CN112513219B - Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device Download PDF

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CN112513219B
CN112513219B CN201980049338.7A CN201980049338A CN112513219B CN 112513219 B CN112513219 B CN 112513219B CN 201980049338 A CN201980049338 A CN 201980049338A CN 112513219 B CN112513219 B CN 112513219B
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resin composition
photosensitive resin
formula
carbon atoms
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CN112513219A (en
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岩井悠
吉田健太
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/06—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/07—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C233/58—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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    • C07—ORGANIC CHEMISTRY
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    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/14—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/12—Oxygen or sulfur atoms
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/16—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with acylated ring nitrogen atom
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
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Abstract

In the present invention, the thermal alkaline agent is represented by formula (N1). The photosensitive resin composition includes a thermal alkaline generator and a precursor of a heterocyclic polymer. In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group, R C1 Represents a hydrogen atom or a protecting group, and L represents a 2-valent linking group. The cured film is obtained by curing the photosensitive resin composition. The laminate has 2 or more layersA cured film with a metal layer between the cured films. The method for producing the cured film includes a film formation step of applying the photosensitive resin composition onto a substrate to form a film. The semiconductor device has a cured film or a laminate.

Description

Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device
Technical Field
The invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing the cured film, and a semiconductor device.
Background
The resin cured by cyclization such as polyimide resin and polybenzoxazole resin is excellent in heat resistance and insulation properties and therefore suitable for various applications. The application is not particularly limited, but when a semiconductor device for actual mounting is used as an example, use of a material or a protective film as an insulating film or a sealing material is exemplified. (refer to non-patent documents 1 and 2, etc.). And also as a base film, a cover layer, or the like of the flexible substrate.
Such polyimide resins and the like generally have low solubility in solvents. Therefore, a method of dissolving a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor in a solvent is often used. This can realize excellent handleability, and can be applied to a substrate or the like in various forms and processed when manufacturing each product as described above. The polymer precursor is then heated and cyclized, thereby enabling the formation of a cured product. In addition to the high performance of polyimide resins and the like, the development of applications in the production of polyimide resins is increasingly desired from the viewpoint of excellent adaptability to such production.
Patent document 1 discloses a thermosetting resin composition comprising a thermal alkaline agent and a thermosetting resin, wherein the thermal alkaline agent comprises at least 1 selected from acidic compounds which generate alkali when heated to 40 ℃ or higher, and ammonium salts having anions and ammonium cations with pKa1 of 0 to 4.
Patent document 2 discloses a resin composition containing a polyimide precursor having a specific structural unit, a compound that generates a radical upon irradiation with an activating light, a compound having a propylene oxide oligomer structure, and a solvent.
Technical literature of the prior art
Patent literature
Patent document 1: WO2015/199219 booklet
Patent document 2: japanese patent application laid-open No. 2014-201695
Non-patent literature
Non-patent document 1: science & technology co., ltd, "high functionalization of polyimide and application technology of polyimide", month 4 of 2008
Non-patent document 2: basic and development of polyimide material of persimmon Benyanming/prison and CMC technical library, release 11 months in 2011
Disclosure of Invention
Technical problem to be solved by the invention
By the techniques of patent documents 1 and 2, a polymer precursor can be cyclized at a low temperature to obtain a cured product. On the other hand, in order to meet the recent diversified technical demands made on such resins, further research and development are required.
Accordingly, an object of the present invention is to provide a novel thermoalcifer and to achieve enrichment of materials in the field of photosensitive resin compositions containing precursors of heterocyclic polymers. Further, it is an object of the present invention to provide a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device, which can realize excellent storage stability in the photosensitive resin composition and can improve the elongation at break of the cured film formed from the photosensitive resin composition.
Means for solving the technical problems
Based on the above-described problems, the present inventors have found that a specific thermoalcifer comprising a carboxyl group or an ester thereof and a site having an amide structure can solve the above-described problems, and have completed the present invention. Specifically, the above problems are solved by the following method.
<1> a thermal alkaline agent represented by the following formula (N1);
[ chemical formula 1]
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group, R C1 Represents an oxygen atom or a protecting group, and L represents a 2-valent linking group.
<2> the thermal alkaline generator according to <1>, wherein L in the above formula (N1) is a 2-valent organic group having a chain length of 1 to 5.
<3>According to<1>Or (b)<2>The thermoalcogenics, wherein R in the formula (N1) N1 R is R N2 Are each independently a hydrocarbyl group.
<4>According to<1>～<3>The thermal alkaline generator according to any one of the above formulas (N1), wherein R is N1 R is R N2 Each independently is an aliphatic hydrocarbon group.
<5> the thermal alkaline agent according to any one of <1> to <4>, wherein L in the above formula (N1) is 1, 2-ethylene, 1, 3-propanediyl, 1, 2-cyclohexanediyl, cis-ethylene, 1, 2-phenylene methylene or 1, 2-ethyleneoxy-1, 2-ethylene.
<6>According to<1>～<5>The thermal alkaline generator according to any one of the above formulas (N1), wherein R is C1 Is a hydrogen atom.
<7> the thermal alkaline agent according to any one of <1> to <6>, wherein the compound produced by decomposition of the thermal alkaline agent represented by the above formula (N1) is a compound represented by the following formula (N2), and the boiling point of the compound represented by the above formula (N2) is 50℃or higher.
[ chemical formula 2]
In the formula (N2), R N1 R is R N2 Each independently represents a 1-valent organic group.
<8> a photosensitive resin composition comprising the thermal alkaline generator of any one of <1> to <7> and a heterocyclic polymer-containing precursor.
<9> the photosensitive resin composition according to <8>, further comprising a photo radical polymerization initiator and a radical polymerizable compound.
<10> the photosensitive resin composition according to <8> or <9>, wherein the heterocyclic polymer-containing precursor comprises a polyimide precursor or a polybenzoxazole precursor.
The photosensitive resin composition according to any one of <8> to <10>, wherein the heterocyclic polymer-containing precursor comprises a polyimide precursor.
The photosensitive resin composition according to any one of <8> to <10>, wherein the heterocyclic polymer-containing precursor has a structural unit represented by the following formula (1).
[ chemical formula 3]
In the formula (1), A 1 A is a 2 Each independently represents an oxygen atom or NH, R 111 Represents a 2-valent linking group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group.
<13> the photosensitive resin composition according to <12>, wherein,
r in the above formula (1) 113 R is R 114 At least one of which contains a radically polymerizable group.
<14> the photosensitive resin composition according to any one of <8> to <13>, which is used for forming an interlayer insulating film for a re-wiring layer.
<15> a cured film obtained by curing the photosensitive resin composition according to any one of <8> to <14 >.
<16> a laminate comprising 2 or more layers of the cured film of <15>, and a metal layer between the cured films.
<17> a method for producing a cured film, comprising a film forming step of applying the photosensitive resin composition according to any one of <8> to <16> to a substrate to form a film.
<18> the method for producing a cured film according to <17>, comprising the step of heating the film at 50 to 450 ℃.
<19> a semiconductor device having the cured film of <15> or the laminate of <16 >.
Effects of the invention
According to the present invention, a novel thermal alkaline generator can be provided, and enrichment of materials in the field of photosensitive resin compositions containing precursors of heterocyclic polymers can be achieved. Further, according to the present invention, excellent storage stability in the photosensitive resin composition can be achieved, and the elongation at break of the cured film formed from the photosensitive resin composition can be improved.
Detailed Description
The following describes the present invention in detail. In the present specification, "to" means that the numerical values before and after the "to" are used as meanings included in the lower limit value and the upper limit value.
The following description of the constituent elements of the present invention is sometimes made based on the representative embodiments of the present invention, but the present invention is not limited to these embodiments.
In the present specification, the term "label for a group (radical)" means that a substituted or unsubstituted label is not defined and includes both a group (radical) having no substituent and a group (radical) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the case of an alkyl group, the alkyl group may be chain-shaped or cyclic, and in the case of a chain-shaped, the alkyl group may be straight-chain or branched. These meanings are also the same for alkenyl or alkylene, alkenylene.
The term "exposure" in the present specification is not particularly limited, and includes exposure by a particle beam such as an electron beam or an ion beam, as well as exposure by light. The light used for exposure generally includes an active light ray such as an extreme ultraviolet ray, an extreme ultraviolet ray (EUV light), an X-ray, and an electron beam, and a radiation, which are represented by an open line spectrum of a mercury lamp and an excimer laser.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" means either or both of "acryl" and "methacryl".
In the present specification, the term "process" includes not only an independent process but also a process that exhibits an intended function even when it cannot be clearly distinguished from other processes.
The physical properties in the present invention are set to values at a temperature of 23℃and a gas pressure of 101325Pa unless otherwise specified.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC measurement) and are defined as styrene conversion values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8220 (manufactured by TOSOH CORPORATION) as a column and using a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). In this measurement, THF (tetrahydrofuran) was used as an eluent unless otherwise specified. Further, unless otherwise specified, it is assumed that a 254nm wavelength detector of UV (ultraviolet) light is used for detection.
< thermal alkaline Agents >
The thermal alkaline agent of the present invention is represented by the following formula (N1). Hereinafter, this thermal alkaline agent may be referred to as a "specific thermal alkaline agent" in some cases, as distinguished from other thermal alkaline agents.
[ chemical formula 4]
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group, R C1 Represents a hydrogen atom or a protecting group, and L represents a 2-valent linking group.
L is a 2-valent linking group, preferably a 2-valent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length of the bond is the number of atoms present in the atomic arrangement that forms the shortest distance between 2 carbonyl groups in the formula, and represents the number of atoms required for bonding between 2 carbonyl carbons adjacent to the linking group L. The chain length of the linking chain of the exemplified compound B-1 described later is 2.
The particular thermal alkaline generator preferably undergoes a decomposition reaction within the molecule. Specifically, it is preferable that the reaction is carried out by heating or the like, and in the formula, the carbonyl group at the (L-C (=O) -N-) position of the amide structure is dissociated from the nitrogen atom to produce an amine (preferably a secondary amine). From the viewpoint of allowing the decomposition reaction to proceed rapidly, it is preferable that the linking group L has the above-mentioned linking chain length, but it is more preferable that the linking group is constituted within the range of the number of carbon atoms of each linking group exemplified below. In addition, from the viewpoint of the intramolecular decomposition reaction, when the linking group L is an alkenylene group, it is preferable that the carbonyl group bonded to both ends of L have a cis-type three-dimensional configuration with respect to L. However, the invention should not be construed in a limiting sense as a result of this description.
The thermal alkaline agent of the present invention is acidic or neutral at ordinary temperature, and therefore does not promote cyclization of a precursor of a heterocyclic polymer. That is, the photosensitive resin composition containing the thermal alkaline agent of the present invention maintains storage stability. The cyclisation of the heterocyclic polymer-containing precursor is efficiently carried out by the base generated from the thermal alkaline generator after heating, and therefore the resulting cured film is excellent in elongation at break. In the present invention, the following configuration is also possible: when a base is generated from a specific thermal alkaline generator, the decomposed products other than the generated base volatilize and substantially do not remain in the film. Wherein "substantially no residue" preferably means 1 mass% or less, 0.5 mass% or less, or may be 0.1 mass% or less.
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group (preferably, a carbon number of 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), preferably a hydrocarbon group (preferably, a carbon number of 1 to 24, more preferably 1 to 12, still more preferably 1 to 10), specifically, an aliphatic hydrocarbon group (preferably, a carbon number of 1 to 24, more preferably 1 to 12, still more preferably 1 to 10) or an aromatic hydrocarbon group (preferably, a carbon number of 6 to 22, more preferably 6 to 18, still more preferably 6 to 10), preferably an aliphatic hydrocarbon group. As R N1 R is R N2 If an aliphatic hydrocarbon group is used, the alkali generated is preferably highly basic. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, an aliphatic hydrocarbon group having an oxygen atom in a hydrocarbon chain is exemplified.
As a constituent R N1 R is R N2 Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain.
The linear or branched chain alkyl group is preferably a group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
The cyclic alkyl group is preferably a C3-C12 group, more preferably a C3-C6 group. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.
The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably a group having 4 to 24 carbon atoms, more preferably 4 to 18, and still more preferably 4 to 12. Examples of the group related to the combination of the chain alkyl group and the cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, and the like.
The alkyl group having an oxygen atom in the chain is preferably a carbon number of 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be straight-chain or branched.
Wherein R is from the viewpoint of increasing the boiling point of the base formed by decomposition, which will be described later N1 R is R N2 Preferably an alkyl group having 5 to 12 carbon atoms. In the case where a long chain alkyl group is used in the photosensitive resin composition, there is a case where adhesion is reduced when a layer of metal (for example, copper) is laminated, and in a formulation where this part is emphasized, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable from the viewpoint that the adhesion is suppressed to maintain good adhesion to the metal layer.
R N1 R is R N2 Can be connected with each other to form a ring structure. When the cyclic structure is formed, an oxygen atom or the like may be present in the chain. And, from R N1 R is R N2 The cyclic structure formed may be a single ring or a condensed ring, but is preferably a single ring. The cyclic structure to be formed is preferably a 5-or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolinidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and examples thereof include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
R C1 Represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and examples thereof include protecting groups which are decomposed by an acid.
Examples of the groups which are released by an acid include-C (R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 ) Etc.
In the above formula, R 36 ～R 39 Each independently represents an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms) or an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms). R is R 36 ～R 38 Can be linked to each other to form a ring. And R is 36 、R 37 、R 39 Can be linked to each other to form a ring. Alkyl is a straight, branched or cyclic alkyl.
R 01 R is R 02 Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), or an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms). R is R 39 Can be linked to a carbon atom (C) in the formula to form a ring.
R 36 ～R 39 、R 01 R is R 02 The straight-chain or branched alkyl group of (a) is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-group, sec-butyl, hexyl, octyl and the like.
R 36 ～R 39 、R 01 R is R 02 The cycloalkyl group of (2) may be a monocyclic ring type or a polycyclic ring type. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. The polycyclic ring is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include adamantyl and norbornylIce-methyl, camphene, dicyclopentyl, alpha-pinenyl, tricyclodecyl, tetracyclododecyl, androstanyl (androstanyl), etc. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
R 36 ～R 39 、R 01 R is R 02 The aryl group of (a) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl.
R 36 ～R 39 、R 01 R is R 02 The aralkyl group of (a) is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl and the like.
R 36 ～R 39 、R 01 R is R 02 The alkenyl group of (a) is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, cyclohexenyl, and the like.
As R 36 And R is R 37 The ring formed by bonding is preferably cycloalkyl (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl. More preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms, and particularly preferably a monocyclic cycloalkyl group having 5 carbon atoms.
Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl, ethyl, isopropyl, t-butyl, and cyclohexyl. The chain alkyl group having an oxygen atom in the chain includes, specifically, an alkoxyalkyl group, and more specifically, a methoxymethyl (MOM) group, an ethoxyethyl (EE) group, and the like. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a Tetrahydropyran (THP) group.
If R is C1 When a specific thermal alkaline generator is used in the photosensitive resin composition, the acid (carboxyl group) is exposed. In some cases, the stability is lowered by performing reactions other than those required Factors. In this case, R is preferably selected from the viewpoint of suppressing or even preventing the progress of the above reaction and maintaining good stability C1 A protecting group is introduced.
On the other hand, from the viewpoint of exerting the desired action of the specific thermal alkaline agent, it is preferable to release the protecting group at an appropriate period to form a carboxyl group (-COOH) or its anion (-COO) at the terminal of the specific thermal alkaline agent - ). The method of releasing the protecting group in the reaction system at the desired time is not particularly limited, and examples thereof include (1) a method of releasing the protecting group of a specific thermal alkaline agent by the action of an acid generated in the photosensitive resin composition by the presence of an acid or an acid generator in the composition, and (2) a method of releasing the protecting group of a specific thermal alkaline agent by heating the photosensitive resin composition. Examples of the acid generator used for releasing the protecting group in the embodiment (1) include thermal acid generators. The heating temperature for detachment of the protecting group applied to the embodiment of (2) is not particularly limited, and is preferably set to a temperature range in which a decomposition base is generated by the decomposition of the thermal alkaline generator described below. In this way, it is preferable from the standpoint that the release of the acid protecting group is performed simultaneously by the heat treatment for cyclizing and curing the heterocyclic polymer-containing precursor of the photosensitive resin composition, so that not only is the efficiency and energy saving achieved without additional heat treatment or the like, but also the stability of the composition can be maintained until the curing treatment is performed on the photosensitive resin composition.
The 2-valent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have a kind of atom other than carbon atom in the hydrocarbon chain. More specifically, the group is preferably a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a 2-valent aromatic hydrocarbon group, or a group related to a combination of a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a 2-valent aromatic hydrocarbon group, and still more preferably a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain. These groups preferably have no oxygen atoms.
The 2-valent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 6 carbon atoms. The 2-valent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The 2-valent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. The group (for example, an arylene alkyl group) related to the combination of a 2-valent aliphatic hydrocarbon group and a 2-valent aromatic hydrocarbon group is preferably a group having 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and still more preferably 7 to 10 carbon atoms.
The linking group L is specifically preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.
The linear or branched chain alkylene group is preferably a group having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. Examples of the linear or branched chain alkylene group include methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl and the like.
The cyclic alkylene group is preferably a group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkylene group include cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, and cyclohexanediyl group.
The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably a group having 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the group related to the combination of the chain alkylene group and the cyclic alkylene group include methylenecyclohexanediyl group, ethylenecyclohexanediyl group, propylenecyclohexanediyl group, methylenecyclohexanediylmethylene group, ethylenecyclohexanediylethylene group, and the like.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably a carbon atom number of 1 to 12, more preferably 1 to 6, still more preferably 1 to 3. Examples thereof include methoxymethylene, ethoxyethylene, propoxypropylene, and propoxypropylene.
The linear or branched alkenyl group is preferably a linear or branched alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms. The linear or branched alkenyl group is preferably a c=c bond number of 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. Examples of the linear or branched alkenyl group include an ethenylene group, an propenylene group, and a methylarylene group.
The cyclic alkenylene group is preferably a group having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
The cyclic alkenylene group preferably has a c=c bond number of 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2. Examples of the cyclic alkenylene group include cyclopropenediyl group, cyclobutenediyl group, and cyclohexene diyl group.
The arylene group is preferably a group having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, anthracenediyl, phenanthrenediyl and the like.
The arylene alkylene group has preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and still more preferably 7 to 11 carbon atoms. Examples of the arylene alkylene include phenylene methylene, phenylene ethylene, naphthylene methylene, naphthylene ethylene, xylylene and ethylene phenylene ethylene.
Among them, preferred are a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group, and more preferred are a 1, 2-ethylene group, a propane diyl group (particularly a 1, 3-propane diyl group), a cyclohexane diyl group (particularly a 1, 2-cyclohexane diyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1, 2-phenylene group), a phenylene methylene group (particularly a 1, 2-phenylene methylene group), and an ethyleneoxy ethylene group (particularly a 1, 2-ethyleneoxy-1, 2-ethylene group).
The specific thermal alkaline generator represented by the above formula (N1) is preferably decomposed by heating to form a compound represented by the following formula (N2) (hereinafter, this compound may be referred to as "decomposed alkali").
[ chemical formula 5]
In the formula (N2), R N1 R is R N2 Each independently represents a 1-valent organic group. R is R N1 R is R N2 The preferable range of (a) is the same as the range defined in the formula (N1), and the preferable range of the cyclic structure formed by connecting the two is also the same as the range defined in the formula (N1).
The decomposition product alkali produced by the decomposition of the specific thermal alkaline generator preferably has a boiling point (gas pressure 101325 Pa) of 40℃or higher, more preferably 80℃or higher, and still more preferably 100℃or higher. The upper limit is practically 400℃or lower. When the catalyst is used in a photosensitive resin composition, scattering due to volatilization from the inside of the reaction system is suppressed, and the desired action of the base (the action of a catalyst for promoting cyclization of a precursor of a heterocyclic polymer) is more effectively exerted.
From the standpoint of achieving a suitably high boiling point range as above, R N1 R is R N2 The total number of carbon atoms in (a) is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit is actually 24 or less. The preferable range of the number of carbon atoms described above from the viewpoint of this action is also applicable to the formula (N1).
The specific thermal alkali generator is preferably contained in the photosensitive resin composition and used in combination with the heterocyclic polymer-containing precursor (further, more preferably in combination with the radical polymerizable compound and the photo radical polymerization initiator), and preferably functions to decompose by heating to generate a base in the photosensitive resin composition, thereby promoting the cyclization reaction of the polymer precursor and effectively curing the resin composition. The decomposition temperature of the specific thermal alkaline generator is not particularly limited, but is preferably 50℃or higher, more preferably 80℃or higher, still more preferably 120℃or higher, and still more preferably 180℃or higher. The upper limit is preferably 450℃or lower, more preferably 350℃or lower, and still more preferably 250℃or lower. The compound which decomposes at a lower temperature is preferable because it can cure the photosensitive resin composition with lower energy consumption when used in the photosensitive resin composition. On the other hand, when the decomposition temperature is not less than the above lower limit, it is preferable from the viewpoint of suppressing the occurrence of an unexpected alkali generation and an action during storage at normal temperature and improving the storage stability of the photosensitive resin composition.
The specific thermal alkaline generator of the present invention is particularly preferable because it does not cause a reaction with a photo radical polymerization initiator or the like or a radical polymerizable compound or the like possibly contained in the photosensitive resin composition to inhibit photosensitivity thereof, can effectively maintain photosensitivity after curing, and can exhibit favorable development characteristics after exposure.
The molecular weight of the specific thermal alkaline generator is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, and still more preferably 250 or more, from the viewpoints of setting the effective decomposition temperature and setting the boiling point of the above-mentioned decomposition-generated base to an appropriate range. The upper limit is practically 1000 or less. In addition, the preferred range of the molecular weight is also applicable to the case where the carboxyl group of the specific thermal alkaline agent has a protecting group.
The following examples are examples of the thermal alkaline generator represented by the formula (N1), but the present invention should not be construed as being limited thereto.
[ chemical formula 6]
The boiling point of the base (amine compound) and the pKa of the conjugate acid generated from each of the above-described thermal alkaline generators are shown below.
TABLE 1
Numbering of compounds Generating the boiling point of the amine pKa of amine conjugate acid
(B-1) 148℃ 11.0
(B-2) 256℃ 11.4
(B-3) 256℃ 11.4
(B-4) 106℃ 11.2
(B-5) 129℃ 9.0
(B-6) 159℃ 11.0
(B-7) 55℃ 10.8
(B-8) 256℃ 11.4
(B-9) 84℃ 10.8
(B-10) 196℃ 4.8
(B-11) 148℃ 11.0
(B-12) 148℃ 11.0
(B-13) 148℃ 11.0
(B-14) 148℃ 11.0
(B-15) 148℃ 11.0
(B-16) 298℃ 11.1
(B-17) 256℃ 11.4
(B-18) 256℃ 11.4
(B-19) 256℃ 11.4
The following examples are also examples of the thermal alkaline generator represented by the formula (N1), but the present invention should not be construed as being limited thereto.
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
The thermal alkaline agent represented by the above formula (N1) can be produced by a conventional method. Further, a commercially available reagent can be used.
The pKa of the conjugate acid of the base to be produced is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more, with respect to the specific thermal alkaline generator represented by the above formula (N1). The upper limit is not particularly limited, but is practically 14 or less. When the pKa of the specific thermal alkaline generator is set to the above range, the produced alkali can efficiently carry out the cyclization reaction of the polymer precursor, and the elongation at break of the cured film can be improved at a low temperature, which is preferable. The pKa here is set to a value determined by the following method.
The pKa mentioned in the present specification means that the equilibrium constant Ka is expressed by the negative common logarithmic pKa in consideration of the dissociation reaction of hydrogen ions released from an acid. Smaller pKa means stronger acid. Unless otherwise stated, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, reference may be made to the values described in the "reform 5 th edition chemical review base" by the japan chemical society.
The content of the specific thermal alkaline generator is preferably 0.01 to 50% by mass relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.05 mass% or more, and still more preferably 0.1 mass% or more. The upper limit is more preferably 10 mass% or less, and still more preferably 5 mass% or less.
The content of the specific thermal alkaline generator is preferably 0.015 parts by mass or more, more preferably 0.075 parts by mass or more, and still more preferably 0.15 parts by mass or more, based on 100 parts by mass of the polymer precursor. The upper limit is, for example, preferably 15.0 parts by mass or less, more preferably 7.5 parts by mass or less, and still more preferably 1.5 parts by mass or less.
When the content of the specific thermal alkaline generator is not less than the above lower limit, it is preferable from the viewpoint that good storage stability is ensured in the photosensitive resin composition and mechanical properties of the cured film can be preferably achieved.
By setting the upper limit value or less, corrosion resistance of a metal (for example, copper used for wiring or the like) can be ensured.
One or two or more specific thermal alkaline agents can be used. When two or more kinds are used, the total amount is preferably in the above range.
The photosensitive resin composition of the present invention may or may not contain a thermal alkaline agent other than the specific thermal alkaline agent. Examples of the other thermoalcifer include those described in WO2015/199219 and WO2015/199220, which are incorporated herein by reference. In the present invention, the composition may be configured to substantially not include any other thermal alkaline agent than the specific thermal alkaline agent. The content of the specific thermal alkaline generator contained in the photosensitive resin composition of the present invention is not substantially 5% by mass or less, preferably not more than 3% by mass, and more preferably not more than 1% by mass.
The photobase generator may or may not be included together with the specific thermal alkali generator.
Photosensitive resin composition
The photosensitive resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention" or "the resin composition of the present invention") contains a heterocyclic polymer-containing precursor and the above-described specific thermal alkaline generator. Further, the photosensitive resin composition of the present invention preferably contains a photo radical polymerization initiator and a radical polymerizable compound. Hereinafter, the components other than the specific thermal alkaline generator will be described in detail.
< Polymer precursor >
As the precursor of the heterocyclic ring-containing polymer, at least 1 polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors can be exemplified, and more preferably, polyimide precursors.
Polyimide precursor
The polyimide precursor preferably contains a structural unit represented by the following formula (1). By adopting such a structure, a composition having more excellent film strength can be obtained.
[ chemical formula 10]
A 1 A is a 2 Each independently represents an oxygen atom or NH, R 111 Represents a 2-valent linking group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group.
A 1 A is a 2 Each independently is an oxygen atom or NH, preferably an oxygen atom.
<<<R 111 >>>
R 111 Represents a 2-valent linking group, preferably a 2-valent organic group. Examples of the 2-valent organic group include a linear or branched aliphatic group,The cyclic aliphatic group, aromatic group, heteroaromatic group, or group containing a combination thereof is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group containing a combination thereof, more preferably an aromatic group having 6 to 20 carbon atoms.
R 111 Preferably derived from diamines. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. The diamine may be used alone or in combination of two or more.
Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group containing a combination of these, and more preferably contains an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.
[ chemical formula 11]
Wherein A is preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S (=O) 2 -, -NHCO-and combinations of these, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom-O-, -C (=o) -, -S-and-SO 2 The radicals in are further preferably selected from the group consisting of-CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -and-C (CH) 3 ) 2 -a valence 2 group of the group consisting of.
Specific examples of the diamine include a diamine selected from 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-diaminocyclopentane or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane, isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4' -diaminobiphenyl and 3,3' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -diaminodiphenylmethane and 3,3' -diaminodiphenylmethane 4,4' -diaminodiphenyl sulfone and 3,3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide and 3,3' -diaminodiphenyl sulfide, 4' -diaminobenzophenone and 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, and 2,2' -dimethyl-4, 4' -diaminobiphenyl (4, 4' -diamino-2, 2' -dimethylbiphenyl), 3' -dimethoxy-4, 4' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane 2, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino-p-diphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3' -dimethyl-4, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3' -diethyl-4, 4' -diaminodiphenyl methane 3,3' -dimethyl-4, 4' -diaminodiphenylmethane, 4' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3',4,4' -tetraminobiphenyl, 3', 4' -tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3, 3-dihydroxy-4, 4' -diaminobiphenyl, 9' -bis (4-aminophenyl) fluorene, 4' -dimethyl-3, 3' -diaminodiphenyl sulfone, 3',5' -tetramethyl-4, 4' -diaminodiphenyl methane, 2- (3 ', ethyl 5' -diaminobenzoyloxy) methacrylate), 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotoluene, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecaheptane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) hexafluoropropane, 2, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl 4,4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', at least one diamine selected from the group consisting of 5,5' -tetramethyl-4, 4' -diaminobiphenyl, 4' -diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2', 5', 6' -hexafluoro-tolidine and 4,4' -diaminotetrabiphenyl.
Further, diamines (DA-1) to (DA-18) shown below are also preferable.
[ chemical formula 12]
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Further, as a preferable example, a diamine having at least two or more alkylene glycol units in the main chain can be given. The diamine preferably contains two or more ethylene glycol chains or propylene glycol chains in total in one molecule, and more preferably contains no aromatic ring. Specific examples thereof include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN corporation), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (2-aminopropoxy) propane-2-yl) oxy) propane-2-amine, and the like, but are not limited thereto.
The structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176 are shown below.
[ chemical formula 13]
In the above, x, y and z are average values.
From the viewpoint of flexibility of the resulting cured film, R is preferable 111 from-Ar 0 -L 0 -Ar 0 -a representation. Wherein Ar is 0 Each independently represents an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and is preferably a phenylene group. L (L) 0 Represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=o) -, -S (=o) 2 -NHCO-, and a group selected from a combination of these. Preferred ranges are as defined for A above.
From the viewpoint of the i-ray transmittance, R 111 The 2-valent organic group represented by the following formula (51) or (61) is preferable. In particular, from the viewpoint of the i-ray transmittance and availability, the 2-valent organic group represented by formula (61) is more preferable.
[ chemical formula 14]
R 50 ～R 57 Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R 50 ～R 57 At least one of which is a fluorine atom, methyl group, fluoromethyl group, difluoromethyl group or trifluoromethyl group.
As R 50 ～R 57 Examples of the 1-valent organic group (1) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
[ chemical formula 15]
R 58 R is R 59 Each independently is a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.
Examples of the diamine compound having a structure represented by the formula (51) or (61) include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. One of these may be used, or two or more of them may be used in combination
<<<R 115 >>>
R in formula (1) 115 Represents a 4-valent organic group. The 4-valent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).
[ chemical formula 16]
R 112 The meaning of A is the same, the preferred range is also the same.
With respect to R in formula (1) 115 The 4-valent organic group represented is specifically a tetracarboxylic acid residue remaining after removal of an acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
[ chemical formula 17]
R 115 Represents a 4-valent organic group. R is R 115 Meaning of (A) and R of formula (1) 115 The same applies.
Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -diphenylmethane tetracarboxylic dianhydride, 2',3,3' -diphenylmethane tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, and 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2',3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,2,4, 5-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,8,9, 10-phenanthrene tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, at least one of 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.
Further, preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.
[ chemical formula 18]
<<<R 113 R is R 114 >>>
In the formula (1), R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group. R is R 113 R is R 114 At least one of them preferably contains a radical polymerizable group, more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and preferable examples thereof include a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).
[ chemical formula 19]
In the formula (III), R 200 Represents a hydrogen atom or a methyl group, more preferably a methyl group.
In the formula (III), R 201 Represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 Or a (poly) oxyalkylene group having 4 to 30 carbon atoms (as the alkylene group, preferably 1 to 12 carbon atoms, more preferably 1 to 6, particularly preferably 1 to 3; and the repetition number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3). Further, (poly) oxyalkylene means oxyalkylene or polyoxyalkylene.
Preferred R 201 Examples of (C) include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH 2 CH(OH)CH 2 -, more preferably ethylene, propylene, trimethylene, -CH 2 CH(OH)CH 2 -。
R is particularly preferred 200 Is methyl, R 201 Is ethylene.
As a preferred embodiment of the polyimide precursor in the present invention, R is 113 Or R is 114 Examples of the 1-valent organic group include aliphatic groups, aromatic groups, and aralkyl groups having 1,2, or 3 acid groups, preferably 1 acid group. Specifically, examples thereof include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group are exemplified. The acid group is more preferably a hydroxyl group. Namely, R 113 Or R is 114 Preferably a group having a hydroxyl group.
As represented by R 113 Or R is 114 The 1-valent organic group represented may preferably be a substituent that improves the solubility of the developer.
From the viewpoint of solubility in an aqueous developer, R 113 Or R is 114 More preferred are a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group.
From the viewpoint of solubility to organic solvents, R 113 Or R is 114 Preferably a 1-valent organic group. The 1-valent organic group is preferably an alkyl group containing a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic ring). The alkyl group may be any of linear, branched, and cyclic. Examples of the straight-chain or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphene (camphenyl), decalin, tricyclodecyl, tetracyclodecyl, camphordiacyl, dicyclohexyl and pinenyl (pinenyl). The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described below.
The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (examples of the cyclic structure constituting the group include a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indene ring, a perylene ring, a fused pentacene ring, an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a fused tetracene ring, a,Ring, triphenylene ring, etc.) or a substituted or unsubstituted aromatic heterocyclic group (as a cyclic structure constituting a group, a fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthrine ring, thianthrene ring, chromene ring, xanthene ring, phenothiazine ring, or phenazine ring).
In addition, the polyimide precursor preferably has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and more preferably 20 mass% or less. The upper limit is not particularly limited, but is practically 50 mass% or less.
In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by formula (1). Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A) or (1-B).
[ chemical formula 20]
A 11 A is a 12 Represents an oxygen atom or NH, R 111 R is R 112 Each independently represents a 2-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R 113 R is R 114 At least one of (2) is preferably a radical polymerizable group-containing group, more preferably a radical polymerizable group.
A 11 、A 12 、R 111 、R 113 R is R 114 Each independently and preferably within the range A in formula (1) 1 、A 2 、R 111 、R 113 R is R 114 The meaning of the preferred ranges of (2) are the same.
R 112 Is preferably within the range of R in formula (5) 112 Of these, oxygen atoms are more preferable.
In the formula (1-A), the bonding position of the carbonyl group in the benzene ring is preferably 4,5,3',4'. In the formula (1-B), 1, 2, 4,5 are preferable.
In the polyimide precursor, the structural unit represented by the formula (1) may be one kind or two or more kinds. And, a structural isomer of the structural unit represented by formula (1) may be contained. In addition to the structural unit of the above formula (1), the polyimide precursor may contain other types of structural units.
As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total structural units are structural units represented by the formula (1) can be exemplified. The upper limit is practically 100 mol% or less.
The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100000, and even more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The molecular weight of the polyimide precursor is preferably dispersed to a degree of 1.5 to 3.5, more preferably 2 to 3.
Polyimide precursors can be obtained by reacting a dicarboxylic acid or dicarboxylic acid derivative with a diamine. Preferably, the acid is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the resultant with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent may be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone may be exemplified.
In the production of the polyimide precursor, the step of precipitating solids is preferably included. Specifically, the polyimide precursor in the reaction liquid is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid precipitation can be performed.
Polybenzoxazole precursor-
The polybenzoxazole precursor preferably contains a structural unit represented by the following formula (2).
[ chemical formula 21]
R 121 Represents a 2-valent organic group, R 122 Represents a 4-valent organic group, R 123 R is R 124 Each independently represents a hydrogen atom or a 1-valent organic group.
R 121 Represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least one of an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 12 carbon atoms). As a constituent R 121 Examples of the aromatic group of (C) includeR of the formula (1) 111 Is an example of (a). The aliphatic group is preferably a linear aliphatic group. R is R 121 Preferably derived from 4,4' -oxo-dibenzoyl chloride.
In the formula (2), R 122 Represents a 4-valent organic group. R in the above formula (1) is used as a 4-valent organic group 115 The meaning of (2) is the same and the preferred ranges are also the same. R is R 122 Preferably 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R 123 R is R 124 Each independently represents a hydrogen atom or a 1-valent organic group, and the meaning is the same as R in the above formula (1) 113 R is R 114 The same applies to the preferred ranges.
In addition to the structural units of formula (2) described above, the polybenzoxazole precursors may also contain other types of structural units.
From the viewpoint of suppressing the occurrence of warpage of a cured film accompanied by closed-loop, the precursor preferably contains a diamine residue represented by the following formula (SL) as another kind of structural unit.
[ chemical formula 22]
Z has a structure a and a structure b, R 1s Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms), R 2s Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R 3s 、R 4s 、R 5s 、R 6s At least one of them is an aromatic group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, particularly preferably having 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 6 carbon atoms), and may be the same or different. The polymerization of the a and b structures may be block polymerization or random polymerization. In the Z moiety, the structure of a is preferably 5 to 95 mol%, and the structure of b is preferably 95 to 5 mol% and a+b is 100 mol%.
In the formula (SL), preferable Z is R in the b structure 5s R is R 6s Z is phenyl. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the elasticity of the polybenzoxazole precursor after dehydration and ring closure can be reduced, and the effect of suppressing warpage and the effect of improving solubility can be achieved.
When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, it is preferable to further contain a tetracarboxylic acid residue remaining after the removal of the acid dianhydride from the tetracarboxylic acid dianhydride as a structural unit in view of improving the alkali solubility. Examples of the tetracarboxylic acid residues include R in the formula (1) 115 Is an example of (a).
The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, still more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The molecular weight of the polybenzoxazole precursor has a dispersity of preferably 1.5 to 3.5, more preferably 2 to 3.
The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, further preferably 50 mass% or more, further preferably 60 mass% or more, further preferably 70 mass% or more, based on the total solid content of the composition. The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5 mass% or less, more preferably 99 mass% or less, further preferably 98 mass% or less, further preferably 95 mass% or less, based on the total solid content of the composition.
The photosensitive resin composition of the present invention may contain only one polymer precursor or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.
In addition to the above, the photosensitive resin composition of the present invention may contain other components. Specifically, a photopolymerization initiator, a photocuring accelerator, a thermal radical polymerization initiator, a thermal acid generator, and the like can be exemplified.
< photopolymerization initiator >
The photopolymerization initiator that can be used for the sensitizer is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. In addition, an active agent that generates active radicals by acting on a photosensitizing agent that is excited by light may be used.
The photo radical polymerization initiator preferably contains at least one compound having an absorbance of at least about 50 moles in the range of about 300 to 800nm (preferably 330 to 500 nm). The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to measure the content of the organic compound by an ultraviolet-visible light spectrometer (Cary-5 spectrophotometer, manufactured by Varian Co., ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium bases, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0138 to 0151 of Japanese patent application laid-open No. 2016-027357, publication WO2015/199219, and the disclosure of these is incorporated herein by reference.
Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which is incorporated herein by reference. Among the commercial products, KAYACURE DETX (Nippon Kayaku co., ltd.) is also preferably used.
As the photo radical polymerization initiator, it is also preferable to use hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in JP-A-4225898 can also be used.
As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (product names: all are manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: all manufactured by BASF corporation) which are commercially available products can be used.
As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179 having a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm or the like can be used.
Examples of the acylphosphine oxide initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Further, IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF corporation) can be used as a commercial product.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).
The photo radical polymerization initiator is more preferably an oxime compound. By using an oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, those having a wide exposure latitude (exposure margin) and also functioning as a photocuring accelerator are particularly preferable.
Specific examples of the oxime compound include a compound described in JP-A-2001-233836, a compound described in JP-A-2000-080068, and a compound described in JP-A-2006-342166.
Preferable oxime compounds include, for example, 3-benzoyloxy iminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxy iminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxy imino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy imino1-phenylpropane-1-one having the following structures. In the photosensitive resin composition of the present invention, an oxime compound (oxime-based photopolymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > c=n-O-C (=o) -in the molecule.
[ chemical formula 23]
Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above is manufactured by BASF corporation), ADEKA OPTOMERN-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) may also be preferably used. In addition, TR-PBG-304 (manufactured by Hezhou powerful electronic New materials Co., ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Further, DFI-091 (DAITO CHEMIX Co., ltd.) can be used.
Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include a compound described in JP 2010-26261028A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852A, and compound (C-3) described in paragraph 0101 of JP 2013-164471A.
The most preferable oxime compound includes an oxime compound having a specific substituent shown in japanese patent application laid-open No. 2007-269779, an oxime compound having a thioaryl group shown in japanese patent application laid-open No. 2009-191061, and the like.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium base compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and bases thereof, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds.
More preferred photo-radical polymerization initiator is a trihalomethyltriazine compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium hydroxide compound, a benzophenone compound, an acetophenone compound, further preferred is at least one compound selected from the group consisting of trihalomethyltriazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, still further preferred is a metallocene compound or oxime compound, and still further preferred is an oxime compound.
The photo radical polymerization initiator may be a benzoin compound such as benzophenone, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), a benzoin compound such as N, N ' -tetraalkyl-4, 4' -diaminobenzophenone, an aromatic ketone such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone-1, an alkylanthraquinone, a benzoin compound such as benzoin alkyl ether, a benzoin compound such as benzoin, a benzyl derivative such as benzyl dimethyl ketal, or the like. Further, a compound represented by the following formula (I) can also be used.
[ chemical formula 24]
In the formula (I), R I00 Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, or a phenyl or biphenyl group substituted by at least one of an alkyl group having 1 to 4 carbon atoms, R I01 Is a group represented by formula (II), or is a group represented by formula (II) and R I00 The same radicals R I02 ～R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.
[ chemical formula 25]
Wherein R is I05 ～R I07 R is the same as the R of the formula (I) I02 ～R I04 The same applies.
Further, the photo radical polymerization initiator can be a compound described in paragraphs 0048 to 0055 of International publication WO 2015/125469.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The photopolymerization initiator may be contained in one kind or two or more kinds. When two or more photopolymerization initiators are contained, the total thereof is preferably within the above range.
< thermal polymerization initiator >
As the sensitizer, a thermal polymerization initiator may be used, and in particular, a thermal radical polymerization initiator may be used. The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or accelerates the polymerization reaction of a compound having polymerizability. By adding a thermal radical polymerization initiator, cyclization of the polymer precursor can be performed and polymerization reaction of the polymer precursor can be performed, so that higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063254.
When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 5 to 15% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The thermal radical polymerization initiator may be contained in one kind or two or more kinds. When two or more thermal radical polymerization initiators are contained, the total is preferably in the above range.
< polymerizable Compound >
Radical polymerizable Compound
The photosensitive resin composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group. The radical polymerizable group is preferably a (meth) acryloyl group.
The number of radical polymerizable groups in the radical polymerizable compound may be 1 or 2 or more, and the radical polymerizable compound preferably has 2 or more radical polymerizable groups, more preferably 3 or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.
From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one radical polymerizable compound having 2 or more functions and more preferably contains at least one radical polymerizable compound having 3 or more functions. The compound may be a mixture of a 2-functional radical polymerizable compound and a 3-functional or more radical polymerizable compound. Further, the number of functional groups of the radical polymerizable compound indicates the number of radical polymerizable groups in 1 molecule.
Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. Also, the substitution reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and the substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. For a specific example, refer to the descriptions in paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, and these descriptions are incorporated herein.
The radical polymerizable compound preferably has a boiling point of 100℃or higher at normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tri (acryloxyethyl) isocyanato, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerol or trimethylolethane and then subjecting the resultant mixture to (meth) acrylation, and functional acrylates such as those described in Japanese patent application publication No. 48-041708, japanese patent application publication No. 50-006034, the urethane (meth) acrylates described in Japanese patent application publication No. 51-037193, japanese patent application publication No. 48-064183, japanese patent application publication No. 49-043191, and Japanese patent application publication No. 52-030490. Furthermore, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate, and the like can also be mentioned.
Further, as a preferable radical polymerizable compound other than the above, a compound having a fluorene ring and having 2 or more groups containing an ethylenically unsaturated bond or a cardo resin described in japanese unexamined patent publication No. 2010-160418, japanese unexamined patent publication No. 2010-129825, japanese patent publication No. 4364216, and the like can also be used.
Further, examples of the compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 1-040337 and Japanese patent publication No. 1-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 2-025493. Furthermore, a perfluoroalkyl group-containing compound described in Japanese patent application laid-open No. 61-022048 can also be used. Furthermore, those described as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol.20, no.7, pages 300 to 308 (1984) can also be used.
In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication WO2015/199219, which are incorporated herein by reference, can be used.
Further, the compounds described in JP-A-10-062986 as the formula (1) and formula (2) and specific examples thereof can also be used as the radical polymerizable compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant compound.
Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can be used as other radical polymerizable compounds, and these are incorporated herein.
The radical polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330;Nippon Kayaku Co, manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320;Nippon Kayaku Co, manufactured by Ltd.), A-TMMT: shin-Nakamura Chemical Co, manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310;Nippon Kayaku Co, manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; nippon Kayaku Co, manufactured by Ltd., manufactured by A-DPH; shin-Nakamura Chemical Co, manufactured by Ltd.), or a structure in which these (meth) acryloyl groups are bonded via a glycol residue or a propylene glycol residue. These oligomer types can also be used.
Examples of the commercially available products of the radical polymerizable compound include SR-494 as a 4-functional acrylate having 4 ethyleneoxy chains, which is manufactured by Sartomer Company, inc., sartomer Company as a 2-functional methyl acrylate having 4 ethyleneoxy chains, SR-209, 231, 239, nippon Kayaku Co., inc., DPCA-60 as a 6-functional acrylate having 6 pentylene oxygen chains, TPA-330 as a 3-functional acrylate having 3 isobutylene oxygen chains, urethane oligomer UAS-10, urethane oligomer UAB-140 (NIPPON PAPER INDUSTRIES CO., LTD., product), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (Shin-Nakamura Chemical Co., product of Ltd.), DPHA-40H (product of Nippon Kayaku Co., ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha chemical Co., product of Ltd.), BLEMERPME 400 (product of NOF CORPORATION), and the like.
As the radical polymerizable compound, urethane acrylates having an ethylene oxide skeleton as described in Japanese patent application laid-open No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 2-032293, and Japanese patent application laid-open No. 2-016765, japanese patent application laid-open No. 58-049860, japanese patent application laid-open No. 56-017654, japanese patent application laid-open No. 62-039417, and Japanese patent application laid-open No. 62-039418 are also preferred. Further, as the radical polymerizable compound, a compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 can also be used.
The radical polymerizable compound may be a radical polymerizable compound having an acid group such as a carboxyl group or a phosphate group. Among the radically polymerizable compounds having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a radically polymerizable compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride is more preferable. Particularly preferred are radical polymerizable compounds having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, wherein the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of the commercially available products include polyacid-modified acrylic oligomers produced by TOAGOSEI CO., ltd. Include M-510 and M-520.
The acid value of the radical polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, particularly preferably 5 to 30mgKOH/g. The radical polymerizable compound has an acid value within the above range, and thus is excellent in production and handling properties and further excellent in developability. And, the polymerizability is good.
The photosensitive resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as the radical polymerizable compound from the viewpoint of suppressing warpage accompanying control of the elastic modulus of the cured film. As the monofunctional radical polymerizable compound, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate and other allyl compounds can be preferably used. The monofunctional radical polymerizable compound is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure in order to suppress volatilization before exposure.
Polymerizable Compound other than the radically polymerizable Compound described above
The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the radical polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; oxetane compounds; a benzoxazine compound.
Compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl groups
The compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group is preferably a compound represented by the following formula (AM 1), (AM 4) or (AM 5).
[ chemical formula 26]
(wherein t represents an integer of 1 to 20, R 104 Represents a carbon number of 1 to 200t is a valence organic group, R 105 Represented by-OR 106 or-OCO-R 107 A group represented by R 106 R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms 107 An organic group having 1 to 10 carbon atoms. )
[ chemical formula 27]
(wherein R is 404 A 2-valent organic group having 1 to 200 carbon atoms, R 405 Represented by-OR 406 or-OCO-R 407 A group represented by R 406 R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms 407 An organic group having 1 to 10 carbon atoms. )
[ chemical formula 28]
(wherein u represents an integer of 3 to 8, R 504 A u-valent organic group having 1 to 200 carbon atoms, R 505 Represented by-OR 506 Or, -OCO-R 507 A group represented by R 506 R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms 507 An organic group having 1 to 10 carbon atoms. )
Specific examples of the compound represented by the formula (AM 4) include 46DMOC, 46DMOEP (trade name, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34-X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., ltd.), 2, 6-dimethylmethyl-4-t-buthylphenyl (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylmethyl-p-cresol (2, 6-dimethoxymethyl-p-cresol), 2, 6-dimethylmethyl-p-2, 6-dimethylcresol, and the like.
Specific examples of the compound represented by the formula (AM 5) include TriML-P, triML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name above, honshu Chemical Industry Co., ltd.), TM-BIP-A (trade name, ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name above, sanwa Chemical Co., ltd.).
Epoxy Compound (Compound having epoxy group)
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200 ℃ or less, and hardly causes film shrinkage since it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing the epoxy compound, low-temperature curing and warpage of the composition can be effectively suppressed.
The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group represents ethylene oxide having a structural unit number of 2 or more, and preferably having a structural unit number of 2 to 15.
Examples of the epoxy compound include alkylene glycol type epoxy resins such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, and propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; epoxy-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited thereto. Specifically, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICEK (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (trade name, manufactured by DIC Corporation), RIKARESIN (registered trademark) O-60E (trade name, new Japan Chemical Co., manufactured by Ltdder), and the like are manufactured by ORORP 400, and the like. Among these, polyethylene oxide group-containing epoxy resins are preferable in view of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, RIKARESIN (registered trademark) BEO-60E contains a polyethylene oxide group, and is preferable.
Oxetane compound (oxetane-containing Compound) >
Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and the like. As specific examples, TOAGOSEI co.ltd. ARON oxide series (e.g., next-121, next-221, next-191, next-223) can be preferably used, and these may be used alone or two or more kinds may be mixed.
Benzoxazine compound (compound having benzoxazolyl group)
The benzoxazine compound is preferable because it does not generate outgas during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.
Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolak type dihydrobenzoxazine compounds. These may be used alone, or two or more kinds may be mixed.
When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and still more preferably 30 mass% or less.
The other polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used simultaneously, the total amount thereof is preferably within the above range.
< solvent >
The photosensitive resin composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of the esters include preferable esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-alkoxy-2-methyl propionate, and ethyl 2-alkoxypropionate, methyl 2-ethoxypropionate, etc.), methyl 2-ethoxypropionate, etc. (for example, methyl 2-ethoxypropionate, etc.), methyl 2-ethoxypropionate, etc. Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like.
Examples of the ethers include preferably ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.
Examples of the aromatic hydrocarbon include toluene, xylene, anisole, and limonene.
Examples of sulfoxides include dimethyl sulfoxide.
As the amide, preferred are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide and the like.
The solvent is preferably mixed with two or more solvents from the viewpoint of improvement of the coating surface shape and the like.
In the present invention, one solvent or a mixed solvent of two or more solvents selected from methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferable. It is particularly preferred to use dimethyl sulfoxide and gamma-butyrolactone simultaneously.
The content of the solvent is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and still more preferably 40 to 70% by mass, of the total solid content concentration of the photosensitive resin composition of the present invention from the viewpoint of coatability. The content of the solvent may be adjusted according to the desired thickness and coating method.
The solvent may be contained in one kind or two or more kinds. When two or more solvents are contained, it is preferable that the above ranges are combined.
< migration inhibitor >
The photosensitive resin composition of the present invention preferably further comprises a migration inhibitor.
By including the migration inhibitor, transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer can be effectively inhibited.
The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, and triazine ring), compounds having thiourea and mercapto groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
Further, an ion scavenger that traps anions such as halogen ions can be used.
As other migration inhibitors, rust inhibitors described in paragraph 0094 of japanese patent application laid-open publication No. 2013-015701, compounds described in paragraphs 0073 to 0076 of japanese patent application laid-open publication No. 2009-283711, compounds described in paragraph 0052 of japanese patent application laid-open publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of japanese patent application laid-open publication No. 2012-194520, compounds described in paragraph 0166 of international publication No. WO2015/199219, and the like can be used.
Specific examples of migration inhibitors include the following compounds.
[ chemical formula 29]
When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass% relative to the total solid content of the photosensitive resin composition.
The migration inhibitor may be one kind only, or two or more kinds. When the migration inhibitor is two or more, it is preferable that the total thereof is in the above range.
< polymerization inhibitor >
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum base, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-t-butyl) phenylmethane and the like can be preferably used. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International publication WO2015/125469 can also be used.
In addition, the following compound (Me is methyl) can also be used.
[ chemical formula 30]
When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass, relative to the total solid content of the photosensitive resin composition of the present invention.
The polymerization inhibitor may be one kind only, or two or more kinds. When the polymerization inhibitor is two or more, it is preferable that the polymerization inhibitor is incorporated in the above range.
< Metal adhesion improver >
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent.
Examples of the silane coupling agent include a compound described in paragraph 0167 of International publication WO2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication WO2011/080992A1, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-04264, and a compound described in paragraph 0055 of International publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. The following compounds are also preferably used as the silane coupling agent. In the following formula, et represents ethyl.
[ chemical formula 31]
The metal adhesion improver can also be a compound described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 or a sulfide described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935.
The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor. By setting the lower limit value or more, adhesion between the cured film after the curing step and the metal layer is improved, and by setting the upper limit value or less, heat resistance and mechanical properties of the cured film after the curing step are improved. The metal adhesion improver may be one or two or more. When two or more kinds are used, it is preferable that the above ranges are combined.
< other additives >
The photosensitive resin composition of the present invention can be blended with various additives such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, a coagulation inhibitor, and the like as needed within a range that does not impair the effects of the present invention. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.
Thermal acid generator-
The photosensitive resin composition of the present invention may contain a thermal acid generator. When a specific thermal alkaline generator has a protecting group, the thermal acid generator is used for protecting group detachment.
The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymer precursor. Since the crosslinking reaction and cyclization of the polymer precursor are promoted by containing 0.01 parts by mass or more of the thermal acid generator, the mechanical properties and drug resistance of the cured film can be further improved. The content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.
The thermal acid generator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.
< sensitizing dye >
The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a heat curing accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and causes an effect such as electron transfer, energy transfer, heat generation, or the like. Thus, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed to decompose and generate radicals, acids, or bases. For details of the sensitizing dye, reference is made to paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The sensitizing dye may be used alone or in combination of two or more.
Chain transfer agent
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the third edition of the Polymer dictionary (society for Polymer (The Society of Polymer Science, japan) 2005). As the chain transfer agent, for example, a compound group having SH, PH, siH and GeH in the molecule is used. These supply hydrogen to the low-activity radicals to generate radicals, or after oxidation, the radicals can be generated by deprotonation. In particular, a thiol compound can be preferably used.
The chain transfer agent may be a compound described in paragraphs 0152 to 0153 of International publication WO 2015/199219.
When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be one kind only, or two or more kinds. When the chain transfer agent is two or more, the total range is preferably the above range.
Surfactant-
From the viewpoint of further improving coatability, various surfactants may be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The following surfactants are also preferred.
[ chemical formula 32]
The surfactant may be a compound described in paragraphs 0159 to 0165 of International publication WO 2015/199219.
When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number of the surfactants is two or more, the total range is preferably the above range.
Higher fatty acid derivative
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the photosensitive resin composition of the present invention so as to be locally present on the surface of the composition during drying after application.
Further, the higher fatty acid derivative may be a compound described in paragraph 0155 of International publication WO 2015/199219.
When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be one kind only, or two or more kinds. When the number of higher fatty acid derivatives is two or more, the total range is preferably the above range.
< restriction on other substances contained >
From the viewpoint of the coating surface shape, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5 mass%, more preferably less than 1 mass%, and even more preferably less than 0.6 mass%.
The metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulation properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
As a method for reducing metal impurities unexpectedly contained in the photosensitive resin composition of the present invention, there is a method in which a raw material having a small metal content is selected as a raw material constituting the photosensitive resin composition of the present invention, the raw material constituting the photosensitive resin composition of the present invention is filtered by a filter, and the inside of the apparatus is lined with polytetrafluoroethylene or the like to carry out distillation under a condition that contamination is suppressed as much as possible.
In view of the use as a semiconductor material and from the viewpoint of wiring corrosiveness, the content of halogen atoms in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, the halogen ion is preferably present in an amount of less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion is preferably in the above range.
As the container for containing the photosensitive resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 types of 6 layers of resins constituting the inner wall of the container and a bottle having 6 types of resins in a 7-layer structure are preferably used in order to suppress the mixing of impurities into the raw material or the composition. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351.
< preparation of composition >
The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
In order to remove foreign matters such as garbage and fine particles in the composition, filtration using a filter is preferable. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be pre-cleaned with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in parallel or in series. When a plurality of filters are used, filters having different pore diameters or materials may be used in combination. And, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a cyclic filtration. And, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressure at which pressurization is performed is preferably 0.05MPa or more and 0.3MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
< cured film, laminate, semiconductor device, and method for producing the same >
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing these will be described.
The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.
The cured film of the present invention may be laminated in 2 or more layers, and further in 3 to 7 layers, to form a laminate. The laminate having 2 or more layers of the cured film of the present invention is preferably one having a metal layer between the cured films. These metal layers may be preferably used as metal wirings such as a rewiring layer.
Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and a pressure buffer film. In addition, there are a sealing film, a substrate material (a base film or a cap layer of a flexible printed circuit board, an interlayer insulating film), a case where an insulating film for practical mounting as described above is patterned by etching, and the like. For these uses, for example, reference can be made to Science & Technology co., ltd, "high functionalization of polyimide and application Technology of application", 4 th month in 2008, yo-yo/prison, foundation and development of polyimide materials by CMC Technology library ", release 11 th month in 2011, and japanese polyimide/aromatic polymer research institute/code" latest polyimide foundation and application ", NTS, 8 th month in 2010, and the like.
The cured film of the present invention can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, the use of molded parts, the production of protective paint and dielectric layers in electronics, particularly microelectronics, and the like.
The method for producing a cured film of the present invention includes the case of using the photosensitive resin composition of the present invention. Specifically, the method preferably includes the following steps (a) to (d).
(a) Film formation step of forming a film by applying the photosensitive resin composition to a substrate
(b) An exposure step of exposing the film after the film formation step
(c) A developing step of developing the exposed photosensitive resin composition layer
(d) A heating step of heating the developed photosensitive resin composition at 80-450 DEG C
As in this embodiment, the exposed resin layer can be further cured by heating after development. In this heating step, the thermal alkaline agent of the present invention acts to obtain sufficient curability.
The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film according to the present invention. The method for producing a laminate according to the present embodiment is performed by forming a cured film according to the method for producing a cured film described above, and then performing the steps (a) to (c) or (a) to (d) again. In particular, it is preferable to sequentially perform the above steps a plurality of times, for example, 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be formed. It is preferable in the present invention that a metal layer is provided especially on the upper side of the portion where the cured film is provided or between the cured films or both. In addition, in the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, the laminate of the cured film can be obtained by performing at least the step (a), preferably the steps (a) to (c) or the steps (a) to (d) a plurality of times.
Film Forming Process (layer Forming Process)
The production method according to the preferred embodiment of the present invention includes a film formation step (layer formation step) of forming a film (layer) by applying the photosensitive resin composition to a substrate.
The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc., metal substrates such as quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, ni, cu, cr, fe, etc., papers, SOG (Spin 0n Glass), TFT (thin film transistor) array substrates, electrode plates of Plasma Display Panels (PDP), etc.
In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate is more preferable.
When the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a substrate.
As a method for applying the photosensitive resin composition to a substrate, coating is preferable.
Specifically, examples of the application method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of thickness of the photosensitive resin composition layer, spin coating, slit coating, spray coating, and inkjet method are more preferable. By adjusting the appropriate solid content concentration and coating conditions according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and spin coating, spray coating, ink jet method, or the like is preferable if the substrate is a circular substrate such as a wafer, and slit coating, spray coating, ink jet method, or the like is preferable if the substrate is a rectangular substrate. In the case of spin coating, for example, a spin speed of 500 to 2000rpm can be applied for about 10 seconds to 1 minute.
< drying Process >
The production method of the present invention may further include a step of drying the photosensitive resin composition layer after the film forming step (layer forming step) to remove the solvent. The drying temperature is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, still more preferably 90 to 110 ℃. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
< exposure Process >
The production method of the present invention may include an exposure step of exposing the photosensitive resin composition layer. The exposure amount is not particularly limited as long as the photosensitive resin composition can be cured, and for example, it is preferable to irradiate 100 to 10000mJ/cm in terms of exposure energy at a wavelength of 365nm 2 More preferably 200 to 8000mJ/cm 2 。
The exposure wavelength can be appropriately set in the range of 190 to 1000nm, preferably 240 to 550nm.
The exposure wavelength is described in relation to a light source, and examples thereof include (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide (g, h, 3 wavelengths of i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), and (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, etc. The photosensitive resin composition of the present invention is particularly preferably exposed by a high-pressure mercury lamp, and among these, exposure by i-rays is preferable. Thus, particularly high exposure sensitivity can be obtained.
< development treatment Process >
The production method of the present invention may include a development treatment step of developing the exposed photosensitive resin composition layer. By performing development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, spin-coating immersion, spraying, dipping, ultrasonic wave, or other developing methods can be employed.
The development is performed using a developer. The developer is not particularly limited as long as the unexposed portion (non-exposed portion) can be removed. Preferably, the developer contains an organic solvent, and more preferably, the developer contains 90% or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, more preferably contains an organic solvent having a ClogP value of 0 to 3. ClogP values can be obtained as calculated values by inputting structural formulae into chembio draw (chembio map).
Examples of the organic solvent include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, epsilon-caprolactone, 6-valerolactone, and alkyl alkoxyacetate (examples: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like, and as sulfoxides, dimethyl sulfoxide, and the like, may be suitably exemplified.
In the present invention, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The organic solvent is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 90 mass% or more of the developing solution.
Further, 100 mass% of the developer may be an organic solvent.
The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and can be usually set at 20 to 40 ℃.
After the treatment with the developer, further washing can be performed. The rinsing is preferably performed with a solvent different from the developer. For example, the photosensitive resin composition may be rinsed with a solvent contained therein. The rinsing time is preferably 5 seconds to 1 minute.
Heating procedure-
The production method of the present invention preferably includes a film formation step (layer formation step), a drying step, or a developing step, followed by a heating step. In the heating step, cyclization of the polymer precursor is performed. The composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, and may be cured with the radically polymerizable compound other than the unreacted polymer precursor in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, further preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500℃or less, more preferably 450℃or less, still more preferably 350℃or less, still more preferably 250℃or less, and still more preferably 220℃or less.
The heating is preferably performed at a heating rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and still more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the highest heating temperature. The rate of temperature rise is set to 1 ℃/min or more, whereby the excessive volatilization of amine can be prevented while ensuring productivity, and the residual stress of the cured film can be relaxed by setting the rate of temperature rise to 12 ℃/min or less.
The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, still more preferably 25 to 120 ℃. The temperature at the start of heating means the temperature at the start of the step of heating to the highest heating temperature. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably gradually increased from a temperature lower than the boiling point of the solvent contained in the photosensitive resin composition by 30 to 200 ℃.
The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and still more preferably 30 to 240 minutes.
In particular, when forming a multilayer laminate, it is preferable to heat at a heating temperature of 180 to 320 ℃, and more preferable to heat at 180 to 260 ℃ from the viewpoint of adhesion between layers of the cured film. The reason for this is not necessarily clear, but it is considered that the acetylene groups of the polymer precursors between the layers undergo a crosslinking reaction by setting the temperature.
The heating may be performed in stages. As an example, a pretreatment step of heating from 25 ℃ to 180 ℃ at 3 ℃/min and holding at 180 ℃ for 60 minutes, heating from 180 ℃ to 200 ℃ at 2 ℃/min and holding at 200 ℃ for 120 minutes may be used. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. patent No. 9159547. The film characteristics can be improved by these pretreatment steps. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be a two-stage or more step, and for example, the pretreatment step 1 may be performed at 100 to 150 ℃ and the pretreatment step 2 may be performed at 150 to 200 ℃.
Further, the cooling may be performed after the heating, and the cooling rate in this case is preferably 1 to 5 ℃/min.
The heating step is preferably performed under an ambient gas having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, for example, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.
Metal layer forming process
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.
The metal layer is not particularly limited, and a conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese patent application laid-open No. 2007-157879, japanese patent application laid-open No. 2001-521288, japanese patent application laid-open No. 2004-214501, and Japanese patent application laid-open No. 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method using a combination of sputtering, photolithography, and etching, and a patterning method using a combination of photolithography and electrolytic plating are mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, in the thickest wall thickness portion.
Lamination procedure-
The production method of the present invention preferably further comprises a lamination step.
The lamination step is a series of steps including (a) a film formation step (layer formation step), (b) an exposure step, (c) a development treatment step, and (d) a heating step, again performed in this order on the surface of the cured film (resin layer) or the metal layer. Here, the film formation step (a) may be repeated only. The heating step (d) may be performed at the end or in the middle of lamination.
That is, the following modes may be adopted: repeating the steps (a) to (c) a predetermined number of times, and thereafter heating the laminated photosensitive resin composition layer to cure the laminated photosensitive resin composition layer. The developing step (c) may be followed by a metal layer forming step (e), and the heating of (d) may be performed each time or may be performed all at once after being laminated a predetermined number of times. It is needless to say that the lamination step may include the above-described drying step, heating step, and the like as appropriate.
When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, a plasma treatment is exemplified.
The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer such as the resin layer/metal layer/resin layer/metal layer is preferably 3 or more and 7 or less, more preferably 3 or more and 5 or less.
In the present invention, it is more preferable that a cured film (resin layer) of the photosensitive resin composition is formed so as to cover the metal layer, particularly after the metal layer is provided. Specifically, there may be mentioned a method in which (a) the film forming step, (b) the exposing step, (c) the developing step, (e) the metal layer forming step, and (d) the heating step are sequentially repeated, or a method in which (a) the film forming step, (b) the exposing step, (c) the developing step, and (e) the metal layer forming step are sequentially repeated, and (d) the heating step is provided at the end or the middle thereof. By alternately performing the lamination step of laminating the photosensitive resin composition layers (resins) and the metal layer formation step, the photosensitive resin composition layers (resin layers) and the metal layers can be alternately laminated.
Also disclosed herein is a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used for formation of an interlayer insulating film for a re-wiring layer, reference is made to the descriptions in paragraphs 0213 to 0218 and the description in fig. 1 of japanese patent application laid-open publication 2016-027357, and these are incorporated herein by reference.
Examples
The present invention will be described in more detail with reference to the following examples. The materials, amounts used, ratios, treatment contents, treatment order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise indicated, "parts" and "%" are mass references.
Synthesis example 1
[ polyimide precursor A-1: synthesis of polyimide precursor having no radical polymerizable group
Polyimide precursor a-1 was synthesized using pyromellitic dianhydride, 4' -diaminodiphenyl ether and benzyl alcohol.
14.06g (64.5 mmol) of pyromellitic dianhydride (dried at 140℃for 12 hours) and 14.22g (131.58 mmol) of benzyl alcohol were suspended in 50mL of N-methylpyrrolidone, while drying using a molecular sieve. The suspension was heated at 100℃for 3 hours. The reaction mixture was cooled to room temperature and 21.43g (270.9 g was addedMillimoles) of pyridine and 90mL of N-methylpyrrolidone. Next, the reaction mixture was cooled to-10℃and 16.12g (135.5 mmol) of SOCl was added over 10 minutes while maintaining the temperature at-10.+ -. 4 ℃ 2 . Adding SOCl 2 During this time, the viscosity is increased. After dilution with 50mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08g (58.7 mmol) of 4,4' -diaminodiphenyl ether in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-5 to 0℃over 20 minutes. Then, after the reaction mixture was reacted at 0℃for 1 hour, 70g of ethanol was added and stirred at room temperature overnight. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000rpm for 15 minutes. The precipitated polyimide precursor was removed by filtration, followed by stirring again in 4 liters of water for 30 minutes and filtration again. The obtained material was dried at 45℃for 3 days under reduced pressure to obtain polyimide precursor A-1. The polyimide precursor had a weight average molecular weight of 18,000.
A-1
[ chemical formula 33]
Synthesis example 2
[ polyimide precursor A-2: synthesis of polyimide precursor having radical polymerizable group
Polyimide precursor a-2 was synthesized using pyromellitic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate.
14.06g (64.5 mmol) of pyromellitic dianhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 mmol) and 100g of diglyme (diglyme) were mixed and stirred at 60℃for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, through SOCl 2 After the obtained diester was chlorinated, the 4,4' -diaminodiphenyl ether was converted into a polyimide precursor in the same manner as in Synthesis example 1, and a polyimide precursor A-2 was obtained in the same manner as in Synthesis example 1. The polyimide precursor had a weight average molecular weight of 19,000.
A-2
[ chemical formula 34]
< synthetic example 3>
[ polyimide precursor A-3: synthesis of polyimide precursor having radical polymerizable group
Polyimide precursor a-3 was synthesized using 4,4 '-oxydiphthalic anhydride, 4' -diaminodiphenyl ether, and 2-hydroxyethyl methacrylate.
20.0g (64.5 mmol) of 4,4 '-oxydiphthalic anhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 mmol) and 100g of diglyme were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Then, through SOCl 2 After the obtained diester was chlorinated, it was converted into a polyimide precursor by 4,4' -diaminodiphenyl ether in the same manner as in Synthesis example 1, and a polyimide precursor A-3 was obtained in the same manner as in Synthesis example 1. The polyimide precursor had a weight average molecular weight of 18,000.
A-3
[ chemical formula 35]
< synthetic example 4>
[ polyimide precursor A-4: synthesis of polyimide precursor having radical polymerizable group
Polyimide precursor a-4 was synthesized using 4,4' -oxydiphthalic anhydride, 4' -diamino-2, 2' -dimethylbiphenyl (diphthaline) and 2-hydroxyethyl methacrylate.
20.0g (64.5 mmol) of 4,4 '-oxydiphthalic anhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g of pyridine (258 mmol) and 100g of diglyme were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. Then, through SOCl 2 After the obtained diester was chlorinated, 4 '-diamino-2, 2' -dimethylbiphenyl was converted into a polyimide precursor in the same manner as in Synthesis example 1, and a polyimide precursor A-4 was obtained in the same manner as in Synthesis example 1. The polyimide precursor had a weight average molecular weight of 19,000.
A-4
[ chemical formula 36]
Synthesis example 5
[ Synthesis of polybenzoxazole precursor A-5 ]
Polybenzoxazole precursor (A-5) was synthesized using 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -oxo-dibenzoyl chloride
To 100mL of N-methyl-2-pyrrolidone was added 13.92g of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the mixture was dissolved with stirring. Next, 11.21g of 4,4' -oxybenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5℃and stirring was continued for 60 minutes. Next, the polybenzoxazole precursor was precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at 5000rpm for 15 minutes. The precipitated polybenzoxazole precursor was filtered, followed by stirring again in 6 liters of water for 30 minutes and again filtering. The obtained material was dried at 45℃for 3 days under reduced pressure to obtain polybenzoxazole precursor A-5. The weight average molecular weight of the polybenzoxazole precursor was 15,000.
A-5
[ chemical formula 37]
< examples and comparative examples >
The components described in the following table were mixed to obtain each photosensitive resin composition. The obtained photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm.
/>
< composition of photosensitive resin composition >
(A) Precursors for heterocyclic-containing polymers: a-1 to A-5 synthesized in the above
(B) Specific thermal alkaline agents: exemplary Compounds B-1 to B-19 described previously
Thermal alkaline generator for comparative example: the following compounds
[ chemical formula 38]
The boiling point of the base (amine compound) and the pKa of the conjugate acid generated from the thermal alkaline generators of the above comparative examples are shown below.
TABLE 4
Numbering of compounds Generating the boiling point of the amine pKa of amine conjugate acid
(RB-1) 184℃ 4.6
(RB-2) 184℃ 4.6
(C) Photo radical polymerization initiator
C-1: IRGACURE OXE 01 (manufactured by BASF corporation)
C-2: IRGACURE OXE 02 (manufactured by BASF corporation)
C-3: IRGACURE 369 (BASF corporation)
(D) Radical polymerizable compound
D-1: A-DPH (Shin-Nakamura Chemical Co., ltd., dipentaerythritol hexaacrylate)
D-2: SR-209 (Sartomer Company, manufactured by Inc., the following Compounds)
[ chemical formula 39]
D-3: A-TMMT (Shin-Nakamura Chemical Co., ltd., pentaerythritol tetraacrylate)
(E) Polymerization inhibitor
E-1:2, 6-di-tert-butyl-4-methylphenol (Tokyo Chemical Industry co., ltd.)
E-2: p-benzoquinone (Tokyo Chemical Industry Co., ltd.)
E-3: p-methoxyphenol (Tokyo Chemical Industry Co., ltd.)
(F) Migration inhibitors
F-1: the following compounds
F-2: the following compounds
F-3: the following compounds
F-4: the following compounds
[ chemical formula 40]
(G) Metal adhesion improver
G-1: the following compounds
G-2: the following compounds
6-3: the following compounds
[ chemical formula 41]
(H) Solvent(s)
H-1: gamma-butyrolactone (SANWAYUKA INDUSTRY CORPORATION system)
H-2: dimethyl sulfoxide (Wako Pure Chemical Industries, ltd.)
H-3: n-methyl-2-pyrrolidone (manufactured by Ashland Co., ltd.)
< storage stability >
The viscosity (0 days) of the photosensitive resin composition after filtration was measured using an E-type viscometer. After the photosensitive resin composition was allowed to stand at 25℃for 14 days in a closed container, the viscosity (14 days) was measured again using an E-type viscometer. The viscosity change rate was calculated according to the following formula. The lower the viscosity change rate, the higher the storage stability.
Viscosity change rate= |100× {1- (viscosity (14 days)/viscosity (0 days)) } |
The measurement of viscosity was performed at 25℃except that the viscosity was measured in accordance with JIS Z8803: 2011.
A: a viscosity change of 5% or less
B: a viscosity change rate of more than 5% and less than 10%
C: the viscosity change rate exceeds 10% and is less than 15%
D: a viscosity change rate of more than 15% and less than 20%
E: viscosity change rate exceeding 20%
< elongation at break >
The photosensitive resin composition layers were formed on the silicon wafer by applying each of the above-described filtered photosensitive resin compositions in a layer form by spin coating. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried at 100℃for 5 minutes on a heating plate, thereby forming a photosensitive resin composition layer having a uniform thickness of 20. Mu.m on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm 2 The photosensitive resin composition layer on the silicon wafer was exposed to light, and the exposed photosensitive resin composition layer (resin layer) was heated at a heating rate of 10 ℃/min under a nitrogen atmosphere to 180 ℃. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin film 1.
The elongation at break of the resin film 1 was set to a crosshead speed of 300 mm/min, a width of 10mm, and a sample length of 50mm using a tensile Tester (TENSILON), and was measured in the longitudinal direction and the width direction of the film in accordance with JIS-K6251 under an environment of 25 ℃ and 65% Relative Humidity (RH): 2017, the elongation at break was measured. Elongation at break through E b ＝(L b -L 0 )/L 0 (E b : elongation at cutting, L 0 : length of test sample before test, L b : the length of the test sample when the test sample has been cut). In the evaluation, the elongation at break in each of the longitudinal direction and the width direction was measured 5 times, and the average value in the longitudinal direction and the width direction was used.
A: elongation at break exceeding 60%
B: elongation at break exceeding 55% and 60% or less
C: elongation at break exceeding 50% and 55% or less
D: elongation at break exceeding 40% and 50% or less
E: elongation at break of 40% or less
< evaluation of resolution of minimum line-width pattern >
Each of the photosensitive resin compositions after filtration was spin-coated on a silicon wafer. The silicon wafer to which the photosensitive resin composition was applied was dried on a hot plate at 100℃for 5 minutes, thereby forming a photosensitive resin composition layer having a thickness of 20 μm and a uniform film thickness on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed by a stepper (Nikon NSR 2005 i9 c). Exposure at a wavelength of 365nm at 200, 300, 400, 500, 600, 700, 800mJ/cm 2 The resin layer was obtained by exposing the substrate to light from 5 μm to 25 μm using a 1 μm scale line-space photomask.
The resin layer was developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (line pattern) is, the more fine patterns can be formed, and this is a preferable result. Further, the smaller the minimum line width that can be formed, the less likely the variation in exposure amount is changed, and the greater the randomness of the exposure amount in the fine pattern formation is, and this is a preferable result. The measurement limit was 5. Mu.m.
A: is 5 μm or more and 8 μm or less
B: more than 8 μm and less than 10 μm
C: more than 10 μm and less than 15 μm
D: more than 15 μm and less than 20 μm
E: exceeding 20 μm
F: failure to obtain a pattern having line width with edge sharpness
< evaluation conditions for copper adhesion >
The respective photosensitive resin compositions after filtration were applied in layers by spin coating on a copper substrate to form photosensitive resin composition layers. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried at 100℃for 5 minutes on a heating plate, thereby forming a photosensitive resin composition layer having a uniform thickness of 20. Mu.m on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) and using100 μm square photomask at 500mJ/cm 2 The photosensitive resin composition layer on the silicon wafer was exposed to light and then developed with cyclopentanone for 60 seconds, thereby obtaining a 100 μm square resin layer. Further, the temperature was raised at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere to 250 ℃, and then the temperature was maintained for 3 hours to obtain a resin film 2.
The shear force was measured on the 100 μm square resin film 2 on the copper substrate by an adhesion tester (manufactured by XYZTEC Co., ltd., condorSigma) under an atmosphere of 65% Relative Humidity (RH) at 25 ℃. The greater the shear force, the greater the adhesion force and the preferred results obtained.
A: shear force exceeding 40gf
B: the shearing force exceeds 35gf and is less than 40gf
C: the shearing force exceeds 30gf and is less than 35gf
D: the shearing force exceeds 25gf and is less than 30gf
E: a shear force of 25gf or less
TABLE 5
The value of the "resolution evaluation of minimum line width pattern" is exposure energy in mJ/cm 2 . The evaluation results of the resolution of the pattern in each exposure energy are shown.
From the above results, it is clear that the photosensitive resin composition containing the specific thermal alkaline generator of the present invention and the heterocyclic polymer-containing precursor is excellent in storage stability. It is also known that R of formula (N1) is optionally modified by specific thermal alkaline generator N1 ，R N2 The use of an alkyl group having a relatively large number of carbon atoms (particularly, an alkyl group having a cyclic structure) can provide a cured film of the photosensitive resin composition with excellent elongation at break. Further, it is found that the obtained photosensitive cured film can be made excellent in pattern resolution and also good in adhesion to copper by combining with a polymer precursor having a radical polymerizable group or the like as needed.
< example 100>
The photosensitive resin composition of example 1 was applied to a resin substrate having a copper thin layer formed thereon by spin-forming (3500 rpm, 30 seconds) after passing through a filter having a pore width of 1.0 μm and pressure-filtering. After the photosensitive resin composition applied to the resin substrate was dried at 100℃for 2 minutes, exposure was performed by using a stepper (manufactured by Nikon Corporation, NSR1505 i 6). Exposure through a mask at a wavelength of 365nm at 200mJ/cm 2 Is performed. After exposure, baking was performed while developing with cyclopentanone for 30 seconds, and the pattern was obtained by rinsing with PGMEA for 20 seconds.
Next, the interlayer insulating film for a rewiring layer was formed by heating at 230 ℃ for 3 hours. The interlayer insulating film for a rewiring layer is excellent in insulation properties.

Claims (15)

1. A photosensitive resin composition comprising a thermal alkaline agent and a precursor of a heterocyclic-containing polymer, the thermal alkaline agent being represented by the following formula (N1);
in the formula (N1), R N1 R is R N2 Each independently represents a 1-valent hydrocarbon group, R C1 Represents a hydrogen atom or a chain or cyclic alkyl group having an oxygen atom in the chain, L represents a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain,
the precursor of the heterocyclic polymer has a structural unit represented by the formula (1) or a structural unit represented by the formula (2),
In the formula (1), A 1 A is a 2 Each independently represents an oxygen atom or NH, R 111 Represents a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a 2-valent group comprising a combination of theseLinker, R 115 Represents a group represented by the following formula (5) or (6), R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R 113 R is R 114 At least one of the groups containing a radical polymerizable group, the radical polymerizable group being a group having an ethylenically unsaturated bond,
in the formula (2), R 121 Represents a 2-valent organic group containing at least one of an aliphatic group and an aromatic group, R 122 Represents a group represented by the following formula (5) or (6), R 123 R is R 124 Each independently represents a hydrogen atom or a 1-valent organic group, R 123 R is R 124 At least one of the groups containing a radical polymerizable group, the radical polymerizable group being a group having an ethylenically unsaturated bond,
R 112 is a single bond or is selected from aliphatic hydrocarbon groups of 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C (=O) -, -S (=O) 2 -, -NHCO-and combinations of these,
the conjugate acid of the base produced by the thermal alkaline generator has a pKa of 8 or more.
2. The photosensitive resin composition according to claim 1, wherein,
L in the formula (N1) is the 2-valent hydrocarbon linking group having a linking chain length of 1 to 5.
3. The photosensitive resin composition according to claim 1, wherein,
r in the formula (N1) N1 R is R N2 Each independently an aliphatic hydrocarbon group.
4. The photosensitive resin composition according to claim 1, wherein,
l in the formula (N1) is 1, 2-ethylene, 1, 3-propylene, 1, 2-cyclohexanediyl, cis-ethylene, 1, 2-phenylene, 1, 2-phenylenemethylene or 1, 2-ethyleneoxy-1, 2-ethylene.
5. The photosensitive resin composition according to claim 1, wherein,
r in the formula (N1) C1 Is a hydrogen atom.
6. The photosensitive resin composition according to any one of claims 1 to 4, wherein,
the compound produced by decomposition of the thermal alkaline generator represented by the formula (N1) is a compound represented by the following formula (N2), the boiling point of the compound represented by the formula (N2) is 50 ℃ or higher,
in the formula (N2), R N1 R is R N2 Each independently represents a 1-valent hydrocarbon group.
7. The photosensitive resin composition according to claim 1, further comprising a photo radical polymerization initiator and a radical polymerizable compound.
8. The photosensitive resin composition according to claim 1, wherein,
The heterocyclic polymer-containing precursor has the structural unit represented by formula (1).
9. The photosensitive resin composition according to claim 1, which is used for forming an interlayer insulating film for a rewiring layer.
10. A cured film obtained by curing the photosensitive resin composition according to any one of claims 7 to 9.
11. A laminate having 2 or more layers of the cured film of claim 10 with a metal layer between the cured films.
12. A method for producing a cured film, comprising a film forming step of applying the photosensitive resin composition according to any one of claims 7 to 9 to a substrate to form a film.
13. The method for producing a cured film according to claim 12, comprising a step of heating the film at 50 to 450 ℃.
14. A semiconductor device having the cured film according to claim 10 or the laminate according to claim 11.
15. A thermal alkaline generator represented by the following formula (N1),
in the formula (N1), R N1 R is R N2 Each independently represents a 1-valent hydrocarbon group, R C1 Represents a hydrogen atom or a chain or cyclic alkyl group having an oxygen atom in the chain, L represents a 1, 3-propylene group, a 1, 2-cyclohexanediyl group, a 1, 2-phenylenemethylene group or a 1, 2-ethyleneoxy-1, 2-ethylene group,
The conjugate acid of the base produced by the thermal alkaline generator has a pKa of 8 or more.
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