or more and uses.
Finally, the obtained embossing pattern is heated, so as to obtain cured relief pattern.Heating temperature is preferred 150 DEG C or more and 300 DEG C or less, more preferable 250 DEG C or less.
The manufacturing method for the cured relief pattern rolled up using the photosensitive layer of the 1st or the 2nd embodiment can be suitable for system Make: semiconductor device, interlayer dielectric, is routed again with insulating film, is used for the surface protection film for showing body device and light emitting device The wiring layer again of fan-out-type wafer-level packaging (FOWLP), high-density base board, has convex block knot at flip-chip device protective film The protective film of the device of structure, the interlayer dielectric of multilayer circuit, flexible copper-clad plate covering coating, solder mask and liquid crystal take To film etc..
More than, the mode that is suitable for carrying out of the invention is illustrated, but the present invention is not limited to above embodiment.This Invention can carry out various modifications within the scope of its spirit.
Embodiment
Hereinafter, being illustrated in further detail according to embodiment to the present invention, but the present invention is not limited to these implementations Example.
[synthesis example 1]
The synthesis > of < phenolic resin (A-1)
In 0.5 liter of capacity of the removable flask with Dien-Stark (Dean-Stark) device, by phloroglucin 100.9g (0.8mol), 4,4 '-bis- (methoxy) biphenyl (hereinafter also referred to " BMMB ") 121.2g (0.5mol), sulfuric acid two Ethyl ester 3.9g (0.025mol) and diethylene glycol dimethyl ether 140g are mixed with 70 DEG C, dissolve solids.
Mixed solution is heated up to 140 DEG C using oil bath, from reaction solution confirm methanol generation, keep the state with 140 DEG C are stirred reaction solution 2 hours.
Then, reaction vessel is cooled down in an atmosphere, the tetrahydrofuran of 100g and stirring is separately added thereto.In high speed Under stirring, dropwise reaction dilution, is precipitated resin dispersion in the water of 4L, is recycled, and is suitable for washing, after dehydration, real Vacuum drying is applied, the copolymer (phenolic resin (A-1)) formed by phloroglucin/BMMB is obtained with yield 70%.
[synthesis example 2]
The synthesis > of < phenolic resin (A-2)
The phloroglucin that synthesis example 1 is replaced using 3,5- methyl dihydroxy benzoate 128.3g (0.76mol), except this it Outside, it is carried out similarly synthesis with synthesis example 1, obtains being total to by what 3,5- methyl dihydroxy benzoate/BMMB was formed with yield 65% Polymers (phenolic resin (A-2)).
[synthesis example 3]
The synthesis > of < phenolic resin (A-3)
The removable flask with Dean and Stark apparatus of capacity 1.0L is subjected to nitrogen displacement, later, removable In flask, by resorcinol 81.3g (0.738mol), BMMB84.8g (0.35mol), p-methyl benzenesulfonic acid 3.81g (0.02mol), It is mixed with propylene glycol monomethyl ether (hereinafter also referred to " PGME ") 116g with 50 DEG C, dissolves solids.
Mixed solution is heated up to 120 DEG C using oil bath, from reaction solution confirm methanol generation, keep the state with 120 DEG C are stirred reaction solution 3 hours.
Then, in another container, by bis- (the hydroxymethyl)-paracresol 24.9g (0.150mol) of 2,6- and PGME249g It is mixed, makes its uniform dissolution, using dropping funel, acquired solution was added drop-wise to above-mentioned removable flask with 1 hour In, after dropwise addition, stir within further progress 2 hours.
After reaction, it carries out similarly handling with synthesis example 1, be obtained with yield 77% by resorcinol/BMMB/2,6- The copolymer (phenolic resin (A-3)) that bis- (hydroxymethyl)-paracresol are formed.
[synthesis example 4]
The synthesis > of < polyimide precursor (A-5)
In the removable flask of capacity 2L, by pyromellitic acid dianhydride 87.2g (0.4mol), isobutanol 59.3g (0.8mol) and gamma-butyrolacton (hereinafter also referred to " GBL ") 320g are mixed under room temperature (25 DEG C), are made it dissolve, Pyridine 63.3g (0.8mol) is added while stirring under ice-cold, after heat release, is cooled to room temperature, places 16 hours.
Then, dicyclohexylcarbodiimide 165g will be dissolved in GBL120g with 40 minutes in ice-cold lower stirring The solution of (0.8mol) is added to above-mentioned removable flask.Then, while will be in GBL150g with 60 minutes in ice-cold lower stirring The suspended matter for being suspended with 4,4 '-diaminodiphenyl ether 74.5g (0.37mol) is added to above-mentioned removable flask.It stirs at room temperature After mixing 2 hours, in above-mentioned removable flask be added ethyl alcohol 30ml, stir 1 hour, further be added dimethyl acetamide (with Down referred to as " DMAc ") after 250ml and tetrahydrofuran (THF) 400ml, precipitating is passed through and filters removal, obtains reaction solution.In 15L Ethyl alcohol in be added gained reaction solution be dried in vacuo after filtering out the precipitating of generation, obtain polyimide precursor (A-5).
[synthesis example 5]
The synthesis > of < polybenzoxazoles precursor (A-6)
In the removable flask of capacity 2L, by bis- (3- the amino-4-hydroxylphenyl)-hexafluoropropane 197.8g of 2,2- (0.54mol), pyridine 75.9g (0.96mol) and DMAc692g are mixed and are made it dissolve under room temperature (25 DEG C).
In gained mixed solution, separately it is added dropwise by dropping funel at dimethyl diethylene glycol (DEG) (hereinafter also referred to " DMDG ") The solution of 5- norbornene -2,3- dicarboxylic anhydride 19.7g (0.12mol) is dissolved in 88g.Time needed for being added dropwise is 40 points Clock, reaction solution temperature are up to 28 DEG C.
After completion of dropwise addition, after reaction solution is heated up to 50 DEG C, stirring 18 hours using hot bath, the IR light of reaction solution is carried out The measurement of spectrum, it is thus identified that 1385cm occur-1And 1772cm-1Imide characteristic absorption.
Then, it utilizes water-bath cooling to 8 DEG C reaction solution, in the reaction solution, is separately added dropwise and is existed by dropping funel The solution of 4,4 '-diphenyl ether diacid chloride 142.3g (0.48mol) is dissolved in DMDG398g.Time needed for being added dropwise is 80 points Clock, reaction solution temperature are up to 12 DEG C.
After completion of dropwise addition after 3 hours, under high velocity agitation, above-mentioned reaction solution is added dropwise in the water of 12L, disperses polymer It is precipitated, is recycled, be suitable for implementing vacuum drying after washing, dehydration, obtaining polybenzoxazoles precursor (A-6).
< resin (A) and (A ') >
A-1: copolymer, the polystyrene formed by phloroglucin/BMMB converts weight average molecular weight (Mw)=15000
A-2: the copolymer that is formed by 3,5- methyl dihydroxy benzoate/BMMB, polystyrene conversion weight average molecular weight (Mw)=21000
A-3: copolymer, the polystyrene formed by bis- (the hydroxymethyl)-paracresol of resorcinol/BMMB/2,6- converts Weight average molecular weight (Mw)=9900
A-4: novolac resin, polystyrene conversion weight average molecular weight (Mw)=10600 (organic material Co., Ltd. of the rising sun System, product name EP-4080G)
A-5: polyimide precursor
A-6: polybenzoxazoles precursor
< photoacid generator (B) >
B-1: photoacid generator shown in following formula:
{ in formula, 83% is structure shown in following below formula among Q, remaining is hydrogen atom.}
< solvent (C) >
C-1: gamma-butyrolacton (GBL)
C-2: methyl ethyl ketone
C-3: acetone
C-4:N, dinethylformamide
< surfactant (D) >
D-1: organic silicon type surfactant D BE821 (trade name, Gelest corporation)
D-2: organic silicon type surfactant D BE224 (trade name, Gelest corporation)
< crosslinking agent (E) >
E-1:1,3,4,6- tetra- (methoxy) glycoluril (SANWA Chemical Co., Ltd. system, trade name； Nikalac MX-270)
[preparation of photosensitive polymer combination]
Composition as described in Table 1 is such, makes resin (A), photoacid generator (B), surfactant (D) and crosslinking agent (E) it is dissolved in solvent (C), is filtered with 0.1 μm of filter, prepares positive type photosensitive organic compound.
[table 1]
[support body thin film]
As support body thin film, preparation has carried out the PET film " PET25X " of demoulding processing with silicon-type compound (Lintec Corporation system, width 290mm, 25 μm of thickness).
[production of photosensitive film]
(embodiment 1)
As support body thin film, used as " PET25X " of demoulding processing PET film, the applying implenent in demoulding process face The solution of the photosensitive polymer combination formed shown in above-mentioned table 1.Then, make to be coated with the molten of photosensitive polymer combination The PET film of liquid was dried in 120 DEG C of hot wind through 5 minutes, formed photosensitive layer.At this point, making the photosensitive layer after heating Thickness becomes 10 μm.For the photosensitive film of the width 300mm of above-mentioned composition, in 3.5 inches of outer diameter of cylindrical plastic pipe On, using the pressure roller configured in parallel relative to spool width direction, pressure is applied with threadiness to plastic tube, with of 7kg Power batches 1000m, obtains photosensitive film volume.
(embodiment 2~13)
Using ingredient, composition and drying condition shown in above-mentioned table 1, in addition to this, according to step same as Example 1 Suddenly, each photosensitive film volume is made.
(comparative example 1~3)
Using ingredient, composition and drying condition shown in above-mentioned table 1, and when obtaining photosensitive film volume photosensitive The covering film that softening temperature is 90 DEG C is set on layer, in addition to this, according to step same as Example 1, is made each photosensitive Property film roll.
< residual solvent amount >
The photosensitive film volume unwinding photosensitive film made respectively from embodiment and comparative example, by photosensitive layer from branch Support body film removing, to the photosensitive layer removed gas chromatograph (Agilent Technologies Ltd. system, trade name " 890N ") it is analyzed, measure the residual solvent amount (mass parts) relative to 100 mass parts of phenolic resin.
< melt viscosity >
The photosensitive film volume unwinding photosensitive film made respectively from embodiment and comparative example, by photosensitive layer from branch Support body film removing, by the photosensitive layer removed with melt viscosity measurement device (TA Instruments Japan, Inc., system, Product name " DHR-2 "), be measured under the following conditions.Melt viscosity at 100 DEG C of temperature is shown in table 1.
Sample shape
Film thickness: 0.5mmt
Diameter: 25mm plectane
Determination condition
Start temperature: 50 DEG C
Heating rate: 5 DEG C/min
End temperature: 220 DEG C
Strain: 0.1%
Frequency: 1Hz
Load: 0.5N (± 0.1N)
< storage stability >
The photosensitive film made respectively in embodiment and comparative example volume is taken care of 1 month or more under room temperature (25 DEG C) Afterwards, it with the unwinding of visual observation volume, is evaluated according to following benchmark.
S (significant good): even if being saved at room temperature 1 month or more with scroll state, photosensitive layer is also not attached to supporter The film back side.
A (good): when being saved at room temperature 1 month with scroll state, a part of photosensitive layer is attached to support body thin film back Face.
The fissility > of < support body thin film
The photosensitive film volume unwinding photosensitive film made respectively from embodiment and comparative example, while photosensitive layer is added Heat is folded on a glass to 130 DEG C of boundary layers, makes the evaluating characteristics sample transferred with photosensitive layer.Then, it is used from evaluating characteristics Sample removing removal support body thin film, evaluates the state of the transfer of photosensitive layer by visual observation.
S (significant good): photosensitive layer is not attached to support body thin film, can remove removal.
A (good): in a part of photosensitive layer, the state removing of support body thin film is attached to photosensitive layer.
B (bad): in the entire surface of photosensitive layer, the state removing of support body thin film is attached to photosensitive layer.
Crackle > when < is cut
The photosensitive film made respectively in embodiment and comparative example volume is carried out with the cutting machine of heating tooth to 100 DEG C Cutting.The beauty of the generation of crackle when evaluation cutting and section by visual observation.
S (significant good): it does not crack, section is also smooth.
A (good): not cracking, but has a little bumps on section.
B (bad): crackle is produced.
The fold > of < covering film
The photosensitive film made in comparative example volume is cut with the cutting machine with the tooth for being heated to 100 DEG C, With the fold generated in visual valuation covering film.
A (good): fold is not generated in covering film.
B (bad): fold is produced in covering film.
< evaluation result >
For each embodiment and comparative example, each evaluating characteristics result is shown in above-mentioned table 1.
Industrial availability
The surface protection that photosensitive layer volume of the invention can be suitable as semiconductor device, show body device and light emitting device Film, interlayer dielectric are routed again with insulating film, the wiring layer again for wafer-level packaging, flip-chip device protective film, height The covering of density substrate, the protective film of device with projection cube structure, the interlayer dielectric of multilayer circuit, flexible copper-clad plate applies It covers, solder mask and liquid crystal orientation film etc. utilize.

Claims (40)

1. a kind of photosensitive layer volume, includes
Support body thin film；With,
Photosensitive layer is set on the support body thin film and includes photosensitive polymer combination,
The photosensitive polymer combination includes selected from by phenolic resin, polyimide precursor, polybenzoxazoles precursor and solvable Property polyimides composition group at least one kind of resin, and the photosensitive layer be with melt viscosity become 500Pas or less Temperature spot layer.
2. photosensitive layer according to claim 1 volume, wherein the photosensitive layer be become with melt viscosity 350Pas with Under temperature spot layer.
3. photosensitive layer according to claim 1 or 2 volume, wherein the melt viscosity at 100 DEG C of the photosensitive layer is 500Pas or less.
4. photosensitive layer volume according to claim 3, wherein the melt viscosity at 100 DEG C of the photosensitive layer is 350Pa S or less.
5. photosensitive layer volume according to any one of claims 1 to 4, wherein be equipped with the support in the photosensitive layer The opposite side of the side of body thin film has covering film, and the softening temperature of the covering film is 90 DEG C or more.
6. photosensitive layer volume according to claim 5, wherein the softening temperature of the covering film is 110 DEG C or more.
7. photosensitive layer described according to claim 1~any one of 6 is rolled up, wherein organic solvent contained in the photosensitive layer Amount relative to the photosensitive layer total amount be 0.1 mass % or more and 15 mass % or less.
8. photosensitive layer volume according to claim 7, wherein the amount of organic solvent contained in the photosensitive layer is relative to institute The total amount for stating photosensitive layer is 1 mass % or more and 15 mass % or less.
9. photosensitive layer volume according to claim 7 or 8, wherein the organic solvent includes selected from by gamma-butyrolacton, third Ketone, methyl ethyl ketone, n-methyl-2-pyrrolidone, the group of dimethyl sulfoxide, propylene glycol monomethyl ether, the tert-butyl alcohol and tetrahydrofurfuryl alcohol composition At least one of.
10. photosensitive layer according to claim 9 volume, wherein the organic solvent include selected from by gamma-butyrolacton, acetone, At least one of methyl ethyl ketone, n-methyl-2-pyrrolidone and group of dimethyl sulfoxide composition.
11. photosensitive layer described according to claim 1~any one of 10 is rolled up, wherein the photosensitive polymer combination includes The polyimide precursor.
12. photosensitive layer described according to claim 1~any one of 10 is rolled up, wherein the photosensitive polymer combination includes The polybenzoxazoles precursor.
13. photosensitive layer described according to claim 1~any one of 10 is rolled up, wherein the photosensitive polymer combination includes The soluble polyimide.
14. photosensitive layer described according to claim 1~any one of 10 is rolled up, wherein the photosensitive polymer combination includes The phenolic resin.
15. photosensitive layer volume according to claim 14, wherein the phenolic resin has to be tied shown in the following general formula (1) Structure is as repetitive unit:
In formula (1), the integer that a is 1~3, the integer that b is 0~3 is 1≤(a+b)≤4, R1It indicates selected from by the 1 of carbon number 1~20 The substituent group for 1 valence in group that organic group, halogen atom, nitro and the cyano of valence form, multiple R when b is 2 or 31Appoint Choosing is same or different to each other, and X indicates the chain fatty race base selected from the divalent by the carbon number 2~10 optionally with unsaturated bond Group, the ester ring type group of divalent of carbon number 3~20, divalent shown in the following general formula (2) alkylidene oxide and there is aromatic ring Divalent organic group composition group in divalent organic group,
-CpH2pO- (formula 2)
In formula (2), p be 1~10 integer.
16. photosensitive layer volume according to claim 15, wherein the X in the general formula (1) is selected from by the following general formula (3) Shown in divalent group and the following general formula (4) shown in divalent group composition group in divalent organic group,
In formula (3), R2、R3、R4And R5Be each independently hydrogen atom, carbon number 1~10 1 valence aliphatic group or hydrogen atom Part or all replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, n1 be 0~4 integer, when The R when integer that n1 is 1~46For the organic group of halogen atom, hydroxyl or 1 valence, at least one R6For hydroxyl, when n1 is 2~4 Integer when multiple R6Optionally it is same or different to each other,
In formula (4), R7、R8、R9And R10Each independently represent hydrogen atom, carbon number 1~10 1 valence aliphatic group or hydrogen it is former Son part or all replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, and W be singly-bound, selected from by The alicyclic ring of the chain fatty race group of the carbon number 1~10 optionally replaced with fluorine atom, the carbon number 3~20 optionally replaced with fluorine atom In the group of the group composition of divalent shown in the alkylidene oxide and following formula (5) of divalent shown in formula group, the following general formula (2) Divalent organic group,
-CpH2pO- (formula 2)
In formula (2), the integer that p is 1~10,
17. photosensitive layer volume according to claim 15 or 16, wherein the X in the general formula (1) is shown in following formula (6) Divalent organic group,
18. photosensitive layer volume according to claim 17, wherein the X in the general formula (1) is divalent shown in following formula (7) Organic group,
19. photosensitive layer described in any one of 5~18 is rolled up according to claim 1, wherein the phenolic resin is in same resin bone There is both repetitive units shown in repetitive unit shown in the following general formula (8) and the following general formula (9) in frame,
In formula (8), R11For the group of 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy, n2 is 1~3 Integer, the integer that n3 is 0~2, the integer that m1 is 1~500 is 2≤(n2+n3)≤4, the R when n3 is 211Optional phase each other It is same or different,
In formula (9), R12And R13It is each independently 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy Group, the integer that n4 is 1~3, the integer that n5 is 0~2, the integer that n6 is 0~3, the integer that m2 is 1~500 are 2≤(n4+ N5)≤4, the R when n5 is 212Optionally it is same or different to each other, the R when n6 is 2 or 313Optionally it is same or different to each other.
20. a kind of photosensitive layer volume, includes
Support body thin film；With,
Photosensitive layer is set on the support body thin film and includes photosensitive polymer combination,
The photosensitive polymer combination includes selected from by phenolic resin, polyimide precursor, polybenzoxazoles precursor and solvable Property polyimides composition group at least one kind of resin, and it is described support body thin film two sides contacted with the photosensitive layer.
21. photosensitive layer according to claim 20 volume, wherein the amount of organic solvent contained in the photosensitive layer relative to The total amount of the photosensitive layer is 0.1 mass % or more and 15 mass % or less.
22. photosensitive layer according to claim 21 volume, wherein the amount of organic solvent contained in the photosensitive layer relative to The total amount of the photosensitive layer is 1 mass % or more and 15 mass % or less.
23. the photosensitive layer according to claim 21 or 22 is rolled up, wherein the photosensitive polymer combination includes the phenolic aldehyde Resin.
24. the photosensitive layer according to any one of claim 21~23 roll up, wherein the organic solvent include selected from by Gamma-butyrolacton, acetone, methyl ethyl ketone, n-methyl-2-pyrrolidone, dimethyl sulfoxide, propylene glycol monomethyl ether, the tert-butyl alcohol and tetrahydro At least one of the group of furfuryl alcohol composition.
25. photosensitive layer volume according to claim 24, wherein the organic solvent includes selected from by gamma-butyrolacton, third At least one of ketone, methyl ethyl ketone, n-methyl-2-pyrrolidone and group of dimethyl sulfoxide composition.
26. the photosensitive layer according to any one of claim 20~25 is rolled up, wherein the photosensitive polymer combination includes The polyimide precursor.
27. the photosensitive layer according to any one of claim 20~25 is rolled up, wherein the photosensitive polymer combination includes The polybenzoxazoles precursor.
28. the photosensitive layer according to any one of claim 20~25 is rolled up, wherein the photosensitive polymer combination includes The soluble polyimide.
29. the photosensitive layer according to any one of claim 20~25 is rolled up, wherein the photosensitive polymer combination includes Phenolic resin.
30. photosensitive layer volume according to claim 29, wherein the phenolic resin has to be tied shown in the following general formula (1) Structure as repetitive unit,
In formula (1), the integer that a is 1~3, the integer that b is 0~3 is 1≤(a+b)≤4, R1It indicates selected from by the 1 of carbon number 1~20 The substituent group for 1 valence in group that organic group, halogen atom, nitro and the cyano of valence form, multiple R when b is 2 or 31Appoint Choosing is same or different to each other, and X indicates the chain fatty race base selected from the divalent by the carbon number 2~10 optionally with unsaturated bond Group, the ester ring type group of divalent of carbon number 3~20, divalent shown in the following general formula (2) alkylidene oxide and there is aromatic ring Divalent organic group composition group in divalent organic group,
-CpH2pO- (formula 2)
In formula (2), p be 1~10 integer.
31. photosensitive layer volume according to claim 30, wherein the X in the general formula (1) is selected from by the following general formula (3) Shown in divalent group and following formula (4) shown in divalent group composition group in divalent organic group,
In formula (3), R2、R3、R4And R5Be each independently hydrogen atom, carbon number 1~10 1 valence aliphatic group or hydrogen atom Part or all replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, n1 be 0~4 integer, when The R when integer that n1 is 1~46For the organic group of halogen atom, hydroxyl or 1 valence, at least one R6For hydroxyl, when n1 is 2~4 Integer when multiple R6Optionally it is same or different to each other,
In formula (4), R7、R8、R9And R10Each independently represent hydrogen atom, carbon number 1~10 1 valence aliphatic group or hydrogen it is former Son part or all replaced with fluorine atom made of carbon number 1~10 1 valence aliphatic group, and W be singly-bound, selected from by The alicyclic ring of the chain fatty race group of the carbon number 1~10 optionally replaced with fluorine atom, the carbon number 3~20 optionally replaced with fluorine atom In the group of the group composition of divalent shown in the alkylidene oxide and following formula (5) of divalent shown in formula group, the following general formula (2) Divalent organic group,
-CpH2pO- (formula 2)
In formula (2), the integer that p is 1~10,
32. the photosensitive layer according to claim 30 or 31 is rolled up, wherein the X in the general formula (1) is shown in following formula (6) Divalent organic group,
33. photosensitive layer volume according to claim 32, wherein the X in the general formula (1) is divalent shown in following formula (7) Organic group,
34. the photosensitive layer according to any one of claim 30~33 is rolled up, wherein the phenolic resin is in same resin bone There is both repetitive units shown in repetitive unit shown in the following general formula (8) and the following general formula (9) in frame,
In formula (8), R11For the group of 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy, n2 is 1~3 Integer, the integer that n3 is 0~2, the integer that m1 is 1~500 is 2≤(n2+n3)≤4, the R when n3 is 211Optional phase each other It is same or different,
In formula (9), R12And R13It is each independently 1 valence of the carbon number 1~10 in the group being made of alkyl and alkoxy Group, the integer that n4 is 1~3, the integer that n5 is 0~2, the integer that n6 is 0~3, the integer that m2 is 1~500 are 2≤(n4+ N5)≤4, the R when n5 is 212Optionally it is same or different to each other, the R when n6 is 2 or 313Optionally it is same or different to each other.
35. a kind of manufacturing method of cutting photosensitive layer volume, the manufacturing method cutting machine is by any one of claims 1 to 34 The photosensitive layer volume cuts and manufactures cutting photosensitive layer volume.
36. the manufacturing method of cutting photosensitive layer volume according to claim 35, wherein heat the tooth of the cutting machine.
37. the manufacturing method of cutting photosensitive layer volume according to claim 36, wherein the tooth of the cutting machine to be heated to 100 DEG C or more.
38. a kind of manufacturing method of cutting photosensitive layer volume comprising process below:
Photosensitive layer described in any one of claims 1 to 34 is rolled up in the side for being equipped with the support body thin film of the photosensitive layer Opposite side have covering film in the case where, by it is described covering film removing process；
The process for being cut the photosensitive layer volume for not having the covering film with cutting machine；With,
On the photosensitive layer volume of cutting, the covering film or different from the covering film of the removing of the removing is attached The process of other covering films.
39. the manufacturing method of cutting photosensitive layer volume according to claim 38, wherein heat the tooth of the cutting machine.
40. the manufacturing method of cutting photosensitive layer volume according to claim 39, wherein the tooth of the cutting machine to be heated to 100 DEG C or more.
CN201780078288.6A 2016-12-20 2017-12-18 Double-layer photosensitive layer roll Active CN110088680B (en)

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